Research ArticleElectronic Structure Spectroscopic (IR Raman UV-Vis NMR)Optoelectronic and NLO Properties Investigations of RubescinE (C31H36O7) Molecule in Gas Phase and Chloroform SolutionUsing Ab Initio and DFT Methods
Richard Arnaud Yossa Kamsi 12 GehWilson Ejuh 234 Fidegravele Tchoffo1
Pierre Mkounga5 and Jean-Marie Bienvenu Ndjaka 12
1University of Yaounde I Faculty of Science Department of Physics PO Box 812 Yaounde Cameroon2CETIC (Centre drsquoExcellence Africain en Technologies de lrsquoInformation et de la Communication)Universite de Yaounde I BP 8390 Yaounde Cameroon3University of Bamenda National Higher Polytechnic Institute Department of Electrical and Electronic EngineeringP O Box 39 Bambili Cameroon4University of Dschang IUT Bandjoun Department of General and Scientific Studies PO Box 134 Bandjoun Cameroon5University of Yaounde I Faculty of Science Department of Chemistry PO Box 812 Yaounde Cameroon
Correspondence should be addressed to Richard Arnaud Yossa Kamsi richardkamsiyahoofr
Received 12 October 2018 Accepted 28 November 2018 Published 2 January 2019
Academic Editor Jorg Fink
Copyright copy 2019 Richard Arnaud Yossa Kamsi et al This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited
Quantum chemical methods were used to study the electronic structure and some physicochemical properties of Rubescin Emolecule Good agreement with experiment was found for 3JH-H coupling constant IR 1H NMR and 13C NMR The excitationenergy and oscillator strength calculated by TD-DFT also complement with experiment Large values were obtained for dipolemoment polarizability first static hyperpolarizability electric susceptibility refractive index and dielectric constant meaning thatRubescin E has strong optical and phonon application and can be a good candidate as NLOs material The 3D analysis of the titlemolecule leads us to the conclusion that electron can easily be transferred from furan to tetrahydrofuran ringThe global reactivitydescriptors were evaluated Mulliken ESP and NBO charges comparisons were carried out and described
1 Introduction
Many molecules from plant research were found nowadaysto have application in the field of medicine where thereare use for the treatment of many diseases among whichwe found malaria caused by plasmodium falciparum Thenew limonoid name Rubescin E (C31H36O7) extracted fromthe roots of Trichilia Rubescens collected from Cameroonhas been evaluated against erythrocytic stages of strain3D7 plasmodium falciparum and also exhibited significantantiplasmodial in vitro activity with IC50 value of 113120583M [1]The FT-IR performed on Rubescin E molecule revealed the
presence of 120572 120573-unsaturated carbonyl moiety at 1720 cmminus1and 1664 cmminus1 These values can be obtained theoreticallyby performing the vibrational frequencies calculation on thetitle molecule and used to explain the different motion ofatoms or group of atoms in a molecular system The 1D(1H 13C NMR) and 2D NMR spectra were run on a BrukerAV spectrometer [1] in order to predict the structure ofthe title molecule and were done in this work in order totake out similarities between experiment done previously andtheoretical calculation performed here
In this work quantum chemical calculation was per-formed in order to take out the electronic structure (energy
HindawiAdvances in Condensed Matter PhysicsVolume 2019 Article ID 4246810 22 pageshttpsdoiorg10115520194246810
2 Advances in Condensed Matter Physics
gap charge distributions NLO properties vibrational fre-quencies NMR and UV-vis calculation) and some physico-chemical properties (3JH-H chemical coupling-coupling con-stant the global reactivity descriptors and some geometricalparameters such as bonds lengths and bonds angles) ofRubescin E molecule To the best of our knowledge notheoretical studywas performed yet on the titlemolecule thatis what motivated us to investigate the electronic structurethe spectroscopic and some physicochemical propertiesof Rubescin E molecule Except for NMR UV-vis 3JH-Hchemical coupling-coupling constant and the vibrationalfrequencies obtained for the two 120572 120573-unsaturated carbonylmoiety most of our results were not compared and weare optimistic that it can be used as threshold for futureexperimental or theoretical research Hartree Fock andDFT (using B3LYP and B3PW91 functionals) methods wereused for these purposes These properties were calculatedby employing the triple split valence basis set along withpolarization functions with and without diffuse functions asimplemented in Gaussian 09 Rev A02 in both gas phase andin a solution of chloroformThe methods and basis sets usedare among the most widely used [2ndash5] and provide excellentresults which are generally very close to experiments [6ndash8]
2 Computational Methods
Theoretical calculations were performed on Rubescin Eusing HF and DFT methods at the B3LYP and B3PW91levels as implemented in Gaussian 09W code [9] All thesecalculations were done in gas phase and in a solution ofchloroform No geometry restriction was applied duringthe optimization procedure The solvent effects were treatedwithin the conductor-like polarizable continuum model(CPCM) For the geometry optimization the 6-311G(dp) and6-311++G(dp) basis set were used in both gas and solventConvergence criteria in which both the maximum force anddisplacement are smaller than the cut-off of 0000015 and0000060 and RMS force and displacement less than thecut-off values of 0000010 and 0000040 were used in thecalculations in order to increase the accuracy of our resultsThe chemical 3JH-H proton-proton coupling constant func-tion of angle between two C-H vectors was calculated fromthe optimization output using the original Karplus equation[10] The optimized form of our molecule was then used todetermine the global reactivity descriptors electronic andNLOs properties The net charges were also evaluated usingMPA ESP and NBOs methods at the three levels mentionedabove and all this was done in both gas phase and chloroformwith the 6-311++G(dp) basis set In order to confirm thestability of our molecule the vibrational frequencies (IR andRaman) were evaluated at the 6-311G(dp) and no imaginaryfrequencies were found leading us to the results that ourmolecule was stable at the levels and basis set consideredThetime dependent density functional theory (TD-DFT) fieldwas used in gas phase with the 6-311++G(dp) basis in orderto understand the electronic transition of our molecule andthe obtained results were compared to experimentTheGIAO(gauge independent atomic orbital) method was used on theoptimized form of our molecule in a solution of chloroform
to determine the 1H and 13C NMR spectra parameters at thethree levels and with the 6-311++G(dp) basis set In orderto compare the calculated values of 1H and 13C chemicalshift with experimental results the reference and widelyusedmolecule TMS (tetramethylsilane) for this purpose wereexploited at the same level at the same phase and with thesame basis set
3 Results and Discussion
31 Optimized Structure The optimized geometry ofRubescin E obtained using the B3LYP6-311++G(dp)method in chloroform is shown in Figure 1 The value ofthe total electronic energy of the molecule obtained at theB3LYP shows that Figure 1 is the most stable structure of themolecule The total electronic energy calculated within thetwo methods in gas and in a solution of chloroform with the6-311++G(dp) is given in Table 1
32 Structural Properties A part of the optimized geometri-cal parameters (bond length bond angle) and total electronicenergy of the title molecule both in gas and in a solution ofchloroform are given in Table 1 using the three levels andwith the 6-311++G(dp) basis set The total description of themolecular geometry of Rubescin Emolecule in gas phase andin a solution of chloroform using ab initio (RHF) and DFT(B3LYP and B3PW91) methods with the 6-311++G(dp) basisset can be obtained from Supplementary Material S1
The atom numbering scheme adopted for this purposeis the same as in Figure 1 The energy differences betweenthe two used phases increase when we move from B3PW91to B3LYP and to RHF and are found to be approximatively048 eV 049 eV and 057 eV respectively The optimizedbond length and bond angle of Rubescin E are also listedin Table 1 with some specific experimental values [12ndash14]found in the literature for some groups of compounds suchas furan ethylene oxide and tetrahydrofuran present in ourmolecule It can be observed fromTable 1 that the values of thebond length obtained at B3LYP are slightly higher than thoseobtained at the B3PW91 level These differences are foundbetween 00034 A and 00107 A for C-C 00061 A and 00095A for C-O and 00007 A and 00013 A for C=C in gas phaseThe value of C=O bond length is better at the DFT methodssince its values are closer to 210 A found in literature [11] Itcan also been observed that the calculated bonds length usingHartree Fock and DFT methods are very close to the valuesfound in literature for the specific groups of compoundspresent in our molecule These observed differences variedfrom 00012 A at the B3LYP level to 00363 A at the RHF levelfrom 00002 A at the B3PW91 level to 00288 A at the B3LYPlevel and from 00019 A at the B3LYP level to 00259 A at theRHF level for C-C C-O and C=C bonds both in gas phaseand in chloroform solution respectively
The bonds angles of the studied molecule are slightlydifferent when we move from one phase to another at eachlevel with larger values obtained at the RHF level From ourresults it can be seen that the C-C-C bond angle varies from963773∘ to 1293418∘ from 966032∘ to 1288385∘ and from964146∘ to 1287371∘ at the gas phase respectively at the RHF
Advances in Condensed Matter Physics 3
Table 1 Optimized geometric parameters in gas phase and in chloroform solution of Rubescin E at the RHF B3LYP and B3PW91 level withthe 6-311++G (dp) basis sets
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
Bond lengthR1 (C1-C2) 15503 15490 15603 15583 15521 15500R2 (C1-C3) 15698 15672 15811 15777 15719 15684R3 (C1-C20) 15167 15157 15221 15215 15153 15147R4 (C1-C22) 15474 15481 15510 15509 15439 15438R5 (C2=O7) 11900 11948 12167 12213 12152 12197 210bR6 (C2-C34) 15041 14992 14966 14910 14920 14867R7 (C3-C4) 15898 15887 15973 15968 15866 15860R8 (C3-C40) 14814 14800 14972 14958 14931 14918 1462bR9 (C3-O59) 13994 14024 14311 14335 14236 14256 1428bR10 (C4-C5) 15515 15518 15549 15548 15473 15471R11 (C4-C12) 15707 15733 15756 15787 15676 15707R12 (C4-C36) 15501 15503 15543 15543 15471 15472R13 (C5-C6) 15428 15442 15477 15487 15401 15410R14 (C5-C46) 14556 14553 14720 14717 14686 14684 1462bR15 (C5-O61) 14206 14235 14568 14590 14473 14492 1428bR16 (C6-C26) 15259 15260 15306 15307 15246 15248R17 (C6-C42) 15352 15350 15373 15373 15298 15298R18 (C6-C51) 15703 15708 15810 15814 15724 15728R19 (C8-C16) 15423 15424 15477 15481 15405 15408R20 (C8-C20) 15256 15244 15348 15335 15276 15264 1536cR21 (C8-C29) 15405 15402 15479 15468 15416 15406 1536cR22 (C8-C32) 15036 15036 15010 15010 14958 14960R23 (C9-O11) 14120 14133 14389 14411 14304 14324 1428cR24 (C9-C12) 15288 15302 15357 15373 15311 15329R25 (C9-C20) 14997 14993 15044 15042 14999 14998 1536cR26 (O11-C29) 14261 14287 14530 14551 14438 14457 1428cR27 (C12-O60) 14104 14131 14339 14369 14255 14283R28 (C14-C51) 15035 15041 15003 15010 14953 14959R29 (C14-C53) 14493 14505 14428 14438 14387 14397 1430aR30 (C14=C57) 13411 13410 13621 13619 13614 13614 1364aR31 (O15-C55) 13382 13412 13609 13638 13548 13574 1364aR32 (O15-C57) 13467 13496 13659 13686 13592 13616 1364aR33 (C26-C40) 15162 15158 15190 15181 15137 15129R34 (C32=C34) 13270 13285 13431 13445 13422 13436R35 (C40-O59) 14010 14054 14353 14395 14282 14320 1428bR36 (C46-C48) 15086 15076 15135 15123 15088 15077R37 (C46-O61) 14005 14051 14326 14376 14254 14297 1428bR38 (C48-C51) 15407 15405 15478 15475 15408 15405R39 (C53=C55) 13381 13381 13567 13567 13559 13559 1364aR40 (O60-C62) 13485 13397 13805 13700 13743 13650R41 (C62-C63) 15033 15030 14998 15000 14956 14952R42 (C62=O65) 11810 11873 12059 12113 12046 12098R43 (C63=C64) 13222 13230 13402 13403 13394 13398R44 (C63-C71) 15153 15159 15127 15135 15071 15083
4 Advances in Condensed Matter Physics
Table 1 Continued
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
R45 (C64-C67) 15001 15002 14954 14959 14898 14901Bond anglesA1 (C2-C1-C3) 1153869 1151538 1153519 1150591 1153042 1149661A2 (C2-C1-C20) 1049116 1052360 1048861 1053058 1050195 1054353A3 (C2-C1-C22) 1046632 1048093 1048467 1050548 1047619 1050065A4 (C3-C1-C20) 1054487 1049239 1060693 1053428 1059491 1051727A5 (C3-C1-C22) 1100598 1104677 1093407 1099326 1094774 1101062A6 (C20-C1-C22) 1166507 1165134 1166409 1164160 1166212 1164196A7 (C1-C2-O7) 1226712 1221731 1225890 1220461 1226012 1220599A8 (C1-C2-C34) 1188294 1190297 1185520 1188580 1185112 1188095A9 (O7-C2-C34) 1183115 1186060 1186750 1189135 1186899 1189368A10 (C1-C3-C4) 1174677 1172546 1175179 1173499 1174703 1172908A11 (C1-C3-C40) 1204116 1203391 1205229 1203696 1204781 1203201A12 (C1-C3-O59) 1135239 1136346 1132288 1134708 1132740 1135007A13 (C4-C3-C40) 1197989 1198618 1196777 1197275 1197605 1198264A14 (C4-C3-O59) 1109192 1113348 1106687 1110566 1107288 1111433A15 (C3-C4-C5) 1082815 1080767 1085292 1083020 1084460 1081898A16 (C3-C4-C12) 1169097 1169148 1166545 1168466 1168336 1170260A17 (C3-C4-C36) 1073533 1075825 1072145 1073890 1072213 1073820A18 (C5-C4-C12) 1109502 1112590 1108879 1111131 1110310 1113284A19 (C5-C4-C36) 1082096 1083900 1082857 1085557 1080890 1083471A20 (C12-C4-C36) 1047402 1042361 104883 1042585 1047988 1041530A21 (C4-C5-C6) 1223963 1225160 1222095 1222513 1222181 1222697A22 (C4-C5-C46) 1261434 1260858 1262488 1261993 1261315 1260739A23 (C4-C5-O61) 1137557 1135947 1137382 1136922 1140173 1139553A24 (C6-C5-C46) 1084092 1084312 1082407 1082667 1082513 1082900A25 (C6-C5-O61) 1093436 1091575 1097850 1096384 1096935 1095481A26 (C5-C6-C26) 1069225 1071323 1071725 1073025 1071359 1072931A27 (C5-C6-C42) 1147934 1148607 1144807 1145006 1145313 1145541A28 (C5-C6-C51) 1018612 1018830 1019281 1020115 1018916 1019777A29 (C26-C6-C42) 1088679 1086162 1091102 1089149 1091443 1089314A30 (C26-C6-C51) 1138205 1138653 1139931 1140014 1139406 1139367A31 (C42-C6-C51) 1105307 1104727 1101102 1100888 1101443 1101222A32 (C16-C8-C20) 1178467 1178806 1175220 1175381 1173986 1173974A33 (C16-C8-C29) 1083950 1085431 1084117 1085195 1085270 1086672A34 (C16-C8-C32) 1095455 1094283 1095034 1093293 1096190 1094415A35 (C20-C8-C29) 963773 964321 966032 966193 964146 964285 1015cA36 (C20-C8-C32) 1063315 1062487 1064280 1063876 106432 1063732A37 (C29-C8-C32) 1182843 1182659 1183155 1184200 1183462 1184575A38 (O11-C9-C12) 1132108 1131065 1132048 1132060 1131493 1131724A39 (O11-C9-C20) 1033360 1031494 1038285 1036622 1038971 1037399 1040cA40 (C12-C9-C20) 1092549 1094574 1087908 1089954 1084814 1086640A41 (C9-O11-C29) 1111841 1112217 1098976 1099018 1098190 1098362 1106cA42 (C4-C12-C9) 1104259 1106951 1100123 1103980 1098110 1101418A43 (C4-C12-O60) 1111499 1114570 1109644 1114849 1113257 1119073
Advances in Condensed Matter Physics 5
Table 1 Continued
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
A44 (C9-C12-O60) 1090864 1087044 1087314 1082508 1084512 1079972A45 (C51-C14-C53) 126042 1260928 1261043 1261692 1262986 1263771A46 (C51-C14-C57) 1293418 1291716 1288385 1286558 1287371 1285448A47 (C53-C14-C57) 1045893 1047043 1050493 1051666 1049597 1050728 10614aA48 (C55-O15-C57) 1071084 1071499 1067602 1068013 1068133 1068678 10674aA49 (C1-C20-C8) 1211479 1210073 1209097 1207705 1209914 1208439A50 (C1-C20-C9) 1187226 1185220 1187478 1183732 1186818 1182898A51 (C8-C20-C9) 1038120 1039439 1042023 1043600 1040389 1042216 1044cA52 (C6-C26-C40) 1114945 1116304 1114804 1115216 1114199 1114969A53 (C8-C29-O11) 1044386 1044819 1046594 104594 1046712 1046043 1075cA54 (C8-C32-C34) 1204664 1204528 1205688 1204387 1204312 1202925A55 (C2-C34-C32) 1252907 1249802 1255569 1252584 1255114 1251913A56 (C3-C40-C26) 1247594 1251561 1243752 1247373 1243541 1247241A57 (C26-C40-O59) 1161404 1159652 1160868 1160753 1159905 1159607A58 (C5-C46-C48) 1100006 1100212 1098202 1098537 1096430 1096699A59 (C48-C46-O61) 1115740 1115456 1117313 1117203 1118859 1118641A60 (C46-C48-C51) 1026704 1027788 1028570 1030253 1026915 1028703A61 (C6-C51-C14) 1168638 1168705 1166829 1166156 1163993 1163329A62 (C6-C51-C48) 1044966 1045425 1042867 1043539 1043511 1044332A63 (C14-C51-C48) 1149685 1148714 1152826 1151809 1152757 1151468A64 (C14-C53-C55) 1061668 1062381 1067966 1068606 1066618 1067168 10614aA65 (O15-C55-C53) 1107484 1106455 1103339 1102350 1104305 1103331 11049aA66 (C14-C57-O15) 1113857 1112607 1110591 1109356 1111339 1110086 11049aA67 (C12-O60-C62) 1231805 1234264 1224520 1222629 1218099 1215920A68 (O60-C62-C63) 1183342 1191473 1186681 1194932 1186273 1193485A69 (O60-C62-O65) 1183753 1179395 1175454 1171467 1176414 1172568A70 (C63-C62-O65) 1230766 1226884 1234720 1230718 1234069 1231015A71 (C62-C63-C64) 1169655 1171950 1162922 1167661 1161754 1166519A72 (C62-C63-C71) 1178479 1173833 1194971 1185815 1197175 1190158A74 (C64-C63-C71) 1250717 1252904 1241105 1245124 1239876 1241815A75 (C63-C64-C67) 1272664 1272197 1272301 1272514 1269123 1267855Total energy (Hartree) -171915539 -171917648 -172982917 -172984726 -172917724 -172919498
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
IP (eV) 7151 5662 7875 6819 7861 6819EA (eV) -0841 0684 0461 1804 0450 1825120583119888119901 (eV) -3155 -3173 -4168 -4312 -4156 -4322X (eV) 3155 3173 4168 4312 4156 4322H (eV) 3996 2489 3707 2508 3706 2497s (eV)minus1 0250 0402 0270 0399 0270 0400120596 (eV) 1245 2022 2343 3707 2330 3740
HOMO
LUMO
RHF6-311G(dp) B3PW916-311G(dp) B3LYP6-311G(dp)
EH = -8636 eV
EL = eV
Eg=11146 eVEH = -6275 eV
EL = -1922 eV
Eg=4353 eVEH = -6232 eV
EL = -1896 eV
Eg=4 eV
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
2 Advances in Condensed Matter Physics
gap charge distributions NLO properties vibrational fre-quencies NMR and UV-vis calculation) and some physico-chemical properties (3JH-H chemical coupling-coupling con-stant the global reactivity descriptors and some geometricalparameters such as bonds lengths and bonds angles) ofRubescin E molecule To the best of our knowledge notheoretical studywas performed yet on the titlemolecule thatis what motivated us to investigate the electronic structurethe spectroscopic and some physicochemical propertiesof Rubescin E molecule Except for NMR UV-vis 3JH-Hchemical coupling-coupling constant and the vibrationalfrequencies obtained for the two 120572 120573-unsaturated carbonylmoiety most of our results were not compared and weare optimistic that it can be used as threshold for futureexperimental or theoretical research Hartree Fock andDFT (using B3LYP and B3PW91 functionals) methods wereused for these purposes These properties were calculatedby employing the triple split valence basis set along withpolarization functions with and without diffuse functions asimplemented in Gaussian 09 Rev A02 in both gas phase andin a solution of chloroformThe methods and basis sets usedare among the most widely used [2ndash5] and provide excellentresults which are generally very close to experiments [6ndash8]
2 Computational Methods
Theoretical calculations were performed on Rubescin Eusing HF and DFT methods at the B3LYP and B3PW91levels as implemented in Gaussian 09W code [9] All thesecalculations were done in gas phase and in a solution ofchloroform No geometry restriction was applied duringthe optimization procedure The solvent effects were treatedwithin the conductor-like polarizable continuum model(CPCM) For the geometry optimization the 6-311G(dp) and6-311++G(dp) basis set were used in both gas and solventConvergence criteria in which both the maximum force anddisplacement are smaller than the cut-off of 0000015 and0000060 and RMS force and displacement less than thecut-off values of 0000010 and 0000040 were used in thecalculations in order to increase the accuracy of our resultsThe chemical 3JH-H proton-proton coupling constant func-tion of angle between two C-H vectors was calculated fromthe optimization output using the original Karplus equation[10] The optimized form of our molecule was then used todetermine the global reactivity descriptors electronic andNLOs properties The net charges were also evaluated usingMPA ESP and NBOs methods at the three levels mentionedabove and all this was done in both gas phase and chloroformwith the 6-311++G(dp) basis set In order to confirm thestability of our molecule the vibrational frequencies (IR andRaman) were evaluated at the 6-311G(dp) and no imaginaryfrequencies were found leading us to the results that ourmolecule was stable at the levels and basis set consideredThetime dependent density functional theory (TD-DFT) fieldwas used in gas phase with the 6-311++G(dp) basis in orderto understand the electronic transition of our molecule andthe obtained results were compared to experimentTheGIAO(gauge independent atomic orbital) method was used on theoptimized form of our molecule in a solution of chloroform
to determine the 1H and 13C NMR spectra parameters at thethree levels and with the 6-311++G(dp) basis set In orderto compare the calculated values of 1H and 13C chemicalshift with experimental results the reference and widelyusedmolecule TMS (tetramethylsilane) for this purpose wereexploited at the same level at the same phase and with thesame basis set
3 Results and Discussion
31 Optimized Structure The optimized geometry ofRubescin E obtained using the B3LYP6-311++G(dp)method in chloroform is shown in Figure 1 The value ofthe total electronic energy of the molecule obtained at theB3LYP shows that Figure 1 is the most stable structure of themolecule The total electronic energy calculated within thetwo methods in gas and in a solution of chloroform with the6-311++G(dp) is given in Table 1
32 Structural Properties A part of the optimized geometri-cal parameters (bond length bond angle) and total electronicenergy of the title molecule both in gas and in a solution ofchloroform are given in Table 1 using the three levels andwith the 6-311++G(dp) basis set The total description of themolecular geometry of Rubescin Emolecule in gas phase andin a solution of chloroform using ab initio (RHF) and DFT(B3LYP and B3PW91) methods with the 6-311++G(dp) basisset can be obtained from Supplementary Material S1
The atom numbering scheme adopted for this purposeis the same as in Figure 1 The energy differences betweenthe two used phases increase when we move from B3PW91to B3LYP and to RHF and are found to be approximatively048 eV 049 eV and 057 eV respectively The optimizedbond length and bond angle of Rubescin E are also listedin Table 1 with some specific experimental values [12ndash14]found in the literature for some groups of compounds suchas furan ethylene oxide and tetrahydrofuran present in ourmolecule It can be observed fromTable 1 that the values of thebond length obtained at B3LYP are slightly higher than thoseobtained at the B3PW91 level These differences are foundbetween 00034 A and 00107 A for C-C 00061 A and 00095A for C-O and 00007 A and 00013 A for C=C in gas phaseThe value of C=O bond length is better at the DFT methodssince its values are closer to 210 A found in literature [11] Itcan also been observed that the calculated bonds length usingHartree Fock and DFT methods are very close to the valuesfound in literature for the specific groups of compoundspresent in our molecule These observed differences variedfrom 00012 A at the B3LYP level to 00363 A at the RHF levelfrom 00002 A at the B3PW91 level to 00288 A at the B3LYPlevel and from 00019 A at the B3LYP level to 00259 A at theRHF level for C-C C-O and C=C bonds both in gas phaseand in chloroform solution respectively
The bonds angles of the studied molecule are slightlydifferent when we move from one phase to another at eachlevel with larger values obtained at the RHF level From ourresults it can be seen that the C-C-C bond angle varies from963773∘ to 1293418∘ from 966032∘ to 1288385∘ and from964146∘ to 1287371∘ at the gas phase respectively at the RHF
Advances in Condensed Matter Physics 3
Table 1 Optimized geometric parameters in gas phase and in chloroform solution of Rubescin E at the RHF B3LYP and B3PW91 level withthe 6-311++G (dp) basis sets
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
Bond lengthR1 (C1-C2) 15503 15490 15603 15583 15521 15500R2 (C1-C3) 15698 15672 15811 15777 15719 15684R3 (C1-C20) 15167 15157 15221 15215 15153 15147R4 (C1-C22) 15474 15481 15510 15509 15439 15438R5 (C2=O7) 11900 11948 12167 12213 12152 12197 210bR6 (C2-C34) 15041 14992 14966 14910 14920 14867R7 (C3-C4) 15898 15887 15973 15968 15866 15860R8 (C3-C40) 14814 14800 14972 14958 14931 14918 1462bR9 (C3-O59) 13994 14024 14311 14335 14236 14256 1428bR10 (C4-C5) 15515 15518 15549 15548 15473 15471R11 (C4-C12) 15707 15733 15756 15787 15676 15707R12 (C4-C36) 15501 15503 15543 15543 15471 15472R13 (C5-C6) 15428 15442 15477 15487 15401 15410R14 (C5-C46) 14556 14553 14720 14717 14686 14684 1462bR15 (C5-O61) 14206 14235 14568 14590 14473 14492 1428bR16 (C6-C26) 15259 15260 15306 15307 15246 15248R17 (C6-C42) 15352 15350 15373 15373 15298 15298R18 (C6-C51) 15703 15708 15810 15814 15724 15728R19 (C8-C16) 15423 15424 15477 15481 15405 15408R20 (C8-C20) 15256 15244 15348 15335 15276 15264 1536cR21 (C8-C29) 15405 15402 15479 15468 15416 15406 1536cR22 (C8-C32) 15036 15036 15010 15010 14958 14960R23 (C9-O11) 14120 14133 14389 14411 14304 14324 1428cR24 (C9-C12) 15288 15302 15357 15373 15311 15329R25 (C9-C20) 14997 14993 15044 15042 14999 14998 1536cR26 (O11-C29) 14261 14287 14530 14551 14438 14457 1428cR27 (C12-O60) 14104 14131 14339 14369 14255 14283R28 (C14-C51) 15035 15041 15003 15010 14953 14959R29 (C14-C53) 14493 14505 14428 14438 14387 14397 1430aR30 (C14=C57) 13411 13410 13621 13619 13614 13614 1364aR31 (O15-C55) 13382 13412 13609 13638 13548 13574 1364aR32 (O15-C57) 13467 13496 13659 13686 13592 13616 1364aR33 (C26-C40) 15162 15158 15190 15181 15137 15129R34 (C32=C34) 13270 13285 13431 13445 13422 13436R35 (C40-O59) 14010 14054 14353 14395 14282 14320 1428bR36 (C46-C48) 15086 15076 15135 15123 15088 15077R37 (C46-O61) 14005 14051 14326 14376 14254 14297 1428bR38 (C48-C51) 15407 15405 15478 15475 15408 15405R39 (C53=C55) 13381 13381 13567 13567 13559 13559 1364aR40 (O60-C62) 13485 13397 13805 13700 13743 13650R41 (C62-C63) 15033 15030 14998 15000 14956 14952R42 (C62=O65) 11810 11873 12059 12113 12046 12098R43 (C63=C64) 13222 13230 13402 13403 13394 13398R44 (C63-C71) 15153 15159 15127 15135 15071 15083
4 Advances in Condensed Matter Physics
Table 1 Continued
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
R45 (C64-C67) 15001 15002 14954 14959 14898 14901Bond anglesA1 (C2-C1-C3) 1153869 1151538 1153519 1150591 1153042 1149661A2 (C2-C1-C20) 1049116 1052360 1048861 1053058 1050195 1054353A3 (C2-C1-C22) 1046632 1048093 1048467 1050548 1047619 1050065A4 (C3-C1-C20) 1054487 1049239 1060693 1053428 1059491 1051727A5 (C3-C1-C22) 1100598 1104677 1093407 1099326 1094774 1101062A6 (C20-C1-C22) 1166507 1165134 1166409 1164160 1166212 1164196A7 (C1-C2-O7) 1226712 1221731 1225890 1220461 1226012 1220599A8 (C1-C2-C34) 1188294 1190297 1185520 1188580 1185112 1188095A9 (O7-C2-C34) 1183115 1186060 1186750 1189135 1186899 1189368A10 (C1-C3-C4) 1174677 1172546 1175179 1173499 1174703 1172908A11 (C1-C3-C40) 1204116 1203391 1205229 1203696 1204781 1203201A12 (C1-C3-O59) 1135239 1136346 1132288 1134708 1132740 1135007A13 (C4-C3-C40) 1197989 1198618 1196777 1197275 1197605 1198264A14 (C4-C3-O59) 1109192 1113348 1106687 1110566 1107288 1111433A15 (C3-C4-C5) 1082815 1080767 1085292 1083020 1084460 1081898A16 (C3-C4-C12) 1169097 1169148 1166545 1168466 1168336 1170260A17 (C3-C4-C36) 1073533 1075825 1072145 1073890 1072213 1073820A18 (C5-C4-C12) 1109502 1112590 1108879 1111131 1110310 1113284A19 (C5-C4-C36) 1082096 1083900 1082857 1085557 1080890 1083471A20 (C12-C4-C36) 1047402 1042361 104883 1042585 1047988 1041530A21 (C4-C5-C6) 1223963 1225160 1222095 1222513 1222181 1222697A22 (C4-C5-C46) 1261434 1260858 1262488 1261993 1261315 1260739A23 (C4-C5-O61) 1137557 1135947 1137382 1136922 1140173 1139553A24 (C6-C5-C46) 1084092 1084312 1082407 1082667 1082513 1082900A25 (C6-C5-O61) 1093436 1091575 1097850 1096384 1096935 1095481A26 (C5-C6-C26) 1069225 1071323 1071725 1073025 1071359 1072931A27 (C5-C6-C42) 1147934 1148607 1144807 1145006 1145313 1145541A28 (C5-C6-C51) 1018612 1018830 1019281 1020115 1018916 1019777A29 (C26-C6-C42) 1088679 1086162 1091102 1089149 1091443 1089314A30 (C26-C6-C51) 1138205 1138653 1139931 1140014 1139406 1139367A31 (C42-C6-C51) 1105307 1104727 1101102 1100888 1101443 1101222A32 (C16-C8-C20) 1178467 1178806 1175220 1175381 1173986 1173974A33 (C16-C8-C29) 1083950 1085431 1084117 1085195 1085270 1086672A34 (C16-C8-C32) 1095455 1094283 1095034 1093293 1096190 1094415A35 (C20-C8-C29) 963773 964321 966032 966193 964146 964285 1015cA36 (C20-C8-C32) 1063315 1062487 1064280 1063876 106432 1063732A37 (C29-C8-C32) 1182843 1182659 1183155 1184200 1183462 1184575A38 (O11-C9-C12) 1132108 1131065 1132048 1132060 1131493 1131724A39 (O11-C9-C20) 1033360 1031494 1038285 1036622 1038971 1037399 1040cA40 (C12-C9-C20) 1092549 1094574 1087908 1089954 1084814 1086640A41 (C9-O11-C29) 1111841 1112217 1098976 1099018 1098190 1098362 1106cA42 (C4-C12-C9) 1104259 1106951 1100123 1103980 1098110 1101418A43 (C4-C12-O60) 1111499 1114570 1109644 1114849 1113257 1119073
Advances in Condensed Matter Physics 5
Table 1 Continued
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
A44 (C9-C12-O60) 1090864 1087044 1087314 1082508 1084512 1079972A45 (C51-C14-C53) 126042 1260928 1261043 1261692 1262986 1263771A46 (C51-C14-C57) 1293418 1291716 1288385 1286558 1287371 1285448A47 (C53-C14-C57) 1045893 1047043 1050493 1051666 1049597 1050728 10614aA48 (C55-O15-C57) 1071084 1071499 1067602 1068013 1068133 1068678 10674aA49 (C1-C20-C8) 1211479 1210073 1209097 1207705 1209914 1208439A50 (C1-C20-C9) 1187226 1185220 1187478 1183732 1186818 1182898A51 (C8-C20-C9) 1038120 1039439 1042023 1043600 1040389 1042216 1044cA52 (C6-C26-C40) 1114945 1116304 1114804 1115216 1114199 1114969A53 (C8-C29-O11) 1044386 1044819 1046594 104594 1046712 1046043 1075cA54 (C8-C32-C34) 1204664 1204528 1205688 1204387 1204312 1202925A55 (C2-C34-C32) 1252907 1249802 1255569 1252584 1255114 1251913A56 (C3-C40-C26) 1247594 1251561 1243752 1247373 1243541 1247241A57 (C26-C40-O59) 1161404 1159652 1160868 1160753 1159905 1159607A58 (C5-C46-C48) 1100006 1100212 1098202 1098537 1096430 1096699A59 (C48-C46-O61) 1115740 1115456 1117313 1117203 1118859 1118641A60 (C46-C48-C51) 1026704 1027788 1028570 1030253 1026915 1028703A61 (C6-C51-C14) 1168638 1168705 1166829 1166156 1163993 1163329A62 (C6-C51-C48) 1044966 1045425 1042867 1043539 1043511 1044332A63 (C14-C51-C48) 1149685 1148714 1152826 1151809 1152757 1151468A64 (C14-C53-C55) 1061668 1062381 1067966 1068606 1066618 1067168 10614aA65 (O15-C55-C53) 1107484 1106455 1103339 1102350 1104305 1103331 11049aA66 (C14-C57-O15) 1113857 1112607 1110591 1109356 1111339 1110086 11049aA67 (C12-O60-C62) 1231805 1234264 1224520 1222629 1218099 1215920A68 (O60-C62-C63) 1183342 1191473 1186681 1194932 1186273 1193485A69 (O60-C62-O65) 1183753 1179395 1175454 1171467 1176414 1172568A70 (C63-C62-O65) 1230766 1226884 1234720 1230718 1234069 1231015A71 (C62-C63-C64) 1169655 1171950 1162922 1167661 1161754 1166519A72 (C62-C63-C71) 1178479 1173833 1194971 1185815 1197175 1190158A74 (C64-C63-C71) 1250717 1252904 1241105 1245124 1239876 1241815A75 (C63-C64-C67) 1272664 1272197 1272301 1272514 1269123 1267855Total energy (Hartree) -171915539 -171917648 -172982917 -172984726 -172917724 -172919498
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
IP (eV) 7151 5662 7875 6819 7861 6819EA (eV) -0841 0684 0461 1804 0450 1825120583119888119901 (eV) -3155 -3173 -4168 -4312 -4156 -4322X (eV) 3155 3173 4168 4312 4156 4322H (eV) 3996 2489 3707 2508 3706 2497s (eV)minus1 0250 0402 0270 0399 0270 0400120596 (eV) 1245 2022 2343 3707 2330 3740
HOMO
LUMO
RHF6-311G(dp) B3PW916-311G(dp) B3LYP6-311G(dp)
EH = -8636 eV
EL = eV
Eg=11146 eVEH = -6275 eV
EL = -1922 eV
Eg=4353 eVEH = -6232 eV
EL = -1896 eV
Eg=4 eV
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 3
Table 1 Optimized geometric parameters in gas phase and in chloroform solution of Rubescin E at the RHF B3LYP and B3PW91 level withthe 6-311++G (dp) basis sets
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
Bond lengthR1 (C1-C2) 15503 15490 15603 15583 15521 15500R2 (C1-C3) 15698 15672 15811 15777 15719 15684R3 (C1-C20) 15167 15157 15221 15215 15153 15147R4 (C1-C22) 15474 15481 15510 15509 15439 15438R5 (C2=O7) 11900 11948 12167 12213 12152 12197 210bR6 (C2-C34) 15041 14992 14966 14910 14920 14867R7 (C3-C4) 15898 15887 15973 15968 15866 15860R8 (C3-C40) 14814 14800 14972 14958 14931 14918 1462bR9 (C3-O59) 13994 14024 14311 14335 14236 14256 1428bR10 (C4-C5) 15515 15518 15549 15548 15473 15471R11 (C4-C12) 15707 15733 15756 15787 15676 15707R12 (C4-C36) 15501 15503 15543 15543 15471 15472R13 (C5-C6) 15428 15442 15477 15487 15401 15410R14 (C5-C46) 14556 14553 14720 14717 14686 14684 1462bR15 (C5-O61) 14206 14235 14568 14590 14473 14492 1428bR16 (C6-C26) 15259 15260 15306 15307 15246 15248R17 (C6-C42) 15352 15350 15373 15373 15298 15298R18 (C6-C51) 15703 15708 15810 15814 15724 15728R19 (C8-C16) 15423 15424 15477 15481 15405 15408R20 (C8-C20) 15256 15244 15348 15335 15276 15264 1536cR21 (C8-C29) 15405 15402 15479 15468 15416 15406 1536cR22 (C8-C32) 15036 15036 15010 15010 14958 14960R23 (C9-O11) 14120 14133 14389 14411 14304 14324 1428cR24 (C9-C12) 15288 15302 15357 15373 15311 15329R25 (C9-C20) 14997 14993 15044 15042 14999 14998 1536cR26 (O11-C29) 14261 14287 14530 14551 14438 14457 1428cR27 (C12-O60) 14104 14131 14339 14369 14255 14283R28 (C14-C51) 15035 15041 15003 15010 14953 14959R29 (C14-C53) 14493 14505 14428 14438 14387 14397 1430aR30 (C14=C57) 13411 13410 13621 13619 13614 13614 1364aR31 (O15-C55) 13382 13412 13609 13638 13548 13574 1364aR32 (O15-C57) 13467 13496 13659 13686 13592 13616 1364aR33 (C26-C40) 15162 15158 15190 15181 15137 15129R34 (C32=C34) 13270 13285 13431 13445 13422 13436R35 (C40-O59) 14010 14054 14353 14395 14282 14320 1428bR36 (C46-C48) 15086 15076 15135 15123 15088 15077R37 (C46-O61) 14005 14051 14326 14376 14254 14297 1428bR38 (C48-C51) 15407 15405 15478 15475 15408 15405R39 (C53=C55) 13381 13381 13567 13567 13559 13559 1364aR40 (O60-C62) 13485 13397 13805 13700 13743 13650R41 (C62-C63) 15033 15030 14998 15000 14956 14952R42 (C62=O65) 11810 11873 12059 12113 12046 12098R43 (C63=C64) 13222 13230 13402 13403 13394 13398R44 (C63-C71) 15153 15159 15127 15135 15071 15083
4 Advances in Condensed Matter Physics
Table 1 Continued
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
R45 (C64-C67) 15001 15002 14954 14959 14898 14901Bond anglesA1 (C2-C1-C3) 1153869 1151538 1153519 1150591 1153042 1149661A2 (C2-C1-C20) 1049116 1052360 1048861 1053058 1050195 1054353A3 (C2-C1-C22) 1046632 1048093 1048467 1050548 1047619 1050065A4 (C3-C1-C20) 1054487 1049239 1060693 1053428 1059491 1051727A5 (C3-C1-C22) 1100598 1104677 1093407 1099326 1094774 1101062A6 (C20-C1-C22) 1166507 1165134 1166409 1164160 1166212 1164196A7 (C1-C2-O7) 1226712 1221731 1225890 1220461 1226012 1220599A8 (C1-C2-C34) 1188294 1190297 1185520 1188580 1185112 1188095A9 (O7-C2-C34) 1183115 1186060 1186750 1189135 1186899 1189368A10 (C1-C3-C4) 1174677 1172546 1175179 1173499 1174703 1172908A11 (C1-C3-C40) 1204116 1203391 1205229 1203696 1204781 1203201A12 (C1-C3-O59) 1135239 1136346 1132288 1134708 1132740 1135007A13 (C4-C3-C40) 1197989 1198618 1196777 1197275 1197605 1198264A14 (C4-C3-O59) 1109192 1113348 1106687 1110566 1107288 1111433A15 (C3-C4-C5) 1082815 1080767 1085292 1083020 1084460 1081898A16 (C3-C4-C12) 1169097 1169148 1166545 1168466 1168336 1170260A17 (C3-C4-C36) 1073533 1075825 1072145 1073890 1072213 1073820A18 (C5-C4-C12) 1109502 1112590 1108879 1111131 1110310 1113284A19 (C5-C4-C36) 1082096 1083900 1082857 1085557 1080890 1083471A20 (C12-C4-C36) 1047402 1042361 104883 1042585 1047988 1041530A21 (C4-C5-C6) 1223963 1225160 1222095 1222513 1222181 1222697A22 (C4-C5-C46) 1261434 1260858 1262488 1261993 1261315 1260739A23 (C4-C5-O61) 1137557 1135947 1137382 1136922 1140173 1139553A24 (C6-C5-C46) 1084092 1084312 1082407 1082667 1082513 1082900A25 (C6-C5-O61) 1093436 1091575 1097850 1096384 1096935 1095481A26 (C5-C6-C26) 1069225 1071323 1071725 1073025 1071359 1072931A27 (C5-C6-C42) 1147934 1148607 1144807 1145006 1145313 1145541A28 (C5-C6-C51) 1018612 1018830 1019281 1020115 1018916 1019777A29 (C26-C6-C42) 1088679 1086162 1091102 1089149 1091443 1089314A30 (C26-C6-C51) 1138205 1138653 1139931 1140014 1139406 1139367A31 (C42-C6-C51) 1105307 1104727 1101102 1100888 1101443 1101222A32 (C16-C8-C20) 1178467 1178806 1175220 1175381 1173986 1173974A33 (C16-C8-C29) 1083950 1085431 1084117 1085195 1085270 1086672A34 (C16-C8-C32) 1095455 1094283 1095034 1093293 1096190 1094415A35 (C20-C8-C29) 963773 964321 966032 966193 964146 964285 1015cA36 (C20-C8-C32) 1063315 1062487 1064280 1063876 106432 1063732A37 (C29-C8-C32) 1182843 1182659 1183155 1184200 1183462 1184575A38 (O11-C9-C12) 1132108 1131065 1132048 1132060 1131493 1131724A39 (O11-C9-C20) 1033360 1031494 1038285 1036622 1038971 1037399 1040cA40 (C12-C9-C20) 1092549 1094574 1087908 1089954 1084814 1086640A41 (C9-O11-C29) 1111841 1112217 1098976 1099018 1098190 1098362 1106cA42 (C4-C12-C9) 1104259 1106951 1100123 1103980 1098110 1101418A43 (C4-C12-O60) 1111499 1114570 1109644 1114849 1113257 1119073
Advances in Condensed Matter Physics 5
Table 1 Continued
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
A44 (C9-C12-O60) 1090864 1087044 1087314 1082508 1084512 1079972A45 (C51-C14-C53) 126042 1260928 1261043 1261692 1262986 1263771A46 (C51-C14-C57) 1293418 1291716 1288385 1286558 1287371 1285448A47 (C53-C14-C57) 1045893 1047043 1050493 1051666 1049597 1050728 10614aA48 (C55-O15-C57) 1071084 1071499 1067602 1068013 1068133 1068678 10674aA49 (C1-C20-C8) 1211479 1210073 1209097 1207705 1209914 1208439A50 (C1-C20-C9) 1187226 1185220 1187478 1183732 1186818 1182898A51 (C8-C20-C9) 1038120 1039439 1042023 1043600 1040389 1042216 1044cA52 (C6-C26-C40) 1114945 1116304 1114804 1115216 1114199 1114969A53 (C8-C29-O11) 1044386 1044819 1046594 104594 1046712 1046043 1075cA54 (C8-C32-C34) 1204664 1204528 1205688 1204387 1204312 1202925A55 (C2-C34-C32) 1252907 1249802 1255569 1252584 1255114 1251913A56 (C3-C40-C26) 1247594 1251561 1243752 1247373 1243541 1247241A57 (C26-C40-O59) 1161404 1159652 1160868 1160753 1159905 1159607A58 (C5-C46-C48) 1100006 1100212 1098202 1098537 1096430 1096699A59 (C48-C46-O61) 1115740 1115456 1117313 1117203 1118859 1118641A60 (C46-C48-C51) 1026704 1027788 1028570 1030253 1026915 1028703A61 (C6-C51-C14) 1168638 1168705 1166829 1166156 1163993 1163329A62 (C6-C51-C48) 1044966 1045425 1042867 1043539 1043511 1044332A63 (C14-C51-C48) 1149685 1148714 1152826 1151809 1152757 1151468A64 (C14-C53-C55) 1061668 1062381 1067966 1068606 1066618 1067168 10614aA65 (O15-C55-C53) 1107484 1106455 1103339 1102350 1104305 1103331 11049aA66 (C14-C57-O15) 1113857 1112607 1110591 1109356 1111339 1110086 11049aA67 (C12-O60-C62) 1231805 1234264 1224520 1222629 1218099 1215920A68 (O60-C62-C63) 1183342 1191473 1186681 1194932 1186273 1193485A69 (O60-C62-O65) 1183753 1179395 1175454 1171467 1176414 1172568A70 (C63-C62-O65) 1230766 1226884 1234720 1230718 1234069 1231015A71 (C62-C63-C64) 1169655 1171950 1162922 1167661 1161754 1166519A72 (C62-C63-C71) 1178479 1173833 1194971 1185815 1197175 1190158A74 (C64-C63-C71) 1250717 1252904 1241105 1245124 1239876 1241815A75 (C63-C64-C67) 1272664 1272197 1272301 1272514 1269123 1267855Total energy (Hartree) -171915539 -171917648 -172982917 -172984726 -172917724 -172919498
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
IP (eV) 7151 5662 7875 6819 7861 6819EA (eV) -0841 0684 0461 1804 0450 1825120583119888119901 (eV) -3155 -3173 -4168 -4312 -4156 -4322X (eV) 3155 3173 4168 4312 4156 4322H (eV) 3996 2489 3707 2508 3706 2497s (eV)minus1 0250 0402 0270 0399 0270 0400120596 (eV) 1245 2022 2343 3707 2330 3740
HOMO
LUMO
RHF6-311G(dp) B3PW916-311G(dp) B3LYP6-311G(dp)
EH = -8636 eV
EL = eV
Eg=11146 eVEH = -6275 eV
EL = -1922 eV
Eg=4353 eVEH = -6232 eV
EL = -1896 eV
Eg=4 eV
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
4 Advances in Condensed Matter Physics
Table 1 Continued
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
R45 (C64-C67) 15001 15002 14954 14959 14898 14901Bond anglesA1 (C2-C1-C3) 1153869 1151538 1153519 1150591 1153042 1149661A2 (C2-C1-C20) 1049116 1052360 1048861 1053058 1050195 1054353A3 (C2-C1-C22) 1046632 1048093 1048467 1050548 1047619 1050065A4 (C3-C1-C20) 1054487 1049239 1060693 1053428 1059491 1051727A5 (C3-C1-C22) 1100598 1104677 1093407 1099326 1094774 1101062A6 (C20-C1-C22) 1166507 1165134 1166409 1164160 1166212 1164196A7 (C1-C2-O7) 1226712 1221731 1225890 1220461 1226012 1220599A8 (C1-C2-C34) 1188294 1190297 1185520 1188580 1185112 1188095A9 (O7-C2-C34) 1183115 1186060 1186750 1189135 1186899 1189368A10 (C1-C3-C4) 1174677 1172546 1175179 1173499 1174703 1172908A11 (C1-C3-C40) 1204116 1203391 1205229 1203696 1204781 1203201A12 (C1-C3-O59) 1135239 1136346 1132288 1134708 1132740 1135007A13 (C4-C3-C40) 1197989 1198618 1196777 1197275 1197605 1198264A14 (C4-C3-O59) 1109192 1113348 1106687 1110566 1107288 1111433A15 (C3-C4-C5) 1082815 1080767 1085292 1083020 1084460 1081898A16 (C3-C4-C12) 1169097 1169148 1166545 1168466 1168336 1170260A17 (C3-C4-C36) 1073533 1075825 1072145 1073890 1072213 1073820A18 (C5-C4-C12) 1109502 1112590 1108879 1111131 1110310 1113284A19 (C5-C4-C36) 1082096 1083900 1082857 1085557 1080890 1083471A20 (C12-C4-C36) 1047402 1042361 104883 1042585 1047988 1041530A21 (C4-C5-C6) 1223963 1225160 1222095 1222513 1222181 1222697A22 (C4-C5-C46) 1261434 1260858 1262488 1261993 1261315 1260739A23 (C4-C5-O61) 1137557 1135947 1137382 1136922 1140173 1139553A24 (C6-C5-C46) 1084092 1084312 1082407 1082667 1082513 1082900A25 (C6-C5-O61) 1093436 1091575 1097850 1096384 1096935 1095481A26 (C5-C6-C26) 1069225 1071323 1071725 1073025 1071359 1072931A27 (C5-C6-C42) 1147934 1148607 1144807 1145006 1145313 1145541A28 (C5-C6-C51) 1018612 1018830 1019281 1020115 1018916 1019777A29 (C26-C6-C42) 1088679 1086162 1091102 1089149 1091443 1089314A30 (C26-C6-C51) 1138205 1138653 1139931 1140014 1139406 1139367A31 (C42-C6-C51) 1105307 1104727 1101102 1100888 1101443 1101222A32 (C16-C8-C20) 1178467 1178806 1175220 1175381 1173986 1173974A33 (C16-C8-C29) 1083950 1085431 1084117 1085195 1085270 1086672A34 (C16-C8-C32) 1095455 1094283 1095034 1093293 1096190 1094415A35 (C20-C8-C29) 963773 964321 966032 966193 964146 964285 1015cA36 (C20-C8-C32) 1063315 1062487 1064280 1063876 106432 1063732A37 (C29-C8-C32) 1182843 1182659 1183155 1184200 1183462 1184575A38 (O11-C9-C12) 1132108 1131065 1132048 1132060 1131493 1131724A39 (O11-C9-C20) 1033360 1031494 1038285 1036622 1038971 1037399 1040cA40 (C12-C9-C20) 1092549 1094574 1087908 1089954 1084814 1086640A41 (C9-O11-C29) 1111841 1112217 1098976 1099018 1098190 1098362 1106cA42 (C4-C12-C9) 1104259 1106951 1100123 1103980 1098110 1101418A43 (C4-C12-O60) 1111499 1114570 1109644 1114849 1113257 1119073
Advances in Condensed Matter Physics 5
Table 1 Continued
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
A44 (C9-C12-O60) 1090864 1087044 1087314 1082508 1084512 1079972A45 (C51-C14-C53) 126042 1260928 1261043 1261692 1262986 1263771A46 (C51-C14-C57) 1293418 1291716 1288385 1286558 1287371 1285448A47 (C53-C14-C57) 1045893 1047043 1050493 1051666 1049597 1050728 10614aA48 (C55-O15-C57) 1071084 1071499 1067602 1068013 1068133 1068678 10674aA49 (C1-C20-C8) 1211479 1210073 1209097 1207705 1209914 1208439A50 (C1-C20-C9) 1187226 1185220 1187478 1183732 1186818 1182898A51 (C8-C20-C9) 1038120 1039439 1042023 1043600 1040389 1042216 1044cA52 (C6-C26-C40) 1114945 1116304 1114804 1115216 1114199 1114969A53 (C8-C29-O11) 1044386 1044819 1046594 104594 1046712 1046043 1075cA54 (C8-C32-C34) 1204664 1204528 1205688 1204387 1204312 1202925A55 (C2-C34-C32) 1252907 1249802 1255569 1252584 1255114 1251913A56 (C3-C40-C26) 1247594 1251561 1243752 1247373 1243541 1247241A57 (C26-C40-O59) 1161404 1159652 1160868 1160753 1159905 1159607A58 (C5-C46-C48) 1100006 1100212 1098202 1098537 1096430 1096699A59 (C48-C46-O61) 1115740 1115456 1117313 1117203 1118859 1118641A60 (C46-C48-C51) 1026704 1027788 1028570 1030253 1026915 1028703A61 (C6-C51-C14) 1168638 1168705 1166829 1166156 1163993 1163329A62 (C6-C51-C48) 1044966 1045425 1042867 1043539 1043511 1044332A63 (C14-C51-C48) 1149685 1148714 1152826 1151809 1152757 1151468A64 (C14-C53-C55) 1061668 1062381 1067966 1068606 1066618 1067168 10614aA65 (O15-C55-C53) 1107484 1106455 1103339 1102350 1104305 1103331 11049aA66 (C14-C57-O15) 1113857 1112607 1110591 1109356 1111339 1110086 11049aA67 (C12-O60-C62) 1231805 1234264 1224520 1222629 1218099 1215920A68 (O60-C62-C63) 1183342 1191473 1186681 1194932 1186273 1193485A69 (O60-C62-O65) 1183753 1179395 1175454 1171467 1176414 1172568A70 (C63-C62-O65) 1230766 1226884 1234720 1230718 1234069 1231015A71 (C62-C63-C64) 1169655 1171950 1162922 1167661 1161754 1166519A72 (C62-C63-C71) 1178479 1173833 1194971 1185815 1197175 1190158A74 (C64-C63-C71) 1250717 1252904 1241105 1245124 1239876 1241815A75 (C63-C64-C67) 1272664 1272197 1272301 1272514 1269123 1267855Total energy (Hartree) -171915539 -171917648 -172982917 -172984726 -172917724 -172919498
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
IP (eV) 7151 5662 7875 6819 7861 6819EA (eV) -0841 0684 0461 1804 0450 1825120583119888119901 (eV) -3155 -3173 -4168 -4312 -4156 -4322X (eV) 3155 3173 4168 4312 4156 4322H (eV) 3996 2489 3707 2508 3706 2497s (eV)minus1 0250 0402 0270 0399 0270 0400120596 (eV) 1245 2022 2343 3707 2330 3740
HOMO
LUMO
RHF6-311G(dp) B3PW916-311G(dp) B3LYP6-311G(dp)
EH = -8636 eV
EL = eV
Eg=11146 eVEH = -6275 eV
EL = -1922 eV
Eg=4353 eVEH = -6232 eV
EL = -1896 eV
Eg=4 eV
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 5
Table 1 Continued
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
A44 (C9-C12-O60) 1090864 1087044 1087314 1082508 1084512 1079972A45 (C51-C14-C53) 126042 1260928 1261043 1261692 1262986 1263771A46 (C51-C14-C57) 1293418 1291716 1288385 1286558 1287371 1285448A47 (C53-C14-C57) 1045893 1047043 1050493 1051666 1049597 1050728 10614aA48 (C55-O15-C57) 1071084 1071499 1067602 1068013 1068133 1068678 10674aA49 (C1-C20-C8) 1211479 1210073 1209097 1207705 1209914 1208439A50 (C1-C20-C9) 1187226 1185220 1187478 1183732 1186818 1182898A51 (C8-C20-C9) 1038120 1039439 1042023 1043600 1040389 1042216 1044cA52 (C6-C26-C40) 1114945 1116304 1114804 1115216 1114199 1114969A53 (C8-C29-O11) 1044386 1044819 1046594 104594 1046712 1046043 1075cA54 (C8-C32-C34) 1204664 1204528 1205688 1204387 1204312 1202925A55 (C2-C34-C32) 1252907 1249802 1255569 1252584 1255114 1251913A56 (C3-C40-C26) 1247594 1251561 1243752 1247373 1243541 1247241A57 (C26-C40-O59) 1161404 1159652 1160868 1160753 1159905 1159607A58 (C5-C46-C48) 1100006 1100212 1098202 1098537 1096430 1096699A59 (C48-C46-O61) 1115740 1115456 1117313 1117203 1118859 1118641A60 (C46-C48-C51) 1026704 1027788 1028570 1030253 1026915 1028703A61 (C6-C51-C14) 1168638 1168705 1166829 1166156 1163993 1163329A62 (C6-C51-C48) 1044966 1045425 1042867 1043539 1043511 1044332A63 (C14-C51-C48) 1149685 1148714 1152826 1151809 1152757 1151468A64 (C14-C53-C55) 1061668 1062381 1067966 1068606 1066618 1067168 10614aA65 (O15-C55-C53) 1107484 1106455 1103339 1102350 1104305 1103331 11049aA66 (C14-C57-O15) 1113857 1112607 1110591 1109356 1111339 1110086 11049aA67 (C12-O60-C62) 1231805 1234264 1224520 1222629 1218099 1215920A68 (O60-C62-C63) 1183342 1191473 1186681 1194932 1186273 1193485A69 (O60-C62-O65) 1183753 1179395 1175454 1171467 1176414 1172568A70 (C63-C62-O65) 1230766 1226884 1234720 1230718 1234069 1231015A71 (C62-C63-C64) 1169655 1171950 1162922 1167661 1161754 1166519A72 (C62-C63-C71) 1178479 1173833 1194971 1185815 1197175 1190158A74 (C64-C63-C71) 1250717 1252904 1241105 1245124 1239876 1241815A75 (C63-C64-C67) 1272664 1272197 1272301 1272514 1269123 1267855Total energy (Hartree) -171915539 -171917648 -172982917 -172984726 -172917724 -172919498
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
IP (eV) 7151 5662 7875 6819 7861 6819EA (eV) -0841 0684 0461 1804 0450 1825120583119888119901 (eV) -3155 -3173 -4168 -4312 -4156 -4322X (eV) 3155 3173 4168 4312 4156 4322H (eV) 3996 2489 3707 2508 3706 2497s (eV)minus1 0250 0402 0270 0399 0270 0400120596 (eV) 1245 2022 2343 3707 2330 3740
HOMO
LUMO
RHF6-311G(dp) B3PW916-311G(dp) B3LYP6-311G(dp)
EH = -8636 eV
EL = eV
Eg=11146 eVEH = -6275 eV
EL = -1922 eV
Eg=4353 eVEH = -6232 eV
EL = -1896 eV
Eg=4 eV
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
IP (eV) 7151 5662 7875 6819 7861 6819EA (eV) -0841 0684 0461 1804 0450 1825120583119888119901 (eV) -3155 -3173 -4168 -4312 -4156 -4322X (eV) 3155 3173 4168 4312 4156 4322H (eV) 3996 2489 3707 2508 3706 2497s (eV)minus1 0250 0402 0270 0399 0270 0400120596 (eV) 1245 2022 2343 3707 2330 3740
HOMO
LUMO
RHF6-311G(dp) B3PW916-311G(dp) B3LYP6-311G(dp)
EH = -8636 eV
EL = eV
Eg=11146 eVEH = -6275 eV
EL = -1922 eV
Eg=4353 eVEH = -6232 eV
EL = -1896 eV
Eg=4 eV
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
IP (eV) 7151 5662 7875 6819 7861 6819EA (eV) -0841 0684 0461 1804 0450 1825120583119888119901 (eV) -3155 -3173 -4168 -4312 -4156 -4322X (eV) 3155 3173 4168 4312 4156 4322H (eV) 3996 2489 3707 2508 3706 2497s (eV)minus1 0250 0402 0270 0399 0270 0400120596 (eV) 1245 2022 2343 3707 2330 3740
HOMO
LUMO
RHF6-311G(dp) B3PW916-311G(dp) B3LYP6-311G(dp)
EH = -8636 eV
EL = eV
Eg=11146 eVEH = -6275 eV
EL = -1922 eV
Eg=4353 eVEH = -6232 eV
EL = -1896 eV
Eg=4 eV
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
IP (eV) 7151 5662 7875 6819 7861 6819EA (eV) -0841 0684 0461 1804 0450 1825120583119888119901 (eV) -3155 -3173 -4168 -4312 -4156 -4322X (eV) 3155 3173 4168 4312 4156 4322H (eV) 3996 2489 3707 2508 3706 2497s (eV)minus1 0250 0402 0270 0399 0270 0400120596 (eV) 1245 2022 2343 3707 2330 3740
HOMO
LUMO
RHF6-311G(dp) B3PW916-311G(dp) B3LYP6-311G(dp)
EH = -8636 eV
EL = eV
Eg=11146 eVEH = -6275 eV
EL = -1922 eV
Eg=4353 eVEH = -6232 eV
EL = -1896 eV
Eg=4 eV
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
IP (eV) 7151 5662 7875 6819 7861 6819EA (eV) -0841 0684 0461 1804 0450 1825120583119888119901 (eV) -3155 -3173 -4168 -4312 -4156 -4322X (eV) 3155 3173 4168 4312 4156 4322H (eV) 3996 2489 3707 2508 3706 2497s (eV)minus1 0250 0402 0270 0399 0270 0400120596 (eV) 1245 2022 2343 3707 2330 3740
HOMO
LUMO
RHF6-311G(dp) B3PW916-311G(dp) B3LYP6-311G(dp)
EH = -8636 eV
EL = eV
Eg=11146 eVEH = -6275 eV
EL = -1922 eV
Eg=4353 eVEH = -6232 eV
EL = -1896 eV
Eg=4 eV
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
120572 = 13 (120572119909119909 + 120572119910119910 + 120572119911119911) (2)
120583119863119872 = (1205832119909 + 1205832119910 + 1205832119911)12 (3)
120572 = 1radic2 [(120572119909119909 minus 120572119910119910)
2 + (120572119910119910 minus 120572119911119911)2
+ (120572119911119911 minus 120572119909119909)2 + 61205722119909119911 + 61205722119909119910 + 61205722119910119911]12
(4)
120573 = [(120573119909119909119909 + 120573119909119910119910 + 120573119909119911119911)2 + (120573119910119910119910 + 120573119910119911119911 + 120573119910119909119909)
2
+ (120573119911119911119911 + 120573119911119909119909 + 120573119911119910119910)2]12
(5)
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
120583119863119872 (D) 53966 70953 52074 67654 51176 66663120572119909119909 352266 421425 387992 470193 384258 465488120572119909119910 173299 242341 196436 296995 193544 290512120572119910119910 336148 424889 374795 479493 371091 475445120572119909119911 150612 0677331 0715703 -0411779 0795242 -0371934120572119910119911 339268 -123142 444903 00306216 453244 0450373120572119911119911 278550 371379 305049 415461 301619 411131120572tot (lowast10minus24 esu) 477036 600729 526799 673473 521438 667018Δ120572 (lowast10minus24 esu) 109240 98814 125387 116890 124723 115857120573119909119909119909 585850 116324 778905 117687 820568 124840120573119909119909119910 -343404 -403762 -339536 -665203 -290441 -604155120573119909119910119910 225993 154126 -296091 -106843 -366541 -122127120573119910119910119910 923349 129004 276922 -585834 268972 -636805120573119909119909119911 -163605 -235326 -550267 -817313 -580975 -896785120573119909119910119911 -872859 -0242861 -119414 103722 -128764 624556120573119910119910119911 -389332 -656523 -107633 -207304 -108216 -214866120573119909119911119911 -144537 -583711 -734826 -703072 -794692 -691599120573119910119911119911 -508004 -109450 -777921 -196200 -712685 -182588120573119911119911119911 -638532 239632 -167476 -0675756 -968167 578764120573 (lowast10minus33 esu) 7874783 8669154 17477167 37726270 16788815 37430498
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
E (Vmminus1)lowast 109 33873 35365 29597 30078 29386 29924P (Cmminus2)lowast10minus2 83339 107944 75778 86086 83117 79130120594 27787 34473 28916 32324 31945 29865Elowast10minus11 33458 39377 34457 37475 37139 35297120578 19439 21089 19727 20573 20480 19966D (Cmminus2)lowast10minus2 01133 01393 01020 01127 01091 01056MR (esumolminus1) 1203345 1515366 1328875 1698866 1315351 1682585
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91
H10 36354 44787 45162 444 H41 32764 38070 37375 397H13 37599 45046 44656 55 H43 00206 01390 01217 -H17 11735 13264 12850 - H44 05304 06752 06653 065H18 14006 14842 15205 134 H45 11410 12581 12916 -H19 08843 09632 09055 - H47 29441 34299 33665 345H21 22212 31228 32220 29 H49 18799 20794 20578 211H23 07480 08702 08499 - H50 16401 20098 20019 151H24 09682 12471 12747 143 H52 21382 26231 26453 252H25 16905 17201 17225 - H54 64241 64756 65064 623H27 17833 20352 19975 19 H56 76008 76737 76347 734H28 17575 21239 21319 19 H58 72432 72352 71892 724H30 31956 37283 37158 377 H66 65053 65963 67294 673H31 33513 35791 35410 355 H68 19939 20486 20556 -H33 74298 74428 75055 707 H69 16905 18891 19108 182H35 59894 61274 61740 595 H70 17037 18508 18560 -H37 03741 04953 04827 - H72 13371 15726 15006 -H38 14776 18588 18632 122 H73 17489 18289 18340 187H39 07281 12414 13276 - H74 21737 22617 22408 -
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1] Nuclei Calculated 120575 (ppm) Experimental 120575 (ppm) [1]RHF B3LYP B3PW91 RHF B3LYP B3PW91C1 44217875 56667075 5380495 475 s C34 134341675 139383575 13851605 1313 dC2 206549275 213070575 21062615 2003 s C36 21545175 24454275 2423345 227 qC3 56393275 73459075 7054015 646 s C40 53124275 65723775 6421635 603 dC4 43854075 56324675 5283685 449 s C42 22468475 24495375 2417495 215 qC5 60103575 77293875 7430925 683 d C46 48923175 61540375 5953515 552 dC6 39115675 49868075 4723345 413 s C48 29511075 34706875 3333385 311 tC8 39020275 51568975 4931465 413 s C51 38272375 48003275 4638035 388 dC9 65951775 79364675 7738455 714 d C53 117347375 119574075 11857695 1108 dC12 72763675 87369975 8463375 747 d C55 149815075 151680375 14971195 1429 dC14 130650675 133767875 13173785 1231 s C57 144528075 147708875 14591185 1392 dC16 21641175 23522875 2288275 211 q C62 178475775 182888075 18033025 1674 sC20 44504575 54261975 5316905 506 d C63 132986175 138281375 13647755 1288 sC22 16680575 18585575 1872435 175 q C64 148221575 150697975 15111665 1383 dC26 34988975 41161875 3999065 354 t C67 15275775 17096475 1751975 146 qC29 71816475 83425975 8135795 795 t C71 13518375 15400475 1547155 126 qC32 164415875 166172275 16517515 1516 d
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
B3LYP6-311++G(dp)
Experimental 1H NMR (ppm)
Experimental 1H NMR (ppm)Experimental 1H NMR (ppm)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
Cal
cula
ted
1H N
MR
(ppm
)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8
B3PW916-311++G(dp)
minus1
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
RHF6-311++G(dp)
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
16 Advances in Condensed Matter Physics
Table9Somec
alculatedscaled
andun
scaled
vibrationalfrequ
encies(cmminus1)IR
(kmm
olminus1)andRa
man
scatterin
gactivities(A4am
uminus1)o
fRub
escinEin
gasp
haseandchloroform
solutio
nob
tained
attheB
3LYP
6-311G(dp)level
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns32778244
317948966
801483
154454
327733
813179017957
02265
2605952
Sym
] sC-
Hgrou
pson
furanrin
g32729127
3174725319
16469
668185
32724528
3174279216
10819
837804
Asym
] sC-
Hgrou
pson
furanrin
g3240
2105
3143004185
09505
457116
3240
612
314339
364
16053
1003155
Asym
] sof
(C53-H54C55-H56)
3189511
309382567
35332
664094
318932
443093644
668
83712
1600412
] sC 40-H41
31754637
308019
9789
118025
2011091
31753082
3080048954
198811
3722174
Sym
] s(C34-H35C32-H33)
31727225
3077540
825
48286
432929
31704225
3075309825
129561
1111091
Asym
] sof
CH3(C36)
3164
5342
3069598174
54628
420037
31604647
3065650759
1313
981037241
] sC 64-H66
3140
7401
3046
517897
107253
481146
31418739
3047617683
289110
1114
035
Asym
] sof
CH3(C36C22)
30964047
3003512559
378710
1288493
31039325
3010814525
5335
1325644
8As
ym] sof
(C29-H30C29-H31)
30870614
2994449558
188484
6214
583094289
300146033
372141
110584
Asym
] sof
CH3(C71)] sC 12-H13
30560169
2964
336393
130488
742148
30620737
29702114
89179489
1627148
Sym
] sof
CH3(C22)
3055640
82963971576
144803
1428654
3056849
296514
353
210392
2348621
Asym
] sof
(C67-H69C67-H70)
302316
612932471117
1413
231209272
30290714
293819
9258
234132
2691
079
Sym
] sof
CH3(C71)
30167818
2926278346
239892
3180136
30180608
2927518976
258983
4866073
Sym
] sof
CH3(C67)
29997383
290974
6151
1000
4319507
29989246
2908956862
34528
899972
] sof
C 20-H21
1720
17795912
172620346
41725832
160679
17536214
1701012758
3262675
247567
] sof
C 62=O65and120573 s
ofC 62-C63=C64-C67
1664
17428596
1690573812
1915
410
326047
171916
781667592766
3749763
962937
] sof
C 2=O7and120573 s
ofC 1
-C2-C34-H35
16998624
1648866528
907515
1275998
169274
911641966
627
1590
973
26444
37] sC 63=C64120573
sH66-C64-C67-H68and120573 s
C 62-C63-C71-H72
16554051
160574
2947
209946
487257
16485716
15991144
52540221
1580979
] sC 34=C32120575
sof
H33-C32-C8and120575 s
ofH35-C34-C2
16272588
1578441036
11593
11251
16259499
157717
1403
14847
240532
Asym
] sof
C=Con
furanrin
g15328277
1486842869
173545
520428
153017
121484266
064
235845
1011704
Sym
] sof
C=Con
furanrin
g15310536
148512
1992
43738
61013
15225028
1476827716
54574
134777
scis
sof
(C29-H30C29-H31)
15184514
1472897858
139129
139129
15140912
146866846
4129483
2737
27120591 sof
CH3(C22C16)a
ndscis
wof
(C29-H30C29-H31)
15036728
1458562616
98386
57612
14985877
1453630069
197850
132898
120591 sof
CH3(C16C22C36)
149939
561454413732
51940
74533
14926161
1447837617
93270
174033
120591 sof
CH3(C42)scis
mof
(C26-H27C26-H28)a
ndscis
wof
(C48-H49C48-H50)
14884029
1443750813
09776
28672
1485682
144111154
67043
78167
120591 sof
CH3(C16C22C36)a
nd120575 m
ofC 20-H21
14855561
1440
989417
29100
52938
148174
021437287994
43280
1410
82scis
sof
(C48-H49C48-H50)a
nd120591 sof
CH3(C42)
14836563
143914
6611
04862
78554
14780624
1433720528
14889
212082
scis
sof
(C26-H27C26-H28)a
nd120591 m
ofCH3(C42)
14794465
1435063105
79832
380149
147031
891426209333
127942
586094
120591 sof
CH3(C67C71)
14635075
1419602275
25457
10126
14597847
1415991159
40997
20734
120591 sof
H21-C20-C9-H10and120591 w
ofCH3(C22)
14428169
139953
2393
53126
65726
14410254
1397794638
844
82148596
] mof
C 3-C40]
mof
C 5-C46rock s
of(C26-H27C40-H41)a
nd120591 m
ofH10-C9-C20-H21
14224074
1379735178
428712
4011
14205762
1377958914
6332
16108875
Sym
CH3um
brellamod
e
14187082
137614
6954
06510
12396
141637
111373879967
06332
115796
Asym
CH3um
brellamod
erock m
(C34-H35C32-H33)120575 m
C 51-H52
14179087
137537
1439
67934
35193
14148341
1372389077
52808
126492
] mof
C 14-C53120575
sof
H52-C51andsym
CH3um
brellamod
e14116946
1369343762
36967
2476
614055801
1363412697
63221
387377
asym
CH3um
brellamod
e(C 67C71)a
nd120575 m
ofH66-C64
14040182
1361897654
57921
13462
14020625
1360000
625
1276
8448755
rock m
of(H35-C34C32-H33)CH3um
brellamod
e(C 22C16)
and120591 m
ofH21-C20-C9-H10
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 17Ta
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
13994114
1357429058
73054
26928
1399317
135733
749
54113
66084
120591 sof
H10-C9-C20-H21rock m
of(H35-C34C32-H33)a
nd120575 m
ofH13-C12-O60
13927814
1350997958
44872
77674
13939199
135210
2303
87259
131186
120591 sof
H10-C9-C20-H21rock s
of(H35-C34C32-H33)a
nd120575 s
ofH13-C12-O6
13813486
1339908142
08619
16091
137852
37133716
7989
27575
35116
wagg s
of(C29-H30C29-H31)120591 sof
H10-C9-C20-H21120575
mof
H13-C12-C9andCH3um
brellamod
e(C 16)
13737055
1332494335
43307
90916
13710783
1329945951
50163
1766
6] m
ofC 63-C71C
H3um
brellamod
e(C 67C71)120575 s
ofC 64-H66and
120591 mof
H10-C9-C20-H21
13689888
1327919136
44971
104931
13674102
1326387894
54518
202257
rock so
f(H56-C55C53-H54)120575 s
ofC 51-H52w
agg s
of(C48-H49
C 48H50)a
ndwagg m
of(C26-H27C26H28)
1365648
132467856
42088
10219
1364
8154
1323870938
64354
27506
120591 sof
H10-C9-C12-H13120575
mof
C 64-H66rock m
(H35-C34C32-H33)
wagg m
of(C29-H30C29H31)a
ndCH3um
brellamod
e(C 16C36)
13516819
131113
1443
23942
18233
13514078
1310865566
38793
29367
wagg s
of(C26-H27C26-H28)120575 s
ofC 51-H52
13430612
130276
9364
08245
68235
13432284
1302931548
00396
7840
5120591 m
ofH10-C9-C20-H21120575
sof
C 12-H13120575
sof
C 51-H52
1326340
61286550382
60965
52766
13224392
128276
6024
79781
138929
] sof
C 3-C40120575
sof
C 40-H41
13012149
126217
8453
41883
62643
13017097
126265840
971261
69678
] mof
C 5-C6twist so
f(C 26-H27C26-H28)wagg m
of(C48-H49
C 48-H50)120575 m
ofH47-C46-C5rock s
of(H56-C55C53-H54)
12970244
1258113668
17948
71956
12974084
1258486148
13878
215171
] wof
C 9-C12w
agg s
of(C48-H49C48-H50)120575 m
ofH47-C46-C48
120575 sof
C 51-H52twist m
of(C26-H27C26-H28)
12884675
1249813475
35313
15262
1287909
124927173
15765
1413
67120575 s
ofC 46-H47120575
sof
C 12-H13120591
mof
H10-C9-C20-H21andtw
ist m
of(C26-H27C26-H28)
12782074
1239861178
14763
186173
1278004
41239664
268
29774
2953
26] m
ofC 14-C51120575
sof
C 57-H58twist m
of(C48-H49C48-H50)a
nd120575 s
ofC 51-H52
12734643
1235260371
31680
1013
7512718325
1233677525
42401
209966
120575 sof
C 46-H47120575
sof
C 12-H13120575
sof
C 57-H58120591
sof
H10-C9-C20-H21
andtw
ist m
of(C26-H27C26-H28)
12668541
1228848477
38717
53878
12664233
1228430601
68831
164996
120591 sof
H10-C9-C20-C8and120575 m
ofC 32-H33
12532129
1215616513
5916
571932
8212536896
1216078912
1207089
570914
scis
sof
(C32-H33C34-H35)a
nd120591 m
ofC 2
-C1-C20-C9
12522694
1214701318
07185
48164
12519233
1214365601
060
0887087
120575 mof
CHon
furanrin
gtw
ist so
f(C 48-H49C48-H50)tw
ist m
of(C26-H27C26-H28)a
nd120591 m
ofH52-C51-C6-C42
12459092
120853
1924
1779
705
57457
1246
65
12092505
2548417
9140
4] m
ofC 62C 63120591
mof
H66-C64-C67-H68twist so
f(C 29-H30
C 29H31)
12370891
11999
76427
128957
80876
12365792
11994
81824
1176
25188578
twist so
f(C 29-H30C29-H31)120591 m
ofH21-C20-C8-C16androck w
of(C32-H33C34-H35)
12200711
1183468967
149312
31637
12193148
1182735356
195929
78591
twist so
f(C 26-H27C26-H28)a
ndof
(C48-H49C48-H50)120575 s
ofC 51-H52120575
mof
C 55-H56and120591 m
ofC 6
-C5-C4-C36
12019071
1165849887
34760
67455
11991
897
11632140
09804
22135718
120575 sof
C 40-H41120575
mof
C 46-H47and120591 m
ofH13-C12-C4-C3
118540
6114
984382
154074
03306
118010
07114
4697679
187873
14104
twist so
f(C 48-H49C48-H50)120591 m
ofH52-C51-C14-C57scis s
of(C55-H56C53-H54)
11796
911
1144300367
19628
1119
11782209
1142874273
28925
17435
twist m
of(C48-H49C48-H50)120591 m
ofH28-C26-C40-H41120575
mof
C 51-H52and120591 m
ofC 42-C6-C5-C4
11667314
11317
29458
146259
51602
1164
8183
1129873751
93342
93366
120591 mC 1
-C20-C8-C32tw
ist so
f(C 29-H30C29-H31)120591 m
C 3-C4-C12-C9
11575523
1122825731
1552
9047107
115618
741121501778
2817
22116347
Scis
mof
(C32-H33C34-H35)120575 s
ofC 9
-H10and120591 m
C 12-C4-C5-C6
11485582
111410
1454
1465450
35872
11495
402
1115053994
2000358
66811
] mof
C 62-O60and120573 s
C 63-C64-C67-H68
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
18 Advances in Condensed Matter PhysicsTa
ble9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns
1144341
111001077
178416
35877
11444015
1110069455
270332
78819
twist m
of(C26-H27C26-H28)120591 m
C 4-C5-C6-C4120591
mC 10-C9-C20-C8
11369705
1102861385
16907
96148
113433
71100306
8920658
196536
120591 sH28-C26-C40-H41120591
mH37-C36-C46-C47scis s
(C32-H33
C 34-H35)
11228634
108917
7498
21546
840892
11205923
1086974531
356177
102656
120591 mH33-C32-C8-C20120591
mC 9
-C12-C4-C36120591
mC 41-C40-C26-C28and
120591 mC 42-C6-C51-C48
10994941
1066509277
480338
20757
10962182
106333
1654
6216
955261
] mC 12-O60120575
mof
C 46-H47120575
mof
C 51-H52120591
mC 9
-C20-C1-C22
andtw
ist m
of(C48-H49C48-H50)
10914985
1058753545
281743
16861
10852223
1052665631
299371
30875
] mC 57-O15andscis
sof
(C53-H54C55-H56)
10807072
1048285984
924087
07097
1080906
41048479208
1443970
19949
] mC 12-O60sym120575 s
CH3scis s
of(C32-H33C34-H35)a
nd120591 m
C 2-C1-C3-C40
10717177
1039566169
1231938
67128
10730176
1040
827072
1975919
159455
] mC 62-O60120575
sof
C 46-H47andasym120575 s
ofCH3(C71)
10683452
1036294844
98016
18104
106710
281035089716
2418
7757115
120591 sC 67C 64C 63C 71
10509373
1019409181
133402
07713
1048853
101738741
376705
18533
120575 mof
C 46-H47120575
mof
C 64-H66120591
mC 67-C64-C63-C71
10455983
1014230351
692901
6619
1044
7341
101339
2077
622356
129459
twist m
of(C71-H73C71-H74)120575 m
ofC 26-H27120575
mof
C 53-H54120575
mof
C 48-H50
102714
079963264
7917
797
5289
10272885
996469845
302585
38663
twist s(
C 34H35C32H33)
10224549
9917
81253
09472
27037
102074
06990118
382
63182
41772
] mof
C 48-C51asym120575 s
ofCH3120573
mH66-C64-C63-C62and120591 m
H13-C12-C4-C5
10177638
9872
30886
300425
39798
101531
61984856617
4353
1988798
asym120575 s
ofCH3rock s
of(C29-H30C29-H31)120591 m
C 9-C20-C1-C3
10115509
9812
04373
48801
66943
1009814
9795
1958
63114
137312
120573 sC 51-C14-C53-H54asym120575 m
ofCH3(C42)120573 s
H58-C57-O15-C55
10020581
9719
96357
1216
2625574
9987131
968751707
275923
62284
] mof
C 46-C48120591
mH47-C46-C48-C49120573
mC 1
-C3-C40-C26
9946222
964783534
147581
17537
9931115
963318155
228186
43633
asym120575 m
ofCH3grou
ps120591
mC 3
-C4-C5-C46120591
mC 48-C51-C6-C26
9847888
955245136
99824
21081
9828653
953379341
230630
44849
120591 mC 32-C8-C29-H31asym120575 m
ofCH3grou
ps120591
mH13-C12-C9-H10
9355082
9074
42954
215974
15821
933456
90545232
3516
8943679
rock so
f(C 26-H27C26-H28)asym120575 m
ofCH3120591
mC 40-C3-C1-C22
8944122
8675
79834
67651
61001
8922404
865473188
1614
90132213
twist s(
C 67-H69C67-H70)a
nd120575 s
C 64-H66
8887652
862102244
7164
628098
8863304
8597
40488
95352
61863
120575 sC 64-H66rock m
(C48-H49C48-H50)tw
ist s(
C 67-H69
C 67-H70)
8665271
840531287
11709
06223
8709888
844859136
18110
23985
twist so
f(C 53-H54C55-H56)
8634892
8375
84524
112475
67108
8629942
837104374
104041
1315
53120591 m
H52-C51-C48-H49rock m
(C26-H27C26-H28)rock m
(C22-H23C22-H24)120591 m
H45-C42-C6-H5
84304
888177
57336
1744
6125204
8430694
8177
77318
322094
51332
wagg s
(C34-H35C32-H33)a
nd120591 w
O7=C2-C1-C22
8348182
8097
73654
87574
31907
8313
156
806376132
1517
066936
120591 sH47-C46-C5-C4120591
sC 48-C51-C6-H42
8137477
7893
35269
10138
60149
8100882
785785554
07347
130197
120591 mC 26-C40-C3-C4
8012
001
777164
097
326376
09129
8028851
778798547
5115
8032321
Sym120575 s
CHgrou
pson
furanrin
g7727524
7495
69828
4017
7944199
7696
1974653043
624072
83682
120591 sof
C 71-C63-C62-O60120591
mof
H66-C64-C67-H69
7654691
742505027
71326
7398
7650018
742051746
117201
1419
92Sym120575 m
CHon
furanrin
gand120591 m
C 42-C6-C51-C48
7513
513
728810761
260
4524905
7509877
728458069
50319
44818
120591 mC 5
-C4-C12-C9and120591 m
C 34-C32-C8-C29
7389121
716744737
11644
802055
7391
239
716950183
1619
6300788
Asym120575 s
CHon
furanrin
g7221832
700517704
123489
26117
72344
58701742426
188683
44984
120591 mC 1
-C2-C34-C32120591
mC 4
-C12-O60-C62
6869578
666349066
54224
14738
6858912
6653144
64107183
28493
120591 mH58-C57-C14-C53and120591 m
C 48-C51-C6-C42
668865
64879905
128788
09188
6676
324
6476
03428
184726
18119
120591 mC 9
-C12-C4-C36
6464378
6270
4466
6118100
05746
6467719
6273
68743
219688
1442
120573 mC 67-C64-C63-C71
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 19
Table9Con
tinued
Gas
phase
Chloroform
solutio
nVibrationalfrequ
encies
Vibrationalfrequ
encies
Exp[1]
Unscaled
Scaled
IRRa
man
Unscaled
Scaled
IRRa
man
Approxim
ated
escriptio
ns6195
628
600975916
1453
592821
6179
459
5994
07523
1931
5845248
120591 sC 53-C55-O15-C57
6168961
598389217
44856
16795
6156735
5972
03295
1037
4528885
120591 sC 57-C14-C51-C48
5907602
573037394
22255
80984
5908644
573138468
48686
1574
35120591 m
O60-C62-C63-C71120591
mC 26-C6-C5-C46
5459651
5295
86147
09299
37502
5495
733
533086101
38923
77962
120591 mC 62-C63-C64-C67120575
mof
CH3(C71)
5383894
522237718
171612
04714
5366383
520539151
2519
7711212
120591 mC 4
-C5-C6-C51
5089443
493675971
12889
2069
5075983
492370351
14410
41594
120591 mC 3
-C4-C5-C46rock m
(C26-H27C26-H28)
475643
4613
7371
12962
45398
47440
5946
0173723
24947
107229
120575 sC 16-C8-C29
4615
318
4476
85846
23465
0597
4614
543
4476
10671
40236
09512
120591 mC 48-C46-C5-C4
4510
159
4374
85423
29275
40628
448867
43540
099
49702
88493
120575 sC 32-H33120591
mC 29-C8-C32-C34
4371112
423997864
14877
16801
4373
603
424239491
49702
2869
120591 mO60-C62-C63-C64androck m
(C26-H27C26-H28)
4162717
403783549
70349
29785
413098
40070506
93286
59324
120591 mC 62-C63-C64-C67
3764872
365192584
06057
15014
3759518
364673246
08549
27432
120575 sC 36-C4-C12
3594
3634865292
10513
02212
3576
319
346902943
040
9934574
120591 mC 22-C1-C3-C40
3471844
336768868
02931
13363
3460298
33564
8906
06318
18682
Asym120575 m
ofCH3grou
ps3094
3730015389
14908
0891
3062399
2970
52703
15054
11169
120573 mC 67-C64-C63-C71
2310
043
224074171
35498
08619
2299752
223075944
78008
16674
120573 mO60-C62-C63-C64
427727
41489519
03353
15162
3952
7538341675
05007
42131
twist m
of(C14-C57C14-C53)
120575=bend
ing120591=ou
tofp
lane
deform
ation120573=in
planed
eformation
w=weakm
=mediums
=str
ongwagg=wagging
twist=
twistingrock=
rockingscis
=sciss
oring]=str
etchingsym
=symmetric
alandasym
=anti-symmetric
al
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
20 Advances in Condensed Matter Physics
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000
Gas phaseGas phase
Chloroform solutionChloroform solution
050
100150200250300350400450500550600650700750800
0 500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
0
10
20
30
40
50
60
70
80
90
10005001000150020002500300035004000
Tran
smitt
ance
()
Tran
smitt
ance
()
Wavelength (cmlowastlowast-1)
Wavelength (cmlowastlowast-1) Wavenumber (cmlowastlowast-1)
wavenumber (cmlowastlowast-1)
Ram
an sc
atte
ring
act
iviti
es (A
lowastlowast
4am
u)Ra
man
scat
teri
ng a
ctiv
ities
(Alowastlowast
4am
u)
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Hindawiwwwhindawicom Volume 2018
Active and Passive Electronic Components
Hindawiwwwhindawicom Volume 2018
Shock and Vibration
Hindawiwwwhindawicom Volume 2018
High Energy PhysicsAdvances in
Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom
The Scientific World Journal
Volume 2018
Acoustics and VibrationAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Advances in Condensed Matter Physics
OpticsInternational Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
AstronomyAdvances in
Antennas andPropagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal of
Geophysics
Advances inOpticalTechnologies
Hindawiwwwhindawicom
Volume 2018
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom