Naval Research Laboratory Washington, DC 20375-5320

NRL/MR/6394--19-9918

IR Absorption Spectra for Nitrosamines Calculated Using Density Functional Theory

Samuel G. Lambrakos

Center for Computational Materials Science

Materials Science and Technology Division

L. Massa

Hunter College

New York City, NY

S. Wallace

Lehman CollegeThe Bronx, NY

September 27, 2019

DISTRIBUTION STATEMENT A: Approved for public release, distribution is unlimited.

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IR Absorption Spectra for Nitrosamines Calculated Using Density Functional Theory

Samuel G. Lambrakos, L. Massa*, and S. Wallace**

Naval Research Laboratory4555 Overlook Avenue, SWWashington, DC 20375-5320 NRL/MR/6394--19-9918

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*Hunter College, 695 Park Ave, New York, NY 10065-5024**Lehman College, 250 Bedford Park Blvd W, The Bronx, NY 10468-1527

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Samuel G. Lambrakos

(202) 767-2601

27-09-2019 NRL Memorandum Report

Density functional theory Absorption spectra Spectral signature features

1G69

Office of Naval ResearchOne Liberty Center875 North Randolph Street, Suite 1425Arlington, VA 22203-1995

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Vibration absorption spectra for nitrosamines are calculated using density function theory (DFT). Absorption spectra within the IR range of fre-quencies for electromagnetic-wave excitation, calculated using DFT, can be interpreted with respect to molecular structure. DFT calculated ab-sorption spectra corresponding to vibration excitation states of these molecules in continuous solvent backgrounds can be correlated with addi-tional information obtained from laboratory measurements. The DFT software GAUSSIAN was used for the calculations of excitation states pre-sented here. This study provides proof of concept for using DFT-calculated spectra to construct templates, which are for spectral-feature com-parison and thus detection of spectral-signature features associated with target materials.

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Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2. DFT Calculation of IR Spectra....................................................................................................2

3. Discussion.......……………………………………………………………………….……........3

4. Conclusion....................................................................................................................................3

5. Acknowledgement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

6. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

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1

Introduction Identification of unknown materials using infrared (IR) spectroscopy is by comparison of measured spectra

with reference spectra of known materials. Such comparison entails correlation of measured spectra with spectra

within a database of known molecular structures [1] using signal processing algorithms [2]. Specifically, signature

structure within a measured spectrum is filtered using spectral templates having patterns associated with known

materials. References [3-7] describes algorithms for signal processing of measured spectra for correlation with

reference spectra within a database. For detection in practice, measured spectra can be correlated with different

databases, providing complementary information, which includes different types of information concerning

interpretation of spectral features. Typically, databases of spectra consist of spectroscopic measurements, which

are obtained using different types of spectroscopies, based on transmission and reflection [8,9]. Presented in this

report are calculations of IR absorption spectra of molecular structures using density functional theory (DFT)

and associated software technology (see reference [10] for the case of pure water), which provides complementary

information to that obtained from laboratory measurement.

This report presents DFT calculated IR spectra for N-nitrosodimethylamine (C2H6N2O), N-

nitrosodiethylamine (C4H10N2O), N-nitrosodipropylamine (C6H14N2O), N-nitrsopyrrolidine (C4H8N2O), N-

nitrosomethylethylamine (C3H8N2O) and N-nitrosodibutylamine (C8H18N2O) of isolated molecules and

molecules within different solvent backgrounds. The properties of these molecules are of major importance for

monitoring and detection of nitrosamines, which are among toxic and carcinogenic contaminants commonly

found in the environment [11-16]. The detection of these nitrosamines, especially in the presence of water, is of

particular interest. Specifically, IR spectral signatures, i.e., fingerprint spectra, can be correlated with the presence

of target molecules (see references [17-19]). A previous study [17] introduced and demonstrated the concept of

using DFT calculated IR spectra. The concept of database enhancement using DFT calculated spectra is

independent of specific types of detection technology. Methodologies for comparison of detected spectral features

with database spectra represent a separate problem.

Given in reference [17] is a description of the formalism underlying DFT calculation of IR spectra, and

implementation of this formalism in terms of the DFT software GAUSSIAN16. The commercial computer

program GAUSSIAN16 (G16) is designed to compute the IR spectrum of a molecule, including the effect of a

continuous solvent background [20, 22]. Second derivatives of the energy with respect to the Cartesian nuclear

coordinates are calculated and subsequently changed to mass-weighted coordinates at the equilibrium geometry

of the molecule. The IR spectrum is obtained from the ground state energy surface calculated in the Born-

Oppenheimer approximation by solving the DFT Kohn-Sham equations [23-29]. The electronic density, the

___________Manuscript approved August 28, 2019.

2

potential energy V, and the equilibrium geometry are calculated. The details followed by Gaussian for IR analysis

are given in references [22] and [28].

DFT Calculation of IR Spectra

Results of a computational investigation using DFT concerning C2H6N2O, C4H10N2O, C6H14N2O, C4H8N2O,

C3H8N2O and C8H18N2O molecules in different solvent backgrounds are presented. These results include the

ground-state energies for energy-minimized configuration of these molecules within different backgrounds, and

their ground-state oscillation frequencies and IR intensities. For example, graphical representations of molecular

geometries for stable molecules of C2H6N2O, C4H10N2O, C6H14N2O, C4H8N2O, C3H8N2O and C8H18N2O within

a water background, are shown in Fig. (1). For these calculations, geometry-energy optimization and vibration

analysis was effected using the computer program Gaussian 16 with the DFT chemical model B3LYP [29,30]

and basis functions 6-311++g(3df,3pd) [31,32]. These basis functions designate the 6-311G basis set

supplemented by diffuse functions, indicated by the sign ++, and polarization functions (df), having a set of d and

f functions on heavy atoms [33]. Graphical representations of molecular geometries for stable molecules of

C2H6N2O, C4H10N2O, C6H14N2O, C4H8N2O, C3H8N2O and C8H18N2O within a water background are shown in

Fig. (1). Shown in Figs. (2) through (7) are IR spectra of these molecules. Values of the IR intensities as a function

of frequency for these molecules within different backgrounds are given in Tables 1 through 6.

3

Figure 1. Molecular geometries for C2H6N2O, C4H10N2O, C6H14N2O, C4H8N2O, C3H8N2O and C8H18N2O in water

background.

Discussion

The DFT calculated IR spectra calculated here should provide reasonable templates for filtering of IR

spectral measurements associated with different types of detector schemes and complex spectral-signature

backgrounds. In principle, these templates can be linear combinations of spectra given in the tables below, having

adjustable weight coefficients of the component spectra, as well as correlation-lag parameters for adjustment of

absorption-maxima frequencies. The DFT calculated IR spectra given here are to be adopted as complementary

database information concerning spectral features to that obtained from laboratory measurement.

Conclusion

The DFT calculated absorption spectra given here provide information concerning molecular level dielectric

response structure. The calculations of IR spectra associated with C2H6N2O, C4H10N2O, C6H14N2O and C4H8N2O

molecules within different backgrounds using DFT are meant to serve as reasonable estimates of molecular level

response characteristics, providing interpretation of dielectric response features for comparison with experimental

4

measurements. Specifically, the DFT calculated IR spectra calculated here should provide reasonable templates

for filtering of IR spectral measurements associated with different types of detector schemes.

Figure 2. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosodimethylamine (C2H6N2O)

Figure 2A. N-nitrosodimethylamine (C2H6N2O), Isolated Molecule (Energy: -265.141096 au)

Figure 2B. N-nitrosodimethylamine (C2H6N2O), DMSO Background (Energy: -265.1486773 au)

Figure 2C. N-nitrosodimethylamine (C2H6N2O), Toluene Background (Energy: -265.1445304 au)

5

Figure 2D. N-nitrosodimethylamine (C2H6N2O), Water Background (Energy: -265.1488006 au)

Figure 3. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosodiethylamine (C4H10N2O)

Figure 3A. N-nitrosodiethylamine (C4H10N2O), Isolated Molecule (Energy: -343.7956752 au)

Figure 3B. N-nitrosodiethylamine (C4H10N2O), DMSO Background (Energy: -343.8050967 au)

6

Figure 3C. N-nitrosodiethylamine (C4H10N2O), Toluene Background (Energy: -343.8013687 au)

Figure 3D. N-nitrosodiethylamine (C4H10N2O), Water Background (Energy: -343.8052031 au)

Figure 4. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosodipropylamine (C6H14N2O)

Figure 4A. N-nitrosodipropylamine (C6H14N2O), Isolated Molecule (Energy: -304.4705191 au)

7

Figure 4B. N-nitrosodipropylamine (C6H14N2O), DMSO Background (Energy: -304.4776376 au)

Figure 4C. N-nitrosodipropylamine (C6H14N2O), Toluene Background (Energy: -304.4737994 au)

8

Figure 4D. N-nitrosodipropylamine (C6H14N2O), Water Background (Energy: -304.4777479 au)

Figure 5. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosopyrrolidine (C4H8N2O)

Figure 5A. N-nitrosopyrrolidine (C4H8N2O), Isolated Molecule (Energy: -422.4501449 au)

Figure 5B. N-nitrosopyrrolidine (C4H8N2O), DMSO Background (Energy: -422.4596433 au)

9

Figure 5C. N-nitrosopyrrolidine (C4H8N2O), Toluene Background (Energy: -422.4560395 au)

Figure 5D. N-nitrosopyrrolidine (C4H8N2O), Water Background (Energy: -422.4597461 au)

Figure 6. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosomethylethylamine (C3H8N2O)

Figure 6A. N-nitrosomethylethylamine (C3H8N2O), Isolated Molecule (Energy: -342.5843252 au)

10

Figure 6B. N-nitrosomethylethylamine (C3H8N2O), DMSO Background (Energy: -342.5913857 au)

Figure 6C. N-nitrosomethylethylamine (C3H8N2O), Toluene Background (Energy: -342.5876242 au)

Figure 6D. N-nitrosomethylethylamine (C3H8N2O), Water Background (Energy: -342.5914929 au)

Figure 7. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosodibutylamine (C8H18N2O)

Figure 7A. N-nitrosodibutylamine (C8H18N2O), Isolated Molecule (Energy: -501.106478 au)

11

Figure 7B. N-nitrosodibutylamine (C8H18N2O), DMSO Background (Energy: -501.11395 au)

Figure 7C. N-nitrosodibutylamine (C8H18N2O), Toluene Background (Energy: -501.109886 au)

Figure 7D. N-nitrosodibutylamine (C8H18N2O), Water Background (Energy: -501.11408 au)

Table 1. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosodimethylamine (C2H6N2O)

N-nitrosodimethylamine(DMSO)Frequency(1/cm)Intensity169.05350000001772.10391699972233.92610000005.36862838363247.131400000089.62977249954286.7431000000389.24238370645381.706800000037.14766193096396.3352000000528.89295917547550.9504000000316.83590813348641.7004000000274.67577662659821.8648000000123.788745280310993.8067000000398.0856256907111046.2209000000105.0431354358

12

121106.024100000032.5604923343131170.686200000046.2311418441141214.196500000033.8620054485151270.560700000046.2619254690161328.3584000000442.7066375197171436.72320000000.9499205199181455.19270000004.2161386974191470.969200000028.0516649444201482.916600000016.9654428278211486.004600000048.2817607167221501.612300000048.4656272387231503.058100000039.8242192650242987.245400000093.5844825716253009.220200000087.9044266317263086.955100000036.7723885694273094.228700000036.9173775895283124.961800000025.2540240139293132.939800000028.8431461107303470.201600000012.4258485817

N-nitrosodimethylamineFrequency(1/cm)Intensity177.7663000000892.10904529182221.769100000011.50214657833233.024400000057.75460472804282.3006000000182.57212975365366.5726000000290.69383498286391.547600000090.77501232667539.6638000000229.08675647708645.5613000000127.35196723869829.265300000039.6594349111101007.5937000000165.4608559988111034.696000000065.7780801200121105.48800000008.3928016613131185.793200000010.3644856089141213.458800000017.3622759881151260.112300000017.3725939097161350.6272000000115.8532408409171433.92820000000.2286923891181448.80210000003.3001696909191467.66880000000.5189017868201478.364800000019.7067539084211491.973700000043.4605982055221499.43090000004.8476272263231514.393000000029.7799460233242996.146900000050.5692577180253004.518100000059.2684516654263082.375800000023.5880279342273088.971700000025.5658270175

13

283116.353900000021.7513960682293125.994000000023.4681920845303457.55430000001.8519974537

N-nitrosodimethylamine(Toluene)Frequency(1/cm)Intensity166.87520000001428.45949284042226.78880000007.89651204503236.647800000078.96264998414282.5264000000239.94724388005364.2840000000330.79613085096391.8402000000143.37754973337551.5970000000270.79809394378646.2829000000173.44430437669825.288500000060.4358863579101001.2463000000226.0471641039111037.348100000083.9438281053121104.520800000013.5564719513131181.326400000012.4393607953141211.866400000023.2506775213151262.235800000023.8165516098161344.0983000000198.6117520148171433.96390000000.2359200947181453.56620000002.9358541730191471.20290000003.2515477077201475.303300000022.1462032860211488.611300000051.4043057340221496.63150000009.5166689875231510.169100000039.8760342445242993.230300000065.2356899714253007.962000000071.2555429674263084.360300000030.7128314345273091.760800000029.3150490265283120.133800000024.5383448162293128.899900000025.6155811939303464.32310000005.6900037619

N-nitrosodimethylamine(Water)Frequency(1/cm)Intensity169.60350000001761.51696275792234.19080000005.11044506733247.500400000090.37300294384286.7813000000394.64223293045381.952100000030.41409191416397.3553000000532.82417851577550.8179000000322.27605172538641.5006000000278.70345677089821.7755000000126.072696915410993.7633000000404.7509140982

14

111046.4333000000105.5673653178121105.971700000033.4129599114131170.309500000048.5377856338141214.317600000034.2745474568151270.815400000047.4367757149161327.8409000000451.7229969785171436.73360000001.0187761353181455.15410000004.2200887253191470.831400000028.2696529971201482.931900000017.5867061691211485.950400000048.0123625823221501.629400000057.2061903555231503.371100000032.4640335697242987.218200000094.5492907460253009.113200000088.5498888269263087.077000000037.0363728079273094.277500000037.1654979308283125.160100000025.2092744649293133.054000000028.9276622466303470.470500000012.7402008849

Table 2. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosodiethylamine (C4H10N2O)

N-nitrosodiethylamine(DMSO)Frequency(1/cm)Intensity150.44760000002044.7563526914287.1865000000439.3821118070395.249100000037.12164116724195.1960000000189.89879864875220.498300000011.50692201986271.8330000000133.74746342387272.4002000000101.82182462708320.5443000000643.11399472799371.0471000000433.906400976310438.8745000000111.857785429111526.1247000000181.225849373412677.6047000000155.573644249813754.634600000063.205207290814811.209200000047.671577928115818.461900000026.074862333416928.246800000024.536436507117999.533500000047.1543340872181043.7071000000184.6772260021191066.6865000000107.1776562698201099.168200000013.7139502937211137.6449000000138.0643121771221184.985700000046.9657055164231203.310500000064.2893090824

15

241310.649300000044.8417455621251319.525500000035.4908920570261340.5865000000295.0939892196271387.311500000032.8362671114281403.81920000005.8319770347291410.672600000016.7613374102301414.576600000036.0154405497311466.33420000002.1691825394321481.18250000007.7461804401331482.106500000015.1809619426341486.04820000007.3339712299351490.111400000031.9122577519361502.003900000027.8327475104371508.319400000024.8959211593382986.136000000078.1768712201392992.6448000000108.4802306714403034.635900000042.2118369039413035.594800000036.1246361768423083.32460000003.0364359977433089.546100000012.0882296136443099.353800000051.7041023531453102.094900000035.1681243082463105.740200000079.6791436024473111.760000000092.7560278843483492.761400000016.1493112116

N-nitrosodiethylamineFrequency(1/cm)Intensity152.8251000000759.0073780229278.9556000000249.7857652249397.2489000000128.54004311944199.240100000080.55278893365223.14630000003.16439635806266.493600000086.26137593007280.169300000071.61340061748305.5157000000381.70760366119375.5543000000302.807251412610438.275900000080.911940285411511.627500000090.540261926512672.615200000089.545297578813760.865600000024.253633667714811.049900000021.450422597215822.555800000023.364400340316932.46470000007.606453766717995.899800000034.4232307702181049.1654000000103.9167346579191069.476900000063.1233658883201102.43220000009.5382316076

16

211140.460800000079.4541772621221191.029100000016.1226668802231206.462200000035.7840152769241313.347800000028.5122331294251325.34370000007.8192982051261353.2454000000115.0253381251271388.207900000020.6483619831281406.55870000003.2892364603291417.076900000020.9864135285301419.356900000026.3374556150311451.36580000003.6470009590321491.81740000005.4630948395331494.323100000012.4344041189341496.55450000008.7886169688351502.701700000016.2849104145361510.215300000014.0216572933371516.501300000014.0077316465382985.837900000045.6609048452392997.389400000047.7012445490403038.391700000030.5032700078413039.114500000024.1725533147423080.21810000003.0473988618433088.15360000006.9670171503443101.029900000028.7691828053453102.606600000027.2488660753463108.309500000045.9819544330473112.825700000051.0909837241483470.07540000003.3860855442

N-nitrosodiethylamine(Toluene)Frequency(1/cm)Intensity152.7051000000919.8039520200280.0352000000443.8296318368397.1104000000162.94799289854197.4599000000115.11799317375222.84650000003.27427526866266.5740000000134.77875916107276.894400000094.58189505738305.4915000000519.94720986999371.4534000000330.414022150010438.341000000086.816566773811516.0398000000115.505793327112676.1964000000113.779847796413758.479600000035.911853921714810.338700000031.137278409415821.466400000025.041716533516930.621500000011.626256943917997.686900000037.2969769048

17

181047.5468000000132.9904749373191067.494000000082.5722079146201100.818200000012.2231259765211139.0212000000102.9518564235221188.406900000024.6042742357231204.470000000043.5002538003241310.948200000033.8071424079251322.444900000011.9705008544261351.7066000000175.5913607515271387.606400000024.6455416277281405.15470000004.0062767928291414.102900000017.7159800924301416.897500000033.0211978321311455.55890000002.0736900922321487.04230000009.8294131362331489.303400000011.5960933987341491.57560000008.4384249669351496.895400000020.0299333315361505.341900000020.0002300241371512.136400000016.7204518547382989.115400000040.6611872709392992.796200000081.2560821420403034.624400000035.8484162456413035.623000000029.3593557885423080.45470000003.0485893752433088.25390000008.2977294162443099.258100000037.3863837465453101.047200000027.7235099209463105.750600000059.6333067861473111.522900000067.0313836476483485.51680000008.6555370855

N-nitrosodiethylamine(Water)Frequency(1/cm)Intensity150.71910000002039.1358044940287.2794000000446.8859707657395.167700000034.49568621314195.0909000000192.77806431445220.698500000012.08757666426272.1999000000134.76752148547272.364600000095.76237599378321.6118000000638.52949199829371.3636000000444.073979407310438.9645000000114.573126270111526.6341000000185.143474466812677.6155000000157.176660229213754.506200000064.420968294614811.152600000048.4947655221

18

15818.316600000025.944451157216928.194600000025.136960146117999.601500000047.8208140677181043.5636000000186.6874497294191066.6795000000107.7191657926201099.127700000013.7503886886211137.6353000000139.2581213633221184.859900000048.0791012084231203.259100000065.3483714911241310.596000000046.0441057080251319.410900000037.1953657511261340.1700000000298.8715536344271387.299200000033.1183726808281403.74130000005.8928347408291410.536700000016.6359623828301414.499900000036.0729545254311466.82860000002.2584749147321480.96010000007.7872118169331481.878700000015.1507209482341485.88360000007.3487449565351489.961300000032.4954229024361501.922400000027.8063677828371508.214800000025.2589701080382985.907400000080.1447495168392992.6563000000109.1736727556403034.659700000042.4432717890413035.608600000036.3612908268423083.41690000003.0561406043433089.616800000012.2542630669443099.359900000052.2384328139453102.121100000035.8598359676463105.772100000079.9388239657473111.796700000093.6537608139483492.930500000016.3926035917

Table 3. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosodipropylamine (C6H14N2O)

N-nitrosodipropylamine(DMSO)Frequency(1/cm)Intensity145.177200000067.9069662839255.67450000001639.0820175386372.4464000000313.1818807820484.8317000000223.66136731175132.5788000000165.59248392366155.1423000000178.69221638227205.910500000046.93066799088236.7454000000199.17548276039249.5253000000919.5899677498

19

10259.8264000000183.168127527911317.6261000000183.173151506312355.135400000095.091193256413364.9985000000230.144363114614446.6086000000100.971972641015581.579500000023.245781349116642.1784000000151.971831235417752.28530000001.578714358318766.6110000000100.932491506419846.532800000041.530067764120874.092400000052.582823434021893.54680000006.313052564622908.47260000006.785912745623936.62860000000.9557905616241025.7390000000108.0942851309251031.389500000061.8885069208261059.5943000000159.1690022080271080.424200000092.3448746756281107.367700000040.6369119150291150.953400000043.0459889305301175.921400000010.8066971686311190.28070000005.2785044387321272.84970000001.9849047147331292.10580000004.7557009716341307.64200000006.5223759194351332.30390000008.2847950187361337.842200000071.9852094730371354.6082000000219.6587901858381383.43330000004.6741785372391383.752600000045.9727633899401404.741400000010.4887927423411409.970700000017.7333813935421430.93690000003.8128165387431461.20320000002.6300151212441477.15840000006.8501167878451477.69670000005.4958614161461483.87450000004.3836001316471488.088500000013.8068371115481491.397600000027.5042563437491495.033600000018.7825680894501498.274400000032.3409515016511507.150600000041.3045336807522979.184400000070.8733709995532991.3410000000113.7368770022543022.620700000056.1825946723553023.881000000055.8937361888563027.612800000070.6544380210573030.174300000055.0095723668583054.148100000013.4687228905

20

593055.148400000012.5454251185603073.98820000006.3668379348613079.70700000000.4691874054623084.522400000081.0478769858633087.9478000000214.6025894473643091.374800000070.2826981763653096.829900000083.3292665417663500.259700000020.7590557591

N-nitrosodipropylamineFrequency(1/cm)Intensity142.565000000057.4720658515260.4133000000385.7373450307376.0291000000188.6839919816487.7779000000190.89391453795137.896200000069.76864307496154.559900000085.34259888077205.79210000003.94108661378237.784800000014.47884790119263.2244000000122.732315505010278.2028000000322.647512536011327.0358000000116.960718761712359.742800000012.700898634113386.8558000000411.162158302114451.6097000000118.757110016115584.591700000021.906511124916639.476100000089.864300892717756.30030000002.071447488818773.222300000048.875415942319849.022100000021.772427092520876.046500000031.135685004221896.34480000003.986527558622910.90640000004.515796194423940.24280000000.5498855216241024.438700000063.4494281070251034.416700000029.5135050598261064.0582000000112.5975820341271080.948600000062.8516819826281110.506500000017.9189533867291154.349400000022.6338415588301180.72590000008.3553522621311194.54230000002.1520943057321276.65190000001.8527475781331294.84710000001.6566426875341312.32620000003.4840791528351332.75290000007.5450408514361341.928300000040.5551939334371356.841600000079.6079130561

21

381385.325100000033.4382794759391386.77020000006.5739593542401412.23870000008.1415714169411417.514800000014.9732411709421435.35110000007.4212434755431454.73660000005.5782148070441485.30690000003.0721413474451490.27270000006.1516494364461495.60930000002.8546580265471498.78440000005.7025446624481503.131600000020.9288342435491503.754100000019.0569976246501509.683200000018.0805190919511515.094700000021.7130776072522984.956400000024.2339718381532995.537000000055.2730141702543027.379400000018.9905516327553029.040500000034.7539168444563030.665900000056.6747750214573032.863100000036.9749515206583052.86240000007.9196962549593055.40850000005.6093481939603069.07460000001.8166980366613076.561400000016.8741723303623088.318100000054.2367817647633091.464800000097.6110776094643095.789000000041.8688473734653103.652100000046.1827081153663475.70230000003.6924599157

N-nitrosodipropylamine(Toluene)Frequency(1/cm)Intensity146.758000000075.0304989451258.9419000000678.1824638156375.6147000000284.8962833469487.3399000000167.30914187305136.5078000000103.29757006136156.3042000000116.81499281597207.885000000012.21085486118237.709000000027.32054747729262.8558000000150.300664273610270.5545000000584.906265648611322.8859000000160.364963649512358.016900000034.650403769513375.8681000000380.240200476314449.7001000000112.662083252015583.607500000022.825950289116642.3746000000112.0317263133

22

17754.15660000001.573739095018769.463600000067.154144479719848.405600000028.056789630120875.184000000039.132090876721894.65660000005.211394781222909.61450000005.214729430323938.44330000000.7188576013241025.122900000080.9376983906251032.905100000043.1342531989261061.6079000000134.9560706811271080.877000000074.9202554164281109.000300000025.2799662881291152.808000000030.0192457440301178.06180000009.6099473976311192.53350000003.4041901462321273.97460000001.9436957090331292.84030000002.5161302880341309.19000000005.0129909757351331.92930000007.6212916654361339.657600000047.3317063142371357.8853000000134.5283786516381383.934800000042.6998055122391384.49690000003.3488537628401408.94750000008.1379377547411413.915000000016.7355970565421432.62120000006.1034704859431457.74750000003.7777215635441482.89350000007.0953421072451483.84410000004.0457384983461490.06120000001.3919479992471493.110900000010.1416148622481497.161300000023.1687871005491499.528500000018.8928097498501503.763600000022.6407363853511510.827000000028.3704775580522983.196500000034.5058138539532993.646100000075.6638545905543023.480400000036.5248291558553024.683700000042.8510042572563027.557600000059.8443026081573030.831300000043.5568776648583053.02880000008.4565802737593055.21540000008.1543801447603070.04440000002.7755148744613077.30900000007.5077924047623085.530200000064.2255017202633088.9186000000141.0031484609643092.752300000052.0977311282653099.514400000060.6335389859

23

663490.73240000009.9109439481

N-nitrosodipropylamine(Water)Frequency(1/cm)Intensity144.942200000069.9752563723255.42910000001684.4411828205372.1736000000313.4757100909484.6635000000226.42875979595132.4076000000168.97623258516154.9842000000181.58499374377205.827700000049.67856350058236.5604000000227.51803828229248.6596000000907.081587238110259.6872000000185.209644298411317.4300000000184.011473293012354.998400000098.634081001513364.6463000000222.344014487814446.4585000000100.282131825015581.509600000023.273273089216642.1164000000153.388132557117752.20470000001.570928111218766.5273000000102.156163047819846.462900000041.993959421120874.039700000053.065247563421893.50660000006.314676060122908.43070000006.838045747123936.55710000000.9669385975241025.7531000000108.8842590930251031.351800000062.4396560894261059.5710000000159.9281591641271080.396200000092.8775154999281107.310600000041.2846257371291150.885900000043.5012216379301175.862700000010.8588063082311190.20830000005.3304439888321272.82260000001.9990512888331292.07940000004.8524393678341307.58210000006.5461671982351332.32130000008.2981612636361337.789700000072.8728179145371354.5331000000222.6945312404381383.37920000004.2841823636391383.748200000046.4434212271401404.598100000010.5767742114411409.852500000017.7331703411421430.87800000003.7438291893431461.24110000002.6116549477441476.94110000006.7989929892

24

451477.44180000005.5292120792461483.70000000004.5812059598471487.927000000013.8858217585481491.230300000027.6277277786491494.884800000018.7945787516501498.111800000032.7007644409511507.017400000041.8079784267522979.022400000072.3766862314532991.1595000000115.4605549173543022.585700000056.8470040689553023.854100000056.3913489804563027.617500000071.1085288057573030.112300000055.3522198251583054.160000000013.8807820493593055.123000000012.6038989401603074.10650000006.6055072404613079.76100000000.4978066217623084.484800000081.6284265716633087.9111000000217.1032361528643091.327800000070.9652864322653096.748500000084.0948759863663500.508800000021.1427843299

Table 4. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosopyrrolidine (C4H8N2O)

N-nitrosopyrrolidine(DMSO)Frequency(1/cm)Intensity157.07410000001779.4076384784261.2377000000532.86253398063149.6314000000140.12750553494292.5099000000310.76831244155319.1943000000637.96127888496473.817500000075.19458496257506.1980000000532.56931814238643.35960000004.16389271439733.2300000000122.453492906910760.638400000013.397320865311857.256400000017.353574599312863.885100000068.372311340613896.213100000032.260585953314972.845200000011.640396074415980.529100000024.8922058569161048.365400000093.6443388430171076.0354000000163.3856598266181115.154900000028.9132107932191133.3397000000104.1592954823201218.201100000013.0262778620211221.61110000009.4329319512

25

221250.643800000041.4655041546231274.390900000017.7937034361241314.831300000045.7722996787251326.235400000065.0938451506261336.3784000000218.5809564284271355.208700000025.5511726822281378.632300000010.9302181899291475.93260000003.5000722171301489.01710000003.9288013152311501.468700000021.5089197642321507.50210000001.5161012167331522.662900000014.7897143605342994.843200000082.7754716515353011.272600000077.0554355588363060.027100000036.1867732119373070.108000000082.8913040268383088.040000000074.4667963292393093.555500000013.8258800780403100.560700000011.1891367363413117.2777000000109.4826299804423482.305300000013.2741803778

N-nitrosopyrrolidineFrequency(1/cm)Intensity153.437600000030.6534457129292.4676000000660.09910663173142.218000000070.11137725544286.7634000000261.74232262355324.7229000000351.80145958726462.5108000000221.47582077407484.1436000000119.81699378028644.99980000001.95078500589740.900900000075.104393520110762.185300000010.482445888311858.34060000005.714008120012869.695800000029.509848530113898.510500000019.523620734414974.67150000004.574004256415984.003500000010.4117225717161053.008000000041.9281344272171083.2919000000107.7285291925181116.833500000010.7822661467191127.082400000040.7437419667201220.40430000007.8656622344211225.95740000001.5704323683221254.347800000025.3654050246231276.18890000007.7178411675241320.66430000007.4700140070

26

251329.30650000002.2286256074261352.822600000083.8632344658271357.555400000026.5469970894281384.61760000006.0960997532291457.20840000001.5120309364301493.79080000002.5969433119311510.257200000015.7197753476321515.49040000001.1408880130331533.25410000007.0126822818343003.408000000040.4400606204353007.322900000036.0807357744363057.914900000021.4615461849373067.779600000056.6502618648383081.018500000045.5631507095393089.49040000008.9060878056403096.636000000010.8436244617413115.072900000063.6885025198423472.54900000002.6214193024

N-nitrosopyrrolidine(Toluene)Frequency(1/cm)Intensity157.489900000066.4507495405282.02260000001154.60259604303146.723500000086.56992484364284.1318000000397.03049090005312.5636000000419.36563760906463.3005000000236.96116651937483.5783000000170.05115733148644.72050000002.71458506049738.334500000096.533178376410761.26990000009.453773098911857.86140000008.043794341512867.295700000043.037223466313897.613200000025.470701115314974.06050000006.853637532515983.315600000013.6922644880161051.860200000052.8775397619171081.4163000000130.9992260485181115.623200000018.1739805909191126.997300000056.7964823628201219.84110000009.9316230703211224.09410000002.5919312483221252.868900000032.4760738951231275.149800000010.4519318586241319.391700000011.5809360972251329.06570000005.0349769702261348.9921000000144.2789247453271357.181200000025.9637764771

27

281383.31660000007.7938387073291462.07770000001.3738405207301491.45740000003.2501878869311506.440400000018.0132457180321512.70330000001.0696741282331529.07800000009.6225931407343002.198300000052.4689371931353008.265400000052.7592369496363058.829300000027.1468927769373068.757400000068.0823880259383084.087200000056.9789881422393091.513700000011.1492291165403098.239200000011.6816710124413116.052400000079.8174607621423479.40710000006.9554612971

N-nitrosopyrrolidine(Water)Frequency(1/cm)Intensity156.14290000002098.2833728497261.0140000000286.74570227023150.0432000000141.45786655914292.4324000000314.11795913065319.8697000000639.40670190906473.679400000075.57360676877507.8510000000538.91754815018643.28760000004.24001799419732.9254000000123.271318878010760.622000000013.931017538811857.254700000018.145667005212863.742700000069.148907618213896.158300000032.239410022214972.794900000011.823080786615980.411100000025.7318101666161048.185600000096.1244083326171075.8690000000165.1470482804181115.202000000029.5047460812191133.7746000000106.8181739974201218.168000000012.8966176618211221.568800000010.1716556024221250.621400000041.8617984323231274.416500000018.2625887265241314.648800000050.1539007646251325.998500000074.4748528224261335.8313000000214.6602688524271355.145300000025.2382551244281378.490000000011.0120900623291476.48610000003.7489610545301488.96950000003.9139228275

28

311501.319600000021.6255838027321507.30050000001.5589161325331522.460400000015.0055030566342994.496100000084.2218907861353011.381600000077.8944072995363060.065700000036.4636130250373070.156900000083.3161907682383088.089800000075.1248345263393093.559500000014.1294297085403100.626700000011.0360454617413117.3248000000110.5444483074423482.068300000013.4660716531

Table 5. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosomethylethylamine (C3H8N2O)

N-nitrosomethylethylamine(Toluene)Frequency(1/cm)Intensity

163.95490000001001.06553561162116.0799000000311.69427902223218.5350000000104.75739334454228.96730000003.33658824325256.5086000000180.82017889556298.0064000000145.29126828727352.4814000000334.58945778948441.0434000000185.98712391799554.2950000000172.569803504110636.8499000000142.778290675311789.297800000041.434149480412819.969700000028.865816319813965.215200000067.0685175682141035.614400000124.1468876505151055.459800000110.8803674747161097.14940000014.0326216548171157.09570000020.3825141889181191.6009000009.5292155344191235.852400000049.8843985842201321.74020000008.5487074113211348.9890000000173.5644518431221395.088400000018.0775451331231413.739600000038.8044590431241444.93540000001.9784982593251466.73460000002.6690552362261481.822600000028.9276706103271486.281400000031.4412898342281492.47640000004.6868475732291502.723500000015.0268403191301507.625300000022.5703064850312995.096400000038.6094639714322999.125700000094.0250515492

29

333037.433000000032.7219233788343075.28920000008.9282749652353084.933000000035.0633618442363101.522200000038.9220394525373110.235400000040.5758989213383120.627800000035.5010506781393470.81820000006.8719848850

N-nitrosomethylethylamine(DMSO)Frequency(1/cm)Intensity169.36890000001441.71528321472113.7804000000305.09421163613214.1136000000150.88690297534230.82950000004.59724475095260.3199000000209.52006862676302.5255000000215.67040307427366.3536000000344.18573029338451.6877000000264.92369121399564.1490000000228.131847472710635.3117000000234.725213854511786.650700000069.862697105312818.169800000045.986060323213966.3029000000114.1931129491141030.1421000000174.0570217879151057.0673000000143.6891718450161096.331500000022.0900665808171151.521000000023.8649264403181189.377100000014.2106989834191239.089100000076.0780364857201320.736400000017.6544168526221337.5162000000323.2741806672231394.967500000021.4417231752241410.569000000045.2424463161251445.12080000001.3819552914261475.48330000002.1438353080271481.088400000062.2168783457281481.17760000008.5404884611291486.241900000012.4437666481301496.902500000031.1848879972311503.984100000024.1146237270322991.438200000084.2265005885333001.2157000000100.7257756142343037.069400000039.6480818942353081.38630000006.2578172401363086.984900000043.1554883437373101.464400000054.0610391788383109.395500000062.0043371375393125.068100000037.0245031538

30

403475.946200000013.1093214251

N-nitrosomethylethylamineFrequency(1/cm)Intensity168.0414000000610.46374418072116.2410000000252.58873333843220.977600000079.09195316654225.62400000001.89900578085255.9863000000139.28729061966295.8947000000103.26643725617356.0705000000280.58957564708439.3566000000156.82404747889550.6203000000140.985148896310637.6495000000106.441572949511791.689700000029.179367318812821.546900000019.938564318413964.551500000048.2714059372141039.099600000095.3025210966151056.362200000086.2879677569161098.331500000010.5984965928171160.825700000018.8509287779181193.28050000006.9986935242191235.205700000036.8090619867201321.71990000006.0638410360211353.0977000000108.9890715242221395.428300000015.4323709368231416.144700000033.3545463987241443.81340000002.4243418678251461.52450000003.8462987587261484.749500000023.8283784054271490.358600000026.0996389903281496.32760000003.4257048480291506.916900000011.7962423245301510.507000000016.1857065204312993.929500000027.3723877531322999.023000000075.1035879208333037.367000000027.6355523852343071.05800000009.9798002811353082.873500000028.8299168606363101.169100000031.4745133370373110.719300000027.1399687219383117.216500000034.2923570095393463.85460000002.4314002215N-nitrosomethylethylamine(Water)Frequency(1/cm)Intensity

31

169.50470000001453.74716265282113.9149000000302.42260853963213.9797000000152.64807884144230.76030000005.09651942825260.5621000000210.49811600926302.7589000000217.18418415837366.3889000000344.81131907668452.1165000000266.36131046189564.4908000000230.262300437510635.2806000000238.756994719211786.545900000071.166391938612818.151100000046.719503605513966.3668000000116.1089106635141029.9856000000176.0278429494151057.1188000000144.4588280006161096.304500000022.4868922877171151.382200000024.0812397821181189.307400000014.5057115574191239.193800000077.1620021475201320.665000000018.7180707914211337.1088000000328.8168525342221394.914900000021.5065947572231410.460300000045.2699747277241445.20960000001.3763495215251475.58670000002.2877870044261480.943900000065.2147063434271481.08760000005.6160713045281486.060000000012.8595153657291496.749700000031.9082555897301503.896700000024.1420216943312991.305000000085.5863212158323001.2632000000101.3975741576333037.029000000039.8963515456343081.61170000006.1417533962353087.073300000043.4389442956363101.431000000054.7196968586373109.344700000062.8880780841383125.229600000037.0259088028393476.096500000013.3138424974

Table 6. DFT Calculated IR Spectra (Arbitrary Units) of N-nitrosodibutylamine (C8H18N2O)

N-nitrosodibutylamine(DMSO)Frequency(1/cm)Intensity138.929200000054.4672049708244.847200000059.7601894957353.31440000001394.6623328414457.8914000000488.9770691297574.190100000093.0911910245

32

6115.476400000041.90932502737122.689800000010.58725168688146.421700000072.97008643429164.3268000000176.810971990010240.84690000004.227142700811241.255400000012.989021817712260.222600000027.834438328613279.8992000000294.382451782814304.0994000000207.509420024515328.7954000000121.361641829016408.989300000080.480638567917432.5144000000254.902476600918484.5101000000320.338227697019580.7074000000152.856481476120670.0772000000156.621176494421738.220400000046.712272036422739.357100000044.651037134723803.85190000007.778276742424812.974200000012.725256627125849.3138000000112.401194985626908.032800000036.430054359727911.807800000059.364858123028943.443600000079.876442982929954.142600000012.6805410652301005.4036000000140.8799022518311021.077800000017.1941257155321039.2603000000178.2683473149331059.81810000006.4183858524341061.640400000022.8310657322351098.8610000000104.8498331848361129.68790000006.0906323668371140.485200000047.9573415713381188.82890000003.8980243622391202.103700000058.6317816568401255.086600000024.2986805775411265.106000000019.4902786667421297.904200000033.9443475091431303.724900000023.3086273351441323.9518000000154.5881479265451327.353600000082.2128914397461328.099600000031.2176973574471336.6822000000110.2896385226481338.828000000019.5142054124491381.37530000002.5446075699501383.94200000005.9854999358511404.199800000023.5806887192521406.24760000009.2210911468531409.940300000017.9654981303541416.92570000005.6755461984

33

551473.38900000002.1677313696561476.17410000003.4146403255571477.61480000004.0636044117581483.79230000007.7357822834591487.27410000000.7778830040601489.558600000026.5727069346611489.736500000025.8215902256621494.63360000007.6420359366631498.27910000003.9516433719641507.408100000039.6381050046651509.231100000038.6568659579662968.284500000094.2492160249672998.080300000055.6533974598683008.141800000054.5099993332693010.301200000041.2865292624703017.857600000042.5920654197713018.675900000042.4817981755723024.0800000000140.4098813256733024.5622000000105.9685880160743032.441300000020.9248437143753034.24960000009.3474909855763053.73040000007.4709171727773062.338400000030.3528067566783071.175800000049.3154039909793078.5516000000130.3526870944803080.3501000000196.6690547825813083.635200000080.0919697461823084.920600000080.5730297987833103.866900000064.1161183685843472.461600000011.7351044853

N-nitrosodibutylamineFrequency(1/cm)Intensity135.6606000000163.0747823519245.59510000007.1834369522357.17290000008.9036432939464.9028000000742.5736956884574.532200000056.64102661676112.972000000016.64661980207122.46130000005.09826935058148.154300000023.86567863179163.1804000000117.989842594710240.66340000009.377421355611241.19340000007.668056557912257.569500000076.879339023813264.0455000000100.137771931114307.964300000096.917323062415334.437900000068.0709220991

34

16412.413300000061.735965155217416.5676000000215.893368345918479.7011000000163.396926397819581.669900000094.341065259620673.750900000070.345342586921739.805200000019.004238279922742.600200000020.413288636023804.72720000002.366192390324815.98830000007.255820548925852.716900000041.214378906626909.192400000024.935697284027913.631700000023.705874545128945.714500000025.608189183529957.53860000007.9776398915301013.424500000046.5670383450311021.897100000010.7576227227321044.2768000000122.4321038378331061.949100000010.3567766853341063.28780000005.6316695167351094.181800000072.3138614851361131.63920000001.7950961347371143.156900000033.3793097074381193.02470000002.6871863986391202.436700000026.9687507623401255.722400000013.2057277581411265.74300000007.8864905144421299.94140000003.4666357253431303.52060000006.8542487224441326.560900000017.2629374723451329.45720000002.2946900347461330.47440000008.9750424995471339.48640000004.6708738032481349.7135000000101.8502446301491383.29880000003.8777910731501387.05720000003.8175261721511406.079000000031.0426340517521412.72450000008.1319943698531417.11250000007.2107489624541421.07210000001.1285407356551458.14880000003.6469986659561488.89030000000.3874475261571490.43570000001.3717909234581492.30920000001.1463131121591493.87330000003.1875157896601500.348100000019.0712767791611500.630200000018.7159745316621501.80000000004.2786805068631503.70040000003.1581947173641514.209400000019.1627941400

35

651515.809800000019.5452363605662975.635400000037.3532986123672991.671500000026.7820371631683006.835800000027.3295942043693009.797500000017.6899926061703020.361800000031.4926516760713020.644000000020.8487419526723025.174900000059.2580500416733025.589200000066.0696197218743032.64220000009.1293390910753032.746200000014.4970759101763050.49940000007.4694140982773062.20010000009.0184193160783070.152100000031.2590834074793082.476600000042.5762852317803083.9800000000112.3664269059813087.089800000045.2948199286823088.655000000049.2097859341833095.305500000061.0987762714843460.15320000001.9106753319

N-nitrosodibutylamine(Toluene)Frequency(1/cm)Intensity134.3419000000158.9978485561245.042600000026.9339635811356.379300000064.1439098941458.77890000001114.7377654945572.240200000070.03515739266112.886800000021.24982419527121.28560000007.60805584178146.018100000049.18918319729163.0126000000141.671395850810240.593000000011.164336728211240.81270000008.291478798612258.095200000054.538750703513266.1524000000177.165719553114304.2884000000153.784480679115331.356500000079.933265799016411.712800000049.362534155617419.7797000000267.498324413718480.3629000000206.824373656519582.1819000000120.249602945220671.657900000095.145696939321738.931000000028.075238874122741.285400000027.975843691823804.24880000003.851256151024814.54810000009.841401786725851.003300000057.9421393658

36

26908.629000000029.632382372227912.869400000033.291542492028945.075600000041.117477026629956.14030000009.8143133951301010.405800000078.9413666351311021.450300000012.3546498361321042.0125000000142.3095162795331060.94710000009.1373412221341062.507200000010.4140401273351094.806200000085.3353798219361130.69990000002.7008790806371141.918900000037.7625726210381190.82980000002.8207831271391201.551500000037.5621441242401254.813200000016.9487199496411265.045700000011.1194522196421299.42850000005.6591464781431303.50840000009.4630895721441325.943300000028.0079106065451329.02560000002.6946674631461329.781300000022.6269034141471339.08480000007.6172108451481345.4695000000153.5162626101491382.54570000003.4632307302501385.76300000005.1295266791511405.283200000030.8739842443521409.94150000008.7617592469531413.51210000009.2041821124541418.66770000002.3410509253551465.81160000003.5266886585561483.56950000000.6243981662571485.08380000001.7482513950581488.23360000002.9551218901591489.48410000003.0678110474601495.645400000022.5622435304611495.764300000020.9943114696621498.14840000005.0672044933631500.49210000003.1024673978641511.086000000024.6166923629651512.767400000025.3646542292662973.628400000052.6364404636672994.779700000034.2354107270683007.234200000037.0340335960693009.988100000024.5890992864703019.290100000036.1877174142713019.781500000029.5755955569723024.641700000084.0432807591733024.967200000082.4789489420743032.482300000019.6138733110

37

753033.20920000006.0647021415763051.07840000007.8103097787773062.121800000015.4207136153783070.068700000038.4792808310793080.981100000072.4574052989803082.4856000000139.7940557856813085.577800000059.7123583132823087.219700000061.1561982722833098.687200000061.1571083145843467.19970000005.7767565463

N-nitrosodibutylamine(Water)Frequency(1/cm)Intensity139.089400000070.5018680478244.842200000056.3416908765353.41670000001319.9582095113458.0936000000556.2354538961574.320200000097.54995125136115.585600000044.14079547297122.786400000011.16700127108146.364300000073.86546406489164.3174000000177.464469757910240.82040000004.394923059011241.261900000012.790245312212260.303700000027.857950716613280.3115000000297.261245157614304.1686000000209.421702617215328.7179000000122.669413668416408.871000000081.625991405517432.9828000000252.777522959918484.7291000000325.480553204319580.6296000000154.736205089120670.0406000000159.696618390721738.199100000047.522633037322739.283700000045.260395672123803.82260000007.964177668924812.886900000012.836064756525849.2753000000115.005839162526908.009500000036.674392591827911.783500000060.542979382828943.369800000081.787802036629954.059900000012.9199854987301005.2918000000142.8194487899311021.066500000017.4959432490321039.1977000000180.1087155117331059.79750000006.3838790365341061.607000000023.3041502260351099.0002000000105.6674653991

38

361129.65020000006.2617618464371140.429200000048.5169524759381188.78340000003.9381083583391202.150000000059.3456670342401255.093000000024.7292525236411265.118900000019.8561870513421297.839800000036.7380325775431303.717400000023.9948172339441323.7690000000168.5600555609451327.217300000086.6729773352461328.043700000024.8262724907471336.5146000000106.8651324853481338.743200000017.3305369047491381.31320000002.5184400822501383.87780000005.9941376360511404.129400000023.2650783993521406.13320000009.2377293417531409.830900000018.2886290174541416.86230000005.8193986368551473.35650000001.9793237388561475.85330000003.5024227716571477.55850000004.3375385245581483.60860000007.8881298342591487.32170000000.8028032137601489.376500000026.7197950148611489.551200000025.9983533284621494.52900000007.7883164402631498.27310000004.1127503505641507.297100000040.2741200853651509.135100000039.1697847126662968.192200000095.9452460535672998.098500000056.8007388036683008.167800000054.9949131690693010.307000000042.0240816544703017.810900000042.6881693676713018.638500000042.9199024060723024.0396000000142.4036593458733024.5538000000107.4368014423743032.428000000020.6764226908753034.28310000009.5315876620763053.85420000007.4433116291773062.293300000031.2853701881783071.243400000049.5724202668793078.4634000000132.6299582479803080.2815000000199.0726825588813083.581500000080.6992297582823084.836600000081.2528753275833104.033500000064.1926184362843472.583700000011.9313710225

39

Acknowledgments

Funding for this project was provided by the Office of Naval Research (ONR) through the Naval Research

Laboratory’s Basic Research Program.

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