ab initio determination of spectroscopic constantsfqm292/senent.pdf · ch+ a simple...
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Ab initio Ab initio determinationdetermination ofof spectroscopicspectroscopicconstantsconstants
(From UV to sub(From UV to sub--millimetermillimeter wavelengths)wavelengths)
M.L.SenentM.L.SenentDepartamento de Astrofísica Molecular e Departamento de Astrofísica Molecular e InfarrojaInfarroja
Instituto de Estructura de la Materia, CSIC.Instituto de Estructura de la Materia, CSIC.
ARENA, Granada 2008ARENA, Granada 2008
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OUTLINEOUTLINE
Characterization of astronomical species and Characterization of astronomical species and processes.processes.Search for stable structures and intermediates.Search for stable structures and intermediates.Electronic spectra: vertical and adiabatic Electronic spectra: vertical and adiabatic transitionstransitionsInfrared spectra: anharmonic analysis and Infrared spectra: anharmonic analysis and rotational parametersrotational parametersCollisional cross sections and ratesCollisional cross sections and ratesOur Fortran codesOur Fortran codes
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OUTLINEOUTLINE
Characterization of astronomical species Characterization of astronomical species and processes.and processes.
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CARBON CHAINSCARBON CHAINSC4 C4 Electronic structure calculations on the C4 cluster, Electronic structure calculations on the C4 cluster, H.MassoH.Masso, , M.L.SenentM.L.Senent, P. , P. RosmusRosmus y M.Hochlaf, y M.Hochlaf, J.Chem.PhysJ.Chem.Phys., 124, 234304 ., 124, 234304 (2006)(2006)Anharmonic spectroscopic study of the ground electronic state ofAnharmonic spectroscopic study of the ground electronic state ofvarious C4 radical isotopomers, various C4 radical isotopomers, M.L.SenentM.L.Senent H. H. MassóMassó y M.Hochlafy M.Hochlaf, , ApJApJ, , 670, 1510 (2007670, 1510 (2007))
C5C5Ab initio characterization of the C5, H. Ab initio characterization of the C5, H. MassóMassó, V. , V. VeryazovVeryazov, P., P.--Å. Å. MalmqvistMalmqvist, B.O. , B.O. RoosRoos y y M.L.SenentM.L.Senent, , J.Chem.PhysJ.Chem.Phys., 127 (15), 154318 ., 127 (15), 154318 (2007)(2007)
C6 C6 MassóMassó, Senent (in , Senent (in preparationpreparation))
C4+ C4+ PhotoionizationPhotoionization of the C4 molecular beam: ab initio of the C4 molecular beam: ab initio calculations, M.Hochlaf, calculations, M.Hochlaf, C.NicolasC.Nicolas and and L.PosissonL.Posisson, , J.Chem.PhysJ.Chem.Phys., ., 127, 014310 (2007)127, 014310 (2007)
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CARBON CHAINSCARBON CHAINSCH+ CH+ A simple variationalA simple variational--numerical approach to the ronumerical approach to the ro--vibrational vibrational spectrum of diatomic molecules. An application to CH+, J.R. Letespectrum of diatomic molecules. An application to CH+, J.R. Letelier lier y y M.L.SenentM.L.Senent, , SpectrochimicaSpectrochimica ActaActa A, 65, 1030A, 65, 1030--1034 (2006)1034 (2006)
C3SiC3Si Ab initio characterization of molecules of the linear lAb initio characterization of molecules of the linear l--SiC3 SiC3 isomers”, N.Inostroza, isomers”, N.Inostroza, M.L.SenentM.L.Senent, M.Hochlaf and , M.Hochlaf and R.LetelierR.Letelier((AstronAstron & Astro, 2008)& Astro, 2008)
C4H C4H Senent Senent andand Hochlaf (in Hochlaf (in preparationpreparation))
C4HC4H-- Senent Senent andand Hochlaf (in Hochlaf (in preparationpreparation
C6H+C6H+ ShuitkoShuitko, , J.FularaJ.Fulara, , A.BalatovA.Balatov, , C.GilleryC.Gillery, , H.MassoH.Masso, , P.RosmusP.Rosmus y y J.P.MaierJ.P.Maier, , J. Phys. Chem. A, 110, 2885J. Phys. Chem. A, 110, 2885--2889, 2006.2889, 2006.
CF+CF+ Theoretical roTheoretical ro--vibrational spectrum of CF+, N. vibrational spectrum of CF+, N. InostrozaInostroza, J. R. , J. R. Letelier, P. Letelier, P. FuentealbaFuentealba and and M.L.SenentM.L.Senent, , SpectrochimicaSpectrochimica ActaActa Part A, Part A, 2008.2008.
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Astrophysical observations (DAMIR)Cernicharo, Goicoechea y Benilan, ApJ (2002)
???
C4 O C4H
174 cm-1
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Astrophysical observations DAMIRA new unidentified far-infrared band in NGC 7027, Goicoechea, Cernicharo, Massó y Senent, ApJ (2004)
???
C5 O C6
band centre at98 µm = 102 cm-1
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COLLISIONAL RATESCOLLISIONAL RATES
SO+ He SO+ He Molecules as Diagnostic Tools in the Interstellar Medium, Molecules as Diagnostic Tools in the Interstellar Medium, A.SpielfiedelA.Spielfiedel, , N.FeautrierN.Feautrier, , C.BalancaC.Balanca, , F.DayouF.Dayou, , F.LiqueF.Lique and and M.L.SenentM.L.Senent, , Mol.PhysMol.Phys., 105 (9), 1263., 105 (9), 1263--1269 (2007)1269 (2007)
SO +H2 SO +H2 Rotationally inelastic collisions of SO (XRotationally inelastic collisions of SO (X33 ΣΣ--) with H2: potential ) with H2: potential energy surface and first results with paraenergy surface and first results with para--H2, H2, F.LiqueF.Lique, , M.L.SenentM.L.Senent, , A.SpielfiedelA.Spielfiedel and and N.FeautrierN.Feautrier, , J. Chem. Phys. 126, 164312 (2007)J. Chem. Phys. 126, 164312 (2007)
SO2 + H2 SO2 + H2 A.SpielfiedelA.Spielfiedel, , L.VincentL.Vincent, , M.L.SenentM.L.Senent,, ,, P.ValironP.Valiron, , F.FaureF.Faure and and N.FeautrierN.Feautrier (in (in preparationpreparation))
C3+HeC3+He Low temperature rate constants for rotational excitations and Low temperature rate constants for rotational excitations and dede--excitations of C3 by collisions with He, D. Ben excitations of C3 by collisions with He, D. Ben AbdallahAbdallah, , K.HammamiK.Hammami, , F.NajarF.Najar, , N.JaidaneN.Jaidane, , Z.BenZ.Ben LakhdarLakhdar, , M.L.SenentM.L.Senent, , C.ChambaudC.Chambaud and M.Hochlaf, and M.Hochlaf, Astrophysical Journal, 2008.Astrophysical Journal, 2008.
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OUTLINEOUTLINE
AtmosphericalAtmospherical andand astronomicalastronomicaluncharacterizeduncharacterized speciesspecies andand processesprocesses..SearchSearch forfor stablestable structuresstructures andandintermediatesintermediates..
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CC44 CC44++ CC44-- CC33SiSi CC44HH CC44HH--isomers
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Isomers: S (singlet); T (triplet); D (doublet)
CC44 CC44++ CC44-- CC33SiSi CC44HH CC44HH--
D D ST D S
DSD D SS
T?S?
D
D
S
S
D D
?T
T
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Relative energies (eV)
CC44 CC44++ CC44-- CC33SiSi CC44HH CC44HH--
0 0 00 0 0
1.30.40.2 1.0 2.40.3
0.5?1.4?
1.1
1.7
3.2
3.2
1.1 0.6
?3.7
3.3
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CC44 CC44++ CC44-- CC33SiSi CC44HH CC44HH--isomers
?? ?
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d-C4
H.Masso, M.L.Senent, P. Rosmus, M.Hochlaf, J.Chem.Phys., 124, 234304 (2006)
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CC44 CC44++ CC44-- CC33SiSi CC44HH CC44HH--isomers
?? ?
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CC44 CC44++ CC44-- CC33SiSi CC44HH CC44HH--isomers
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r-C4
30000 cm-1
H.Masso, M.L.Senent, P. Rosmus y M.Hochlaf, J.Chem.Phys., 124, 234304 (2006)
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ll--CC6 6 XX33ΣΣ--gg
ParametersParameters CASPT2CASPT2 ExperimentalExperimental
Central Central bondbond 1.2651.265
MediumMedium bondbond 1.2761.276
OuterOuter BondBond 1.29511.2951
BB00 0.0480.048 cmcm--11 0.048410 0.048410 (1)(1)
(1) infrared diode laser spectroscopy.Hwang et al. Mol Phys 1993, 79-769
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OUTLINEOUTLINE
Characterization of astronomical species Characterization of astronomical species and processes.and processes.SearchSearch forfor stablestable structuresstructures andandintermediatesintermediates..ElectronicElectronic spectraspectra: vertical : vertical andandadiabaticadiabatic transitionstransitions
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Introduction PurePure C C chainschains VibSpec Conclusions
Absorption spectra for C4
CC66
3.27 eV0.93 eV
Linnartz et al.,JCP, 112,9777 (2000)
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C4
StateState CASSCCASSCFF
MRCIMRCI Exp.Exp.
33 ΣΣgg-- 0.0 0.0 0.0 0.0 0.00.0
11∆∆gg 0.43 0.43 eVeV
0.44 0.44 eVeV
0.33 0.33 eVeV
11 ΣΣgg++ 0.47 0.47
eVeV0.61 0.61 eVeV
0.50 0.50 eVeV
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C5
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1A´
1A"1A´
3A"
O2H+
E (a.u.)
120 80 40 0ang (deg)
-150.27
-150.22
-150.17
-150.12
EV AT
E=0V=0
V=0
exp
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C5
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MRCI
CC44
CC55
33ΣΣgg-- 0.0 0.0 11ΣΣgg++ 0.00.0
11∆∆gg 0.44 0.44 eVeV
0.61 0.61 eVeV
33ΠΠgg 1.74 1.74 eVeV
11ΣΣgg++ 33ΠΠuu 1.84 1.84 eVeV
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Ozone + cations Ozone + cations processesprocesses..
Electronic structure and spectroscopy of Electronic structure and spectroscopy of MgO2+MgO2+ cationcation, , O.YazidiO.Yazidi, A. Ben , A. Ben HouriaHouria and and Z.BenZ.Ben LakhdarLakhdar, , M.L.SenentM.L.Senent and M.Hochlaf, and M.Hochlaf, Chem.PhysChem.Phys, 2008, 2008
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Spin-Orbit (MOLPRO)
3Σg- ∆ E
= 2Aso
< 3Σg-|SO| 1Σg
+> → ∆E=0.2 cm-1
< 3Σg-|SO| 1∆g>
< 3Σg-|SO| 3πu>
< 3Σg-|SO| 3πg> → ∆E < 0.001 cm-1
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ll--SiCCCSiCCC ll--CC66 ll--CC44
∆∆E (XE (X33ΣΣ-- →→ 11ΣΣ++) ) (cm(cm--11))
λ λ (cm(cm--11))
2292229240774077
--0.6050.605
-- 0.5471860.547186b)b)
0.070.07
49194919
0.010.01
b) Deduced from previous measurements.
Ab initio characterization of the linear SiC3 isomers”, N.Inostroza, M.Hochlaf, M.L. Senent and R.Letelier (Astron & Astroph, 2008)
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OUTLINEOUTLINE
Characterization of astronomical species Characterization of astronomical species and processes.and processes.SearchSearch forfor stablestable structuresstructures andandintermediatesintermediates..ElectronicElectronic spectraspectra: vertical : vertical andand adiabaticadiabatictransitionstransitionsInfraredInfrared spectraspectra: anharmonic : anharmonic analysisanalysis. . RotationalRotational parametersparameters
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Astrophysical observations (DAMIR)Cernicharo, Goicoechea y Benilan, ApJ (2002)
???
C4 O C4H
174 cm-1
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Astrophysical observations DAMIRA new unidentified far-infrared band in NGC 7027, Goicoechea, Cernicharo, Massó y Senent, ApJ (2004)
???
C5 O C6
band centre at98 µm = 102 cm-1
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CC44: : bendingbending νν55 ((ππuu) ) (in (in cmcm--11))CalculatedCalculated ExperimentalExperimental172 (H)172 (H)203 (H)203 (H)171.1 171.1 ((anHanH))
MBPT(2)/6MBPT(2)/6--311G(2d)311G(2d)CCSD(TCCSD(T)/PVTZ)/PVTZRCCSD(TRCCSD(T)/)/vQZvQZ(1D)(1D)
160160±±44
172.4 172.4 170.4170.4174174
DiodeDiode laserlaser absorptionabsorption(gas (gas phasephase))IR (IR (ArAr matrixmatrix))
FIR FIR astrophysicalastrophysicalobservationobservation
Anharmonic spectroscopic study of the ground electronic state of various C4 radical isotopomers, M.L.Senent H. Massó y M.Hochlaf, ApJ, 670, 1510 (2007)
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CC55: : bendingbending νν77 ((ππuu) ) (in (in cmcm--11))
CalculatedCalculated ExperimentalExperimental
112 112 (H)(H)130 130 (H)(H)119 119 (H)(H)
HF/6HF/6--31G(d)31G(d)MP2/6MP2/6--31G(d)31G(d)CEPACEPA--l/l/150cGTOs150cGTOs((refinedrefined))
111188±±33
101066
101022
DiodeDiode laserlaserabsorptionabsorption (gas (gas phasephase))AnionAnionphotodetachmenphotodetachmentt spectroscopyspectroscopy(gas (gas phasephase))FIR FIR astrophysicalastrophysicalobservationobservation
Base data
ExperimentalExperimentalCalculatedCalculated
PhotoelectronPhotoelectron spectroscopyspectroscopy(gas (gas phasephase))FIR FIR astrophysicalastrophysicalobservationobservation
9090
102102
B3LYP/B3LYP/cccc--pVTZpVTZCCSD(TCCSD(T)/)/150cGTOs150cGTOs
108 (H)108 (H)108 (H)108 (H)
CC66: : bendingbending νν99 ((ππuu) ) (in (in cmcm--11))
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1529.9 cm-1
168.4 cm-1
Anharmonic spectroscopic study of the ground electronic state of various C4 radical isotopomers, M.L.Senent H. Massó, M.Hochlaf, ApJ, 670, 1510 (2007)
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Anharmonic spectroscopic study of the ground electronic state of various C4 radical isotopomers, M.L.Senent H. Massó, M.Hochlaf, ApJ, 670, 1510 (2007)
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l-C5
J.Chem.Phys,2007
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l-C5
J.Chem.Phys,2007
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l-C5
J.Chem.Phys,2007
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OUTLINEOUTLINE
Characterization of astronomical species and Characterization of astronomical species and processes.processes.SearchSearch forfor stablestable structuresstructures andand intermediatesintermediates..ElectronicElectronic spectraspectra: vertical : vertical andand adiabaticadiabatictransitionstransitionsInfraredInfrared spectraspectra: anharmonic : anharmonic analysisanalysis andandrotationalrotational parametersparametersCollisional cross Collisional cross sectionssections andand ratesrates
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Intensities and band shapes
Transition probability
Radiative probabilitiesEinstein coefficients Collisional probabilities and rates
Cross sections and rates
Excitation and de-excitation rate
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Ab initio calculations of collisional cross sections σ
Van-der Walls SurfaceMolecule + H2 (or He)
Fit4 6 8 10 12
-5000
0
5000
10000
15000
θSO = 0θSO = 45θSO = 75θSO = 90θSO = 135
θΗ2 = 0 ; φ = 0
Inte
ract
ion
ener
gy (c
m-1
)
R (A)
Close Coupling Equations CC (Coupled States CS, Infinite Order Sudden IOS)
K j →i K i →j
Collision packagesMOLSCATHIBRIDONMOLCOL
σ
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TEST OF ACCURACYTEST OF ACCURACYSO+ HeSO+ HeSO +H2SO +H2
SO2 + H2SO2 + H2C3+H2C3+H2
What test to do?
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PotentialPotential Surface (MOLPRO)Surface (MOLPRO)DefinitionDefinition of the of the independentindependent coordinatescoordinatesAb initio Ab initio methodmethod: : RCCSD(T) or MRCI ?RCCSD(T) or MRCI ?Basis Set ?Basis Set ?Bond Bond functionfunction??Extrapolation of the basis Extrapolation of the basis set?set?BSSE correctionsBSSE correctionsS S atomatom corecore: 1s or 1s2s2p ? : 1s or 1s2s2p ? Fitting
4
5
6
7
8
9
10
11
12
13
14
15
16
0
90
180
-200-180-160-140-120-100
-80-60-40-20
020406080
100
Inte
ract
ion
En
erg
y
RHe(ao)
Theta
Potential Surface SO-He80-10060-8040-6020-400-20-20-0-40--20-60--40-80--60-100--80-120--100-140--120-160--140-180--160-200--180
Fitting
Rotationally inelastic collisions of SO (X3 S-) with H2: potential energy surface and first results with para-H2, F.Lique, M.L.Senent, A.Spielfiedel and N.Feautrier, J. Chem. Phys. 126, 164312 (2007)
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WHAT TEST TO PERFORM?WHAT TEST TO PERFORM?
ChoiceChoice of the of the methodmethod(RCCSD(T) or MRCI):(RCCSD(T) or MRCI):
Convergence of the Basis Convergence of the Basis set (AVDZ to AV5Z) set (AVDZ to AV5Z) ((effecteffect of bond of bond functionsfunctions) ) (extrapolation of the Basis (extrapolation of the Basis Set)
Basis set
Slat
er D
eter
min
ants
Exact solution
Hartree-Focklimit
Full CI
Set)
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Convergence of the Basis SetConvergence of the Basis Set
-160
-150
-140
-130
-120
-110
-100
-90
-80
7 7.2 7.4 7.6 7.8 8 8.2RHe(bohr)
n=2
n=3
n=4
n=5
aug-cc-pVnZ == AVnZ
core2
mincore5,1
min
V(RHe, θ=180°, rSO=2.80ao) (µHartree)
DZ
QZ5Z
TZ
CBSlQZ+CT99 0.9cm-1TZ+TP92 2.0cm-1
∆VCBSl
triangles:bond functions@ midbond RHe
-160
-150
-140
-130
-120
-110
-100
-90
-80
2 3 4 5n in AVnZ
y = m1 + m2 / (M0+1)^3 + m3 / (M0+1)^5
ErrorValue
0.40286-162.69m1
67.9272397.2m2
532.71-6084.2m3
NA0.046643Chisq
NA0.99999R
n=2,3,4,5
y = m1 + m2 / (M0+1)^3
ErrorValue
1.991-157.27m1
84.141584.5m2
NA3.2088Chisq
NA0.99859R
n=2,3,4
y = m1 + m2 / (M0+1)^3
ErrorValue
0.15553-161.1m1
14.8391922.1m2
NA0.013975Chisq
NA0.99997R
n=3,4,5
Vmin(RHe, θ=180°, rSO=2.80ao) (µHartree)
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R
l-C3 + He
ν (C-C-C bending) = 63 cm -1
Low temperature rate constants for rotational excitations and de-excitations of C3 (1Σ+g) by collisions +He (1S), D. Ben Abdallah, K.Hammami, F.Najar, N.Jaidane, Z.Ben Lakhdar, M.L.Senent, C.Chambaud and M.Hochlaf(Astrophysical Journal, 2008).
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ratesCross sections
MOLSCATC3 + He
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OUTLINEOUTLINE
Characterization of astronomical species and Characterization of astronomical species and processes.processes.SearchSearch forfor stablestable structuresstructures andand intermediatesintermediates..ElectronicElectronic spectraspectra: vertical : vertical andand adiabaticadiabatictransitionstransitionsInfraredInfrared spectraspectra: anharmonic : anharmonic analysisanalysisRotationalRotational parametersparametersCollisional cross Collisional cross sectionssections andand ratesratesMyMy ownown FortranFortran codescodes
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Second Order Perturbation Theory
http://damir.iem.csic.es/~senent/PROGRAMAS.htm
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(Variational)
FIRhttp://damir.iem.csic.es/~senent/PROGRAMAS.htm