Infrared Spectra Of 12CF2=12CH2 and 12CF2=13CH2, Quantum-chemical Calculations Of Anharmonicity, And Analyses Of Resonances

Title:
Infrared Spectra Of 12CF2=12CH2 and 12CF2=13CH2, Quantum-chemical Calculations Of Anharmonicity, And Analyses Of Resonances
Authors:
McKean, Donald C.; van der Veken, Benjamin; Herrebout, Wouter; Law, Mark M.; Brenner, Michael J.; Nemchick, Deacon J.; Craig, Norman C.
Abstract:
Infrared spectra obtained in gas and liquid argon phases are reported for (CF2)-C-12=(CH2)-C-12 and (CF2)-C-12=(CH2)-C-13. These spectra firmly establish the positions of nu(3)(A(1)) and nu(6)(A(2)) for both isotopomers. Using anharmonicity constants from MP2 calculations, Fermi resonances affecting nu(1)(A(1)), nu(2)(A(1)), nu(3), and nu(8)(B-1) are analyzed. Deperturbed fundamental frequencies from these analyses are used in conjunction with unaffected fundamentals and ab initio anharmonicity data to predict all 12 "observed" harmonic frequencies. A Darling-Dennison type resonance between 2 nu(6) and nu(11) + nu(12) is diagnosed, the calculation of which from ab initio data requires modification of the existing second-order treatment of such constants, where Fermi resonance type terms are also present. Predictions are made of many overtone and combination band frequencies, aiding assignment of observed spectra. From the isolated CH stretching frequency obtained here of 3125.4 cm(-1), the C-H equilibrium bond length is predicted to be 1.0762(11) angstrom.
Citation:
McKean, Donald C., Benjamin van der Veken, Wouter Herrebout, Mark M. Law, et al. 2010. "Infrared Spectra Of 12CF2=12CH2 and 12CF2=13CH2, Quantum-chemical Calculations Of Anharmonicity, And Analyses Of Resonances." Journal Of Physical Chemistry A 114(18): 5728-5742.
Publisher:
American Chemical Society
DATE ISSUED:
2010-05
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1021/jp100438z
PERMANENT LINK:
http://hdl.handle.net/11282/309983

Full metadata record

DC FieldValue Language
dc.contributor.authorMcKean, Donald C.en_US
dc.contributor.authorvan der Veken, Benjaminen_US
dc.contributor.authorHerrebout, Wouteren_US
dc.contributor.authorLaw, Mark M.en_US
dc.contributor.authorBrenner, Michael J.en_US
dc.contributor.authorNemchick, Deacon J.en_US
dc.contributor.authorCraig, Norman C.en_US
dc.date.accessioned2013-12-23T16:22:32Zen
dc.date.available2013-12-23T16:22:32Zen
dc.date.issued2010-05en
dc.identifier.citationMcKean, Donald C., Benjamin van der Veken, Wouter Herrebout, Mark M. Law, et al. 2010. "Infrared Spectra Of 12CF2=12CH2 and 12CF2=13CH2, Quantum-chemical Calculations Of Anharmonicity, And Analyses Of Resonances." Journal Of Physical Chemistry A 114(18): 5728-5742.en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/11282/309983en
dc.description.abstractInfrared spectra obtained in gas and liquid argon phases are reported for (CF2)-C-12=(CH2)-C-12 and (CF2)-C-12=(CH2)-C-13. These spectra firmly establish the positions of nu(3)(A(1)) and nu(6)(A(2)) for both isotopomers. Using anharmonicity constants from MP2 calculations, Fermi resonances affecting nu(1)(A(1)), nu(2)(A(1)), nu(3), and nu(8)(B-1) are analyzed. Deperturbed fundamental frequencies from these analyses are used in conjunction with unaffected fundamentals and ab initio anharmonicity data to predict all 12 "observed" harmonic frequencies. A Darling-Dennison type resonance between 2 nu(6) and nu(11) + nu(12) is diagnosed, the calculation of which from ab initio data requires modification of the existing second-order treatment of such constants, where Fermi resonance type terms are also present. Predictions are made of many overtone and combination band frequencies, aiding assignment of observed spectra. From the isolated CH stretching frequency obtained here of 3125.4 cm(-1), the C-H equilibrium bond length is predicted to be 1.0762(11) angstrom.en_US
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.identifier.doi10.1021/jp100438zen
dc.subject.departmentChemistryen_US
dc.titleInfrared Spectra Of 12CF2=12CH2 and 12CF2=13CH2, Quantum-chemical Calculations Of Anharmonicity, And Analyses Of Resonancesen_US
dc.typearticleen_US
dc.identifier.journalJournal Of Physical Chemistry Aen_US
dc.subject.keywordCorrelated molecular calculationsen_US
dc.subject.keywordResolution ftir spectrumen_US
dc.subject.keywordGaussian-basis setsen_US
dc.subject.keywordForce-fieldsen_US
dc.subject.keywordVibrational anharmonicityen_US
dc.subject.keywordFermien_US
dc.subject.keywordResonanceen_US
dc.subject.keyword1,1-difluoroethyleneen_US
dc.subject.keywordcf2=ch2en_US
dc.subject.keywordBandsen_US
dc.subject.keywordSpectroscopyen_US
dc.subject.keywordChemistry, physicalen_US
dc.subject.keywordPhysics, atomic, molecular & chemicalen_US
dc.identifier.volume114en_US
dc.identifier.issue18en_US
dc.identifier.startpage5728en_US
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