Vibrational and Quantum Chemical Studies of 1,2-Difluoroethylenes: Spectra of 1,2-13C2H2F2 Species, Scaled Force Fields, and Dipole Derivatives

Title:
Vibrational and Quantum Chemical Studies of 1,2-Difluoroethylenes: Spectra of 1,2-13C2H2F2 Species, Scaled Force Fields, and Dipole Derivatives
Authors:
Craig, Norman C.; Petersen, Kathleen L.; McKean, Donald C.
Abstract:
Infrared and Raman spectra are reported for cis and trans 1,2-13C2H2F2. Quantum chemical calculations at B3LYP and MP2 levels have been made for cis and trans 1,2-difluoroethylenes, using 6-311G** and 6-311++G** bases. The resulting harmonic force fields for each compound were scaled with nine independent factors, using frequency data corrected, where necessary, for Fermi resonances and for liquid/gas shifts. The previously accepted assignments for ν7 and ν12 in the trans isomer are interchanged. Several scale factors for bending motions differ markedly between the cis and trans compounds. Centrifugal distortion constants observed with significant accuracy are predicted within 6%. Harmonic contributions to the vibrational dependence of the rotational constants and perpendicular amplitudes are calculated. The C=C and C−H bonds in the cis and trans isomers are essentially identical in respect to length, force constant, and isolated CH stretching frequency. However, the C−F bond is slightly stronger in the cis compound. A revised allocation of observed infrared intensity between the overlapping trans ν7 and ν12 bands is needed. Directions of ∂p/∂Q for the trans Bu bands are given, which differ from those reported earlier. Magnitudes and directions of the bond dipole derivatives ∂μ/∂r for the CH and CF bonds are obtained from calculated atomic polar tensors. In both cis and trans isomers, the vector ∂μ/∂rCF lies within 17° of the bond direction, but for the CH bond, ∂μ/∂r is roughly perpendicular to the CH direction.
Citation:
Craig, Norman C., Kathleen L. Petersen, and Donald C. McKean. 2002. "Vibrational and Quantum Chemical Studies of 1,2-Difluoroethylenes: Spectra of 1,2-13C2H2F2 Species, Scaled Force Fields, and Dipole Derivatives." The Journal of Physical Chemistry A 106(26): 6358-6369.
Publisher:
American Chemical Society
DATE ISSUED:
2002
Department:
Chemistry
Type:
Article
PUBLISHED VERSION:
10.1021/jp020119p
PERMANENT LINK:
http://hdl.handle.net/11282/334099

Full metadata record

DC FieldValue Language
dc.contributor.authorCraig, Norman C.en
dc.contributor.authorPetersen, Kathleen L.en
dc.contributor.authorMcKean, Donald C.en
dc.date.accessioned2014-11-10T14:13:51Z-
dc.date.available2014-11-10T14:13:51Z-
dc.date.issued2002en
dc.identifier.citationCraig, Norman C., Kathleen L. Petersen, and Donald C. McKean. 2002. "Vibrational and Quantum Chemical Studies of 1,2-Difluoroethylenes: Spectra of 1,2-13C2H2F2 Species, Scaled Force Fields, and Dipole Derivatives." The Journal of Physical Chemistry A 106(26): 6358-6369.en
dc.identifier.issn1089-5639en
dc.identifier.urihttp://hdl.handle.net/11282/334099-
dc.description.abstractInfrared and Raman spectra are reported for cis and trans 1,2-13C2H2F2. Quantum chemical calculations at B3LYP and MP2 levels have been made for cis and trans 1,2-difluoroethylenes, using 6-311G** and 6-311++G** bases. The resulting harmonic force fields for each compound were scaled with nine independent factors, using frequency data corrected, where necessary, for Fermi resonances and for liquid/gas shifts. The previously accepted assignments for ν7 and ν12 in the trans isomer are interchanged. Several scale factors for bending motions differ markedly between the cis and trans compounds. Centrifugal distortion constants observed with significant accuracy are predicted within 6%. Harmonic contributions to the vibrational dependence of the rotational constants and perpendicular amplitudes are calculated. The C=C and C−H bonds in the cis and trans isomers are essentially identical in respect to length, force constant, and isolated CH stretching frequency. However, the C−F bond is slightly stronger in the cis compound. A revised allocation of observed infrared intensity between the overlapping trans ν7 and ν12 bands is needed. Directions of ∂p/∂Q for the trans Bu bands are given, which differ from those reported earlier. Magnitudes and directions of the bond dipole derivatives ∂μ/∂r for the CH and CF bonds are obtained from calculated atomic polar tensors. In both cis and trans isomers, the vector ∂μ/∂rCF lies within 17° of the bond direction, but for the CH bond, ∂μ/∂r is roughly perpendicular to the CH direction.en
dc.language.isoen_USen
dc.publisherAmerican Chemical Societyen
dc.identifier.doi10.1021/jp020119pen
dc.subject.departmentChemistryen
dc.titleVibrational and Quantum Chemical Studies of 1,2-Difluoroethylenes: Spectra of 1,2-13C2H2F2 Species, Scaled Force Fields, and Dipole Derivativesen
dc.typeArticleen
dc.identifier.journalJournal of Physical Chemistry Aen
dc.identifier.volume106en
dc.identifier.issue26en
dc.identifier.startpage6358en
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