s-trans-1,3-Butadiene and Isotopomers:  Vibrational Spectra, Scaled Quantum-Chemical Force Fields, Fermi Resonances, and C−H Bond Properties

Title:
s-trans-1,3-Butadiene and Isotopomers:  Vibrational Spectra, Scaled Quantum-Chemical Force Fields, Fermi Resonances, and C−H Bond Properties
Authors:
McKean, Donald C.; Craig, Norman C.; Panchenko, Yurii N.
Abstract:
Quadratic quantum-chemical force fields have been determined for s-trans-1,3-butadiene using B3LYP and MP2 methods. Basis sets included 6-311++G**, cc-pVTZ, and aug-cc-pVTZ. Scaling of the force fields was based on frequency data for up to 11 isotopomers, some of these data being original. A total of 18 scale factors were employed, with, in addition, an alteration to one off-diagonal force constant in the Au species. MP2 calculations without f functions in the basis perform badly in respect of out-of-plane bending mode frequencies. Centrifugal distortion constants and harmonic contributions to vibration−rotation constants (alphas) have been calculated. Existing experimental frequency data for all isotopomers are scrutinized, and a number of reassignments and diagnoses of Fermi resonance made, particularly in the ν(CH) region. The three types of CH bond in butadiene were characterized in terms of bond length and isolated CH stretching frequency, the latter reflecting data in the ν(CD) region. Broad agreement was achieved with earlier results from local mode studies. Differences in CH bond properties resemble similar differences in propene. A simplified sample setup for recording FT-Raman spectra of gases was applied to four isotopomers of butadiene.
Citation:
McKean, Donald C., Norman C. Craig, and Yurii N. Panchenko. 2006. "s-trans-1,3-Butadiene and Isotopomers:  Vibrational Spectra, Scaled Quantum-Chemical Force Fields, Fermi Resonances, and C−H Bond Properties." Journal of Physical Chemistry A 110(26): 8044-8059.
Publisher:
American Chemical Society
DATE ISSUED:
2006
Department:
Chemistry
Type:
Article
PUBLISHED VERSION:
10.1021/jp060566v
PERMANENT LINK:
http://hdl.handle.net/11282/334087

Full metadata record

DC FieldValue Language
dc.contributor.authorMcKean, Donald C.en
dc.contributor.authorCraig, Norman C.en
dc.contributor.authorPanchenko, Yurii N.en
dc.date.accessioned2014-11-10T14:13:39Z-
dc.date.available2014-11-10T14:13:39Z-
dc.date.issued2006en
dc.identifier.citationMcKean, Donald C., Norman C. Craig, and Yurii N. Panchenko. 2006. "s-trans-1,3-Butadiene and Isotopomers:  Vibrational Spectra, Scaled Quantum-Chemical Force Fields, Fermi Resonances, and C−H Bond Properties." Journal of Physical Chemistry A 110(26): 8044-8059.en
dc.identifier.issn1089-5639en
dc.identifier.urihttp://hdl.handle.net/11282/334087-
dc.description.abstractQuadratic quantum-chemical force fields have been determined for s-trans-1,3-butadiene using B3LYP and MP2 methods. Basis sets included 6-311++G**, cc-pVTZ, and aug-cc-pVTZ. Scaling of the force fields was based on frequency data for up to 11 isotopomers, some of these data being original. A total of 18 scale factors were employed, with, in addition, an alteration to one off-diagonal force constant in the Au species. MP2 calculations without f functions in the basis perform badly in respect of out-of-plane bending mode frequencies. Centrifugal distortion constants and harmonic contributions to vibration−rotation constants (alphas) have been calculated. Existing experimental frequency data for all isotopomers are scrutinized, and a number of reassignments and diagnoses of Fermi resonance made, particularly in the ν(CH) region. The three types of CH bond in butadiene were characterized in terms of bond length and isolated CH stretching frequency, the latter reflecting data in the ν(CD) region. Broad agreement was achieved with earlier results from local mode studies. Differences in CH bond properties resemble similar differences in propene. A simplified sample setup for recording FT-Raman spectra of gases was applied to four isotopomers of butadiene.en
dc.language.isoen_USen
dc.publisherAmerican Chemical Societyen
dc.identifier.doi10.1021/jp060566ven
dc.subject.departmentChemistryen
dc.titles-trans-1,3-Butadiene and Isotopomers:  Vibrational Spectra, Scaled Quantum-Chemical Force Fields, Fermi Resonances, and C−H Bond Propertiesen
dc.typeArticleen
dc.identifier.journalJournal of Physical Chemistryen
dc.identifier.volume110en
dc.identifier.issue26en
dc.identifier.startpage8044en
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