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

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.

Publisher

American Chemical Society

Publication Date

1-1-2006

Publication Title

Journal of Physical Chemistry

Department

Chemistry and Biochemistry

Document Type

Article

DOI

https://dx.doi.org/10.1021/jp060566v

Language

English

Format

text

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