Ab initio and resonance Raman studies of hexafluoro-1,3-butadiene

M. S C Foley, Dale A. Braden, Bruce S Hudson, Marek Z. Zgierski

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Abstract

Fluorine substitution can have a major effect on the electronic spectra and sometimes on the ground electronic state conformations of organic compounds. In this work we investigate the effect of perfluorination on the resonance Raman spectra of the simple diene hexafluoro-1,3-butadiene (HFBD) where the preferred ground state geometry is believed to be skew s-cis. Ab initio calculations at the 6-31+G* level (which includes diffuse functions (+) and polarization functions (*) on both C and F atoms) together with MP2, BLYP-DFT, and hybrid B3LYP-DFT/HF treatments of electron correlation were performed. The most stable conformer of HFBD is confirmed to be the skew s-cis form (φ ≈ 58°) with a fundamental vibrational C-C torsional mode at 44 cm-1. Ab initio calculations of the gradient of the potential energy surface of the resonant excited singlet state provide a prediction of the relative resonance Raman intensities. A detailed comparison of theory with experiment is possible, and excellent agreement is observed. Activity in the fundamental transition of the torsional mode confirms the low frequency of this mode and the nonplanar nature of the ground state.

Original languageEnglish (US)
Pages (from-to)1455-1459
Number of pages5
JournalJournal of Physical Chemistry A
Volume101
Issue number8
StatePublished - Feb 20 1997

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butadiene
Discrete Fourier transforms
Ground state
Electron correlations
Potential energy surfaces
Fluorine
Electronic states
Organic compounds
Excited states
Conformations
Raman scattering
Substitution reactions
ground state
dienes
Polarization
organic compounds
electronic spectra
Atoms
fluorine
Geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Foley, M. S. C., Braden, D. A., Hudson, B. S., & Zgierski, M. Z. (1997). Ab initio and resonance Raman studies of hexafluoro-1,3-butadiene. Journal of Physical Chemistry A, 101(8), 1455-1459.

Ab initio and resonance Raman studies of hexafluoro-1,3-butadiene. / Foley, M. S C; Braden, Dale A.; Hudson, Bruce S; Zgierski, Marek Z.

In: Journal of Physical Chemistry A, Vol. 101, No. 8, 20.02.1997, p. 1455-1459.

Research output: Contribution to journalArticle

Foley, MSC, Braden, DA, Hudson, BS & Zgierski, MZ 1997, 'Ab initio and resonance Raman studies of hexafluoro-1,3-butadiene', Journal of Physical Chemistry A, vol. 101, no. 8, pp. 1455-1459.
Foley MSC, Braden DA, Hudson BS, Zgierski MZ. Ab initio and resonance Raman studies of hexafluoro-1,3-butadiene. Journal of Physical Chemistry A. 1997 Feb 20;101(8):1455-1459.
Foley, M. S C ; Braden, Dale A. ; Hudson, Bruce S ; Zgierski, Marek Z. / Ab initio and resonance Raman studies of hexafluoro-1,3-butadiene. In: Journal of Physical Chemistry A. 1997 ; Vol. 101, No. 8. pp. 1455-1459.
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N2 - Fluorine substitution can have a major effect on the electronic spectra and sometimes on the ground electronic state conformations of organic compounds. In this work we investigate the effect of perfluorination on the resonance Raman spectra of the simple diene hexafluoro-1,3-butadiene (HFBD) where the preferred ground state geometry is believed to be skew s-cis. Ab initio calculations at the 6-31+G* level (which includes diffuse functions (+) and polarization functions (*) on both C and F atoms) together with MP2, BLYP-DFT, and hybrid B3LYP-DFT/HF treatments of electron correlation were performed. The most stable conformer of HFBD is confirmed to be the skew s-cis form (φ ≈ 58°) with a fundamental vibrational C-C torsional mode at 44 cm-1. Ab initio calculations of the gradient of the potential energy surface of the resonant excited singlet state provide a prediction of the relative resonance Raman intensities. A detailed comparison of theory with experiment is possible, and excellent agreement is observed. Activity in the fundamental transition of the torsional mode confirms the low frequency of this mode and the nonplanar nature of the ground state.

AB - Fluorine substitution can have a major effect on the electronic spectra and sometimes on the ground electronic state conformations of organic compounds. In this work we investigate the effect of perfluorination on the resonance Raman spectra of the simple diene hexafluoro-1,3-butadiene (HFBD) where the preferred ground state geometry is believed to be skew s-cis. Ab initio calculations at the 6-31+G* level (which includes diffuse functions (+) and polarization functions (*) on both C and F atoms) together with MP2, BLYP-DFT, and hybrid B3LYP-DFT/HF treatments of electron correlation were performed. The most stable conformer of HFBD is confirmed to be the skew s-cis form (φ ≈ 58°) with a fundamental vibrational C-C torsional mode at 44 cm-1. Ab initio calculations of the gradient of the potential energy surface of the resonant excited singlet state provide a prediction of the relative resonance Raman intensities. A detailed comparison of theory with experiment is possible, and excellent agreement is observed. Activity in the fundamental transition of the torsional mode confirms the low frequency of this mode and the nonplanar nature of the ground state.

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