Experimental and Theoretical Study of the OH Vibrational Spectra and Overtone Chemistry of Gas-Phase Vinylacetic Acid

Meghan E. Dunn†‡, George C. Shields§, Kaito Takahashi†, Rex T. Skodje† and Veronica Vaida*†‡
Department of Chemistry and Biochemistry, University of Colorado, Campus Box 215, Boulder, Colorado 80309, CIRES, University of Colorado, Campus Box 215, Boulder, Colorado 80309, and Dean’s Office and Department of Chemistry and Physics, College of Science and Technology, Armstrong Atlantic State University, 11935 Abercorn Street, Savannah, Georgia 31419
J. Phys. Chem. A, 2008, 112 (41), pp 10226–10235
DOI: 10.1021/jp805746t
Publication Date (Web): September 18, 2008
Copyright © 2008 American Chemical Society
†

Department of Chemistry and Biochemistry, University of Colorado.

,
‡

CIRES, University of Colorado.

,
§

Armstrong Atlantic State University.

Abstract

In this study we present the gas-phase vibrational spectrum of vinylacetic acid with a focus on the ν = 1−5 vibrational states of the OH stretching transitions. Cross sections for ν = 1, 2, 4 and 5 of the OH stretching vibrational transitions are derived on the basis of the vapor pressure data obtained for vinylacetic acid. Ab initio calculations are used to assist in the band assignments of the experimental spectra, and to determine the threshold for the decarboxylation of vinylacetic acid. When compared to the theoretical energy barrier to decarboxylation, it is found that the νOH = 4 transition with thermal excitation of low frequency modes or rotational motion and νOH = 5 transitions have sufficient energy for the reaction to proceed following overtone excitation.

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History

  • Published In Issue October 16, 2008
  • Article ASAPSeptember 18, 2008
  • Received: June 30, 2008
    Revised: August 5, 2008

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