Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2008-10-16

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, Veronica Vaida

Index: J. Phys. Chem. A 112(41) , 10226-35, (2008)

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Abstract

In this study we present the gas-phase vibrational spectrum of vinylacetic acid with a focus on the nu = 1-5 vibrational states of the OH stretching transitions. Cross sections for nu = 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 nu OH = 4 transition with thermal excitation of low frequency modes or rotational motion and nu OH = 5 transitions have sufficient energy for the reaction to proceed following overtone excitation.