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

Authors

George C. Shields, Bucknell UniversityFollow
Meghan E. Dunn
Kaito Takahashi
Rex T. Skodje
Veronica Vaida

Publication Date

2008

Description

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 ν_OH = 4 transition with thermal excitation of low frequency modes or rotational motion and ν_OH = 5 transitions have sufficient energy for the reaction to proceed following overtone excitation.

Journal

The Journal of Physical Chemistry A

Volume

112

Issue

41

First Page

10226

Last Page

10235

Department

Chemistry

Link to Published Version

http://dx.doi.org/10.1021/jp805746t

Recommended Citation

Shields, George C.; Dunn, Meghan E.; Takahashi, Kaito; Skodje, Rex T.; and Vaida, Veronica. "Experimental and Theoretical Study of the OH Vibrational Spectra and Overtone Chemistry of Gas-Phase Vinylacetic Acid." The Journal of Physical Chemistry A (2008) : 10226-10235.