title: Experimental and theoretical study of the OH vibrational spectra and overtone chemistry of gas-phase vinylacetic acid.
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.
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado, Campus Box 215, Boulder, Colorado 80309, USA.
authors.forename: Meghan E
authors.initials: ME
authors.lastname: Dunn
authors.forename: George C
authors.initials: GC
authors.lastname: Shields
authors.forename: Kaito
authors.initials: K
authors.lastname: Takahashi
authors.forename: Rex T
authors.initials: RT
authors.lastname: Skodje
authors.forename: Veronica
authors.initials: V
authors.lastname: Vaida
mesh_terms: D002087:Butyrates / Q000737:chemistry*; D003198:Computer Simulation; D005740:Gases / Q000737:chemistry; D006878:Hydroxides / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared / Q000379:methods; D014732:Vibration
chemical_list: D002087:Butyrates; D005740:Gases; D006878:Hydroxides; C479121:3-butenoic acid; C031356:hydroxide ion