Experimental and theoretical study of the OH vibrational spectra and overtone chemistry of gas-phase vinylacetic acid.
Experimental and theoretical study of the OH vibrational spectra and overtone chemistry of gas-phase vinylacetic acid.
复制标题
气相乙烯基乙酸的 OH 振动光谱和泛音化学的实验和理论研究。
DOI：
10.1021/jp805746t
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发表时间：
2008
期刊：
影响因子：
--
通讯作者：
Vaida,Veronica
中科院分区：
文献类型：
--
作者：
Dunn,MeghanE;Shields,GeorgeC;Takahashi,Kaito;Skodje,RexT;Vaida,Veronica
在这项研究中，我们提出了气相振动光谱的乙烯基乙酸的重点是ν = 1−5振动态的OH伸缩跃迁。根据乙烯基乙酸的蒸气压数据，导出了ν = 1，2，4和5时OH伸缩振动跃迁的截面。从头计算被用来协助在实验光谱的频带分配，并确定阈值的乙烯基乙酸的脱羧。与脱羧反应的理论能垒相比，在低频热激发或转动激发下的νOH= 4跃迁和νOH= 5跃迁具有足够的能量使反应在泛音激发下继续进行。
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.