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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photochemistry and Vibrational Spectroscopy of the Trans and Cis Conformers of Acetic Acid in Solid Ar
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Photochemistry and Vibrational Spectroscopy of the Trans and Cis Conformers of Acetic Acid in Solid Ar

机译：固体氩气中乙酸的反式和顺式构象的光化学和振动光谱

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Acetic acid monomer has two stable geometries, the cis and trans conformers. The high-energy cis conformer has been recently detected experimentally for the first time [Ma??as et al. J. Am. Chem. Soc. 2003, 125, 16188]. The cis conformer can be produced in low-temperature rare-gas matrixes upon vibrational excitation of the ground-state trans conformer. Fast tunneling from cis- to trans-acetic acid takes place even at the lowest working temperatures (8 K), limiting the time available to study the high-energy form. Deuteration of the hydroxyl group reduces the tunneling rate by approximately 4 orders of magnitude, increasing accordingly the lifetime of the unstable conformer and its available concentration. In this work, we present a detailed analysis of the vibrational spectra of the cis form of four acetic acid isotopologues (CH_3COOH, CH_3COOD, CD_3COOH and CD_3COOD). Photolysis (193 nm) of the trans and cis forms of the perdeuterated compound was performed to evaluate the possible conformational dependence of photodissociation of acetic acid. However, no evidence of conformer specific photodissociation was found. The UV photolysis of the matrix-isolated acetic acid reveals very different products from the gas phase. Methanol complexed with carbon monoxide is the major product of photolysis of acetic acid isolated in Ar matrixes whereas it has never been observed as a photolysis product in the gas phase.
机译：乙酸单体具有两个稳定的几何结构，即顺式和反式构象体。最近首次通过实验检测到高能顺式构象异构体[Ma？as等人。 J.上午化学Soc。 2003，125，16188]。在基态反式构象异构体的振动激发下，顺式构象异构体可以在低温稀有气体基质中产生。即使在最低工作温度（8 K）下，也可以从顺式乙酸向反式乙酸快速隧穿，从而限制了研究高能形式的时间。羟基的氘化将隧穿速率降低了约4个数量级，从而相应地增加了不稳定构象异构体的寿命及其有效浓度。在这项工作中，我们提供了四个乙酸同位素（CH_3COOH，CH_3COOD，CD_3COOH和CD_3COOD）的顺式振动光谱的详细分析。对氘代化合物的反式和顺式进行光解（193 nm），以评估乙酸光解离的可能构象依赖性。然而，没有发现构象体特异性光解离的证据。基质分离的乙酸的紫外光解显示出与气相截然不同的产物。与一氧化碳络合的甲醇是在Ar基质中分离出的乙酸发生光解的主要产物，而从未在气相中以光解产物的形式被观察到。

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