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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Studies on the Kinetics of Multi-Channel Gas-Phase Unimolecular Decomposition of Acetaldehyde
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Theoretical Studies on the Kinetics of Multi-Channel Gas-Phase Unimolecular Decomposition of Acetaldehyde

机译：乙醛多通道气相单分子分解动力学的理论研究

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摘要

Theoretical kinetic studies are performed on the multichannel thermal decomposition of acetaldehyde. The geometries of the stationary points on the potential energy surface of the reaction are optimized at the MP2(full)/6-311++G(2d,2p) level of theory. More accurate energies are obtained by single point energy calculations at the CCSD(T,full)/augh-cc-pVTZ+2df, CBS-Q and G4 levels of theory. Here, by application of steady-state approximation to the thermally activated species CH3CHO* and CH2CHOH* and performance of statistical mechanical manipulations, expressions for the rate constants for different product channels are derived. Special attempts are made to compute accurate energy-specific rate coefficients for different channels by using semiclassical transition state theory. It is found that the isomerization of CH3CHO to the enol-form CH2CHOH plays a significant role in the unimolecular reaction of CH3CHO. The possible products of the reaction are formed via unimolecular decomposition of CH3CHO and CH2CHOH. The computed rate coefficients reveal that the dominant channel at low temperatures and high pressures is the formation of CH2CHOH due to the low barrier height for CH3CHO → CH2CHOH isomerization process. However, at high temperatures, the product channel CH3 + CHO becomes dominant.]]>
机译：<！[cdata [ src ='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jpcafh/2017/jpcafh.2017.121.issue-37/acs.jpca.7b04771/ 20170915 /图像/介质/ JP-2017-04771W_0006.GIF“>对乙醛的多通道热分解进行理论动力学研究。在反应的电位能表面上的静止点的几何形状在MP2（满）/ 6-311 ++ G（2D，2P）理论水平上进行了优化。通过CCSD（T，Full）/ Augh-CC-PVTZ + 2DF，CBS-Q和G4理论水平的单点能量计算获得更准确的能量。这里，通过将稳态逼近施加到热敏物质CH 3 cho *和ch 2 choh *和统计机械操纵的性能，速率常数的表达式衍生不同的产品频道。通过使用半导体转换状态理论来对不同信道计算精确的能量特定速率系数进行特殊尝试。发现CH 3 cho的异构化在烯醇形式CH 2 choh中在CH 3 的单分子反应中起着重要作用CHO。反应的可能产物通过Ch 3 ChO和Ch 2 Choh的单分子分解形成。计算速率系数揭示了低温和高压下的主导通道是CH 2 ChoH由于CH 3 Cho→Ch 2 氯异构化过程。但是，在高温下，产品通道CH 3 + cho成为主导。]]>

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