CH3CN与CH3自由基反应机理的理论研究  

Theoretical Investigation on the Reaction Mechanism of CH3CN and CH3 Radical

作　　者：李明悦 马咏梅 谢春福[2] Li Mingyue;Ma Yongmei;Xie Chunfu(College of Chemistry and Material,Weinan Normal University,Weinan 714099,China;School of Natural and Applied Sciences,Northwestern Polytechnical University,Xi’an 710072,China)

机构地区：[1]渭南师范学院化学与材料学院,陕西渭南714099 [2]西北工业大学理学院化学化工系,陕西西安710072

出　　处：《山东化工》2021年第1期54-56,共3页Shandong Chemical Industry

基　　金：大学生创新创业训练计划项目(18XK069)。

摘　　要：用量子力学研究了CH3自由基与CH3CN的气相反应机理,并用过渡态理论研究了反应的动力学性质,找到了抽氢和取代两种反应通道。在B3PW91/6-311G(d,p)级别上优化得到了反应物、产物和过渡态的几何构型,用高级别计算方法G3(MP2)和CBS-QB3对单点能进行了校正,得到了反应势能面,用(CVT/SCT)方法计算了反应在200~2000 K温度范围内的速率常数,结果表明计算值与实验值符合的较好,氢抽提反应在计算的整个温度区间内都是主反应通道。The mechanism on the reaction of CH3 radical and CH3CN is explored using the density functional theory.Two kinds of reaction mechanisms are found with hydrogen abstraction reaction and substitution reaction.The geometries of reactants,intermediates and products are optimized at B3PW91/6-311G(d,p)level.In order to establish the accurate potential energy surface,the single point energies are obtained by G3(MP2)and CBS-QB3.The rate constants for each channel are calculated using the canonical variational transition state theory(CVT)in the temperature range of 200~2000 K.The results indicate that the calculated rate constants are in very good agree with the available experimental detections,and the hydrogen abstraction is main channel in all the temperatures.

关 键 词：抽氢反应 取代反应 速率常数 

分 类 号：O641[理学—物理化学]