摘要/Abstract

准经典分子动态学模拟方法结合了经典分子动力学和电子结构理论, 从原子/分子层面研究化学反应的动态机制, 不但能模拟反应体系中相应产物或中间体的统计学分布, 还可提供时间尺度下化学键生成/断裂的信息. 密度泛函理论(DFT)计算在反应机制研究中已被广泛应用, 但从准经典分子动态学角度的研究还相对较少, 比如分叉过渡态的现象及其选择性、环加成协同机制中出现的分步过程以及绕过常见的中间体而直接生成产物等. 这些新颖机制的研究通常需要分子动态学, 有些甚至打破了传统过渡态理论的认知. 综述了近年来有机化学反应机制的准经典分子动态学研究进展, 强调机制中的动态学效应, 旨在加深人们对有机反应机制的理解并拓宽有机化学理论.
关键词: 准经典分子动态学, 分叉过渡态, 协同机制, 分步机制, 动态学效应
Quasi-classical molecular dynamics is a computational method that combines classical molecular dynamics and electronic structure theory, which can not only simulate the statistics of the corresponding products or intermediates in the reaction mechanism, but also provide dynamic information of chemical bond formation/cleavage on time scales. Density functional theory (DFT) calculation has been widely used in the research of reaction mechanism, but there are relatively few studies from the perspective of quasi-classical molecular dynamics, such as the phenomenon of bifurcations of transition states and their selectivity, stepwise processes appear in the concerted mechanism of cycloaddition, bypassing common intermediates and directly generating products, etc. These novel mechanism processes often require molecular dynamics, and some even break the cognition of traditional transition state theory. The recent research progress of quasi-classical molecular dynamics of organic chemical reaction mechanisms is reviewed, with emphasis on the dynamic effect in the mechanism, in order to deepening people's understanding of organic reaction mechanisms and broaden the theory of organic chemistry.
Key words: quasi-classical molecular dynamic, bifurcation of transition state, concerted mechanism, stepwise mechanism, dynamic effect


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