化学反应的内禀反应坐标法VI. 甲胺脱氢反应的反应路径解析

本文用内禀反应坐标(IRC)法对甲胺的1,1-和1,2-脱氢反应途径进行了微观动力学解析。在RHF/4-31G水平上确定了反应的过渡态结构和势能变化曲线,得到了活化能、反应热、频率因子和活化熵等物理量。模式选择研究表明:1,1-和1,2-脱氢反应过程的反应坐标(IRC)分别与反应物中频率为1057和1348cm^-^1的两个变形振动模式相联结。在每条反应途径上都存在正则坐标间的振动耦合。本文的计算为激光诱导和模式选择化学反应的研究提供了重要信息和理论指导。

The TRC method in chemical reactions

The ab initio calculations have been performed on the reaction paths of 1, 1- and 1, 2-dehydrogenation of methylamine by the Intrinsic Reaction Coordinate (IRC) method. The transition state structures and the potential energy curves have been determined, and the activation energies, reaction heats, the activation entropies, and reactional frequency factors have been obtained on the RHF/4-31G level. The mode- selective study reveals the IRC of 1, 1- and 1, 2-H~2 elimination to be connected respectively with the deformation modes of 1057 and 1438cm^-^1 of the reactant. The vibration coupling between the normal coordinates occured in either of these two reaction paths. These results have provided an useful information and theoretical introduction for the studying of laser-inducing and mode-selective chemical reactions.