化学反应的内禀反应坐标法（X）：氨基卡宾脱氢反应的从头计算研究

氨基卡宾作为重要的反应中间体引起了人们的兴趣,它可分别通过1,1-H_2消除和1,2-H_2消除2种脱氢方式分别生成氰和异氰,但对这两个反应过程的细致研究至今未见报道,本文利用内禀反应坐标(IRC)法对氨基卡宾的2种脱氢反应途径进行微观动力学解析,并对反应途径上的振动相关问题做了理论探讨。

The IRC Method in Chemical Reactions ( X ) --The Ab inttio Study on the Dehydrogenations of Amino-Carbene

The ab initio calculations have been performed on the reaction paths of 1,1- and 1,2-dehy-drogenations of amino- carbene. We have determined the geometries and energies of two transition states, and obtained the activation energies, frequency factors and the activation entropies at the RHF/4-31G level. The vibrational correlation from the reactant to the transition state indicated that the IRC of 1,1-H2 elimination was associated with the deformation mode of 1491 cm-1, and the IRC of 1,2-H2 elimination was connected with the C-H bond asymmetrical stretching mode. The vibrational coupling between normal coordinates occuring in the 1,1-H2 elimination path was strong, and that occured in the 1,2-H2 elimination path was weak. The results provided some useful informations and introduction for the study of laser-inducing and mode-selective chemical reaction.