高等学校化学学报

高等学校化学学报 ›› 1991, Vol. 12 ›› Issue (7): 965.

• 论文 • 上一篇    下一篇

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

陈彬, 赵成大, 傅强   

  1. 东北师范大学化学系, 长春, 130022
  • 收稿日期:1989-09-25 出版日期:1991-07-24 发布日期:1991-07-24
  • 通讯作者: 赵成大
  • 基金资助:

    国家自然科学基金

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

Chen Bin, Zhao Cheng-Da, Pu Qiang   

  1. Department of Chemistry, Northeast Normal University, Changchun, 130022
  • Received:1989-09-25 Online:1991-07-24 Published:1991-07-24

PDF (PC)

被引次数

1

摘要： 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-H2消除和1,2-H2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。

关键词: 从头计算, IRC解析, 模式选择

Abstract: 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/4-31Glevel. The vibrational correlation from the reactant to the transition state indicated that the IRC of 1,1-H2elimination was associated with the deformation mode of 1491cm-1, and the IRC of 1,2-H2elimination was connected with the C-H bond asymmetrical stretching mode. The vibrational coupling between normal coordinates occuring in the 1,1-H2elimination path was strong, and that occured in the 1,2-H2elimination path was weak. The results provided some useful informations and introduction for the study of laser-inducing and mode-selective chemical reaction.

Key words: Ab initio, IRC analysis, Mode-selection

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