高等学校化学学报

高等学校化学学报 ›› 1995, Vol. 16 ›› Issue (3): 444.

• 论文 • 上一篇    下一篇

C2H2++H2→C2H3++H反应振动选态速率常数的理论研究

于浩, 刘若庄, 李宗和, 马思渝   

  1. 北京师范大学化学系, 北京 100875
  • 收稿日期:1994-05-26 修回日期:1994-09-16 出版日期:1995-03-24 发布日期:1995-03-24
  • 通讯作者: 刘若庄
  • 作者简介:于浩,男,28岁,博士研究生.
  • 基金资助:

    国家自然科学基金

Theoretical Study on Vibrational State-Selected Rate Constants of the Reaction C2H2++H2→C2H3++H

YU Hao, LIU Ruo-Zhuang, LI Zong-He, MA Si-Yu   

  1. Department of Chemistry, Beijing Normal University, Beijing 100875
  • Received:1994-05-26 Revised:1994-09-16 Online:1995-03-24 Published:1995-03-24

PDF (PC)

摘要： 用从头计算法辅以能一梯度法优化了反应C2H2++H2→C2H3++H的过渡态,用福井谦一的理论求出反应途径,用反应途径哈密顿理论及正则变分过渡态理论计算沿反应途径的动力学性质和反应速率常数。在此基础上对涉及振动激发的选态反应速率常数进行计算,所得结果与现有的实验结果相符合。

关键词: 从头计算, 变分过渡态, 分子反应动力学, 振动选态反应速率常数

Abstract: The reaction path of the reaction C2H2++ H2→C2H3++Hhas been traced by Fukui's theory of intrinsic reaction coordinate by using an ab initio MO method with the gradient technique. Furthermore, the dynamical properties along the reaction path and CVT rate constants with correction of tunneling effect and effect of curvature have been investigated by reaction path Hamiltonian theory and variational transition state theory. On this basis,the enhancement of rate constant by vibrational excitation of C-C stretching mode has beencalculated. The calculated vibrational enhancement is of the same order of magnitude with the experimentally estimated value.

Key words: Ab initio calculation, Variational transition state, Molecular reaction dynamics, Vibrational-state-selected rate constant

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