物理化学学报 >> 1995, Vol. 11 >> Issue (08): 716-718.doi: 10.3866/PKU.WHXB19950809

研究论文 上一篇    下一篇

单分子微正则系综振动选模反应速率常数的计算

冯文林,王艳,张绍文,李宗和   

  1. 北京师范大学化学系|北京 100875
  • 收稿日期:1994-10-07 修回日期:1994-12-05 发布日期:1995-08-15
  • 通讯作者: 冯文林

Calculation on the Microcanonical Unimolecular Rate Constants for the Vibrational-state-selected Reactions

Feng Wen-Lin,Wang Yan,Zhang Shao-Wen,Li Zong-He   

  1. Department of Chemistry,Beijing Normal University,Beijing 100875
  • Received:1994-10-07 Revised:1994-12-05 Published:1995-08-15
  • Contact: Feng Wen-Lin

摘要:

以过渡状态理论为基础,研究了单分子振动选模反应的微正则系综速率常数的计算方法.在计算中考虑了量子力学隧道效应校正及振动对沿IRC运动的耦合作用校正.以反应C=CH(F)→HC≡CF的氢迁移反应和C=CF2→FC≡CF的氟迁移反应为例,研究了它们的面外振动选模反应的速率常数.结果表明,这两个反应在低能区有明显的选模性,在高能区选模性减弱.

关键词: 单分子反应, 速率常数, 振动选模

Abstract:

The calculation on the microcanonical unimolecular rate constants for the vibrational-state-selected reactions has been studied on the basis of the transition state theory. The quantum mechanic tunneling correction and the coupling correction are involved in the calculations. As examples, the vibrational-state-selected rate constants of the out-of-plane vibration mode for both reactions C=CH(F)→HC≡CF and C=CF2→FC≡CF have been calculated. The results show that the out-of-plane vibration exhibits a significant high energy regions.

Key words: Unimolecular reaction, Rate constant, Selected vibration mode