物理化学学报 >> 1999, Vol. 15 >> Issue (01): 10-14.doi: 10.3866/PKU.WHXB19990103

研究论文 上一篇    下一篇

HCN和氯反应动态学及产物振动态分布的计算

张燕军, 李宗和, 曹晓燕   

  1. 中国药品生物制品检定所,北京 100050|北京师范大学化学系,北京 100875
  • 收稿日期:1998-04-06 修回日期:1998-06-02 发布日期:1999-01-15
  • 通讯作者: 曹晓燕

Calculation on the Dynamics and Vibrational State Distribution of Product CN for the Reaction Hydrocyanic Acid and Chlorine

Zhang Yan-Jun, Li Zong-He, Cao Xiao-Yan   

  1. National Institute for the Control of Pharmaceutical Biological Products,Beijing 100050|Chemistry Department,Beijing Normal University,Beijing 100875
  • Received:1998-04-06 Revised:1998-06-02 Published:1999-01-15
  • Contact: Cao Xiao-Yan

摘要:

采用自洽场分子轨道UHF/6-311G**从头计算法,获得了HCN+Cl→HCl+CN反应的内禀反应坐标(IRC). 沿着IRC,计算了反应的动态学性质,根据传统过渡态、变分过渡态理论,得到了反应的理论速率常数,可供实验工作者参考,利用SCP-IOS近似下的产物振动跃迁几率公式,自编程序计算了HCN(004,302)+Cl→HCl+CN反应中产物CN的振动态分布,获得了和实验相一致的结果.

关键词: 氢氰酸, 产物态分布, 从头算

Abstract:

In this paper, based on ab initio methods, the intrinsic reaction coordinate (IRC)of the reaction HCN+Cl→HCl+CN is traced at the basis level of UHF/6-311G. Along the IRC, the dynamical properties of the reaction are investigated. The theoretical rate constants of the conventional transition-state theory and variational transition-state theory are calculated, and they are for experimental reference. The product vibrational state distribution of CN for the reaction HCN(004,302)+Cl→HCl+CN is also calculated by the subroutine which is compiled using vibration transtion probability formula based on SCP-IOS theory. The calculated results are in good agreement with experiments.

Key words: Hydrocyanic acid, Product state distribution, Ab initio