HCN和氯反应动态学及产物振动态分布的计算  

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

作　　者：张燕军[1] 李宗和[2] 曹晓燕[2] 

机构地区：[1]中国药品生物制品检定所,北京100050 [2]北京师范大学化学系,北京100875

出　　处：《物理化学学报》1999年第1期10-14,共5页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金

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。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.

关 键 词：氰氢酸 产物态分布 氯 反应动态学 氰根 振动态 

分 类 号：O613.71[理学—无机化学] O613.42[理学—化学]