摘要
用从头算方法获得了H2＋CN反应的内禀反应坐标（IRC）．沿着IRC，计算了各垂直于IRC的简正模所对应的频率（ω）以及沿IRC运动与垂直于IRC运动的简正模之间的耦合常数（BKF），根据传统过渡态、变分过渡态理论和选态公式，计算了nCN=0及nCN=1时反应的速率常数，并得到了和实验相一致的结果还计算了nCH=1及nCN=1时H＋HCN→H2＋CN反应速率常数。可供实验工作者参考。
In this paper, based on ab initio with gradient technique,the intrinsic reaction coordinate (IRC) of the reaction CN+H2→H+HCN has been traced by using numerical method. Along the IRC, the coupling constants between the IRC and vibrations orthogonal to it, and the vibrational frequencies have all been investigated. The theoretical rate constants for vibrationally excited reactants nCN =1 or nCN = 0 in the conventional transition state theory, variational transition state theory and with tunneling corrections havebeen calculated. They are in good agreement with experimental results. HCN(nCN =1,nCH - 1)+ H→CN+H2 reaction rate constants have also been calculated in this paper, andthe theoretica1 results axe for experimental reference only.
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
1996年第3期239-244,共6页
Acta Physico-Chimica Sinica
基金
国家自然科学基金
关键词
氰基
反应速率常数
选态反应
氢
Cyanide,Intrinsic reaction coordinate(IRC), Reaction rate constant,State-selected reaction
