摘要
电荷密度拓扑分析方法(topological analysis of charge distribution)已经被广泛应用于研究化合物的各种静态性质及反应特性.对IRC反应途径上过渡态附近构型的拓扑性质研究报导较少.本工作是用电荷密度分布的拓扑分析方法对HCN→HNC异构化反应IRC过渡态附近的性质进行了研究.对电荷密度分布拓扑分析和IRC途径确定选用相同的基组,得到了一些新的结论。
In this paper,thermal isomerization of HCN to isocyanide HNC has been studied.The topological properties of the structures of some points on IRC path in the vici-nity of transition state have been analyzed. It is found that the transition state forHCN→HNC isomerization reaction is a bond switching point on IRC path in view ofits topological properties. It is a point wherc the 'old' chemical bond H--C beginsto break and a 'new' bond between H atom and the bond critical point of CN beginsto form and this state lasts for a period about ΔS=0.3 (from S=0.00 to S=0.30)on the IRC path. The changes of other properties along the IRC reaction path hasalso been discussed. Together with the reverse reaction, it is realized that the changing of topolo-gical properties of structures in the vicinity of transition state on IRC path is dif-ferent for exothermal and endothermal reactions.
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
1992年第6期724-727,共4页
Acta Physico-Chimica Sinica
基金
国家自然科学基金
国家教委博士点基金
关键词
过渡态
HCN
异构化反应
氢化氰
Topological analysis
IRC
transition state
HNC
HCN
