NO和HSO偶联及其异构化反应机理

摘要

采用G2M（CC5）//MPW1PW91/6-311+G（2df，p）方法，研究了HSO和NO偶联及其异构化反应机理，获得了各物种的几何构型和频率数据，并构建了标题反应的势能剖面。结果表明，该反应存在3条不同路径，优势路径为R（NO+HSO）→IM1→TS1→IM2，其表观活化能为42.38 kJ· mol-1。此过程为NO中N原子与HSO中O原子偶合形成中间体IM1，接着IM1中SH基团从O（1）原子迁移到O（2）原子上后反应完成。%Coupling and isomeric mechanism of NO and HSO are calculated at the G2 M( CC5 )//MPW1 PW91/6-311+G(2df,p)level. Geometries and frequencies of all the species are obtained,and potential energy surface is constructed. The result shows that the reaction has three paths,and the major path is R→IM1→TS1→IM2 with the apparent activation energy of 42. 38 kJ·mol-1 . The detailed process of the dominant path is the coupling of N atom in NO with O atom in HSO,leading to the formation of IM1. Subsequently,the transfer of SH group in IM1 from O(1)atom to O(2)atom.