CH3SH与CN·自由基的反应机理及电子密度拓扑分析

Reaction Mechanisms and Topological Studies of Electronic Density on the Reaction of CH3SH with CN· Radical

在B3LYP/6-311++G(d,p)水平上研究了CH3SH与CN·自由基的反应机理.找到了三个可能的反应通道,得到了各反应通道的反应物、中间体、过渡态和产物的优化构型、谐振频率.通过内禀反应坐标(IRC)跟踪确认了稳定点与过渡态的连接关系.在CCSD/6-311++G(d,p)水平上进行能量校正,成功地解释了Brian等的实验结论.通过对反应进程中一些重要点的电子密度拓扑分析,讨论了反应进程中化学键的变化规律,发现了六元环状过渡结构.

The reaction mechanism of CH3SH with radical CN＊ was investigated by using B3LYP method with 6- 31 l＋＋G（d,p） basis set, and three reaction channels were found. The geometries of the reactants, intermediates, transition states, and products were optimized. Stationary points of the reaction channels were confirmed by the intrinsic reaction coordinate （IRC） tracing, The energies of the species were corrected at CCSD/6-311＋＋G（d,p） level. The calculated results successfully explained the conclusions of Brian＇s experimental study. The cleavage and formation of the chemical bonds in the reaction process were discussed by the topological analysis of electronic density, and the transition state with six-member-ring structure （STS） was found.