基态N原子与CS2反应机理的理论研究

用密度泛函理论B3LYP/6 311+G 和高级电子相关偶合簇CCSD(T)/6 311+G 方法,计算研究了四重态氮原子与二硫化碳的反应,找到了分别形成CS+NS、NCS+S和CN+S2三个反应通道,优化搜索了各反应的过渡态,并用频率分析和内禀坐标法(IRC)验证了各鞍点构型和反应路径.在三个反应通道中,反应N+CS2→CS+NS由于具有较低的活化能而容易发生,其它两个通道活化能高很难发生,计算结果与实验结果一致.同时,对反应机理进行了详细的讨论.

Theoretical Studies on the Reaction Mechanism of N and CS2

The reaction of N and CS_2 was studied using the density functional method at B3LYP(full)/6-311+G~* and CCSD(T)/6-311+G~*level. Three reaction channels to form CS + NS, NCS + S and CN + S_2 were found. The transition states were obtained by the QST2(or QST3) method and proved by IRC calculations. The reaction channel (1), N + CS_2→CS + NS, is easier to be achieved than the other two because of its low energy barrier. The result is in agreement with the experimental observations. At the same time, the information for the reaction mechanism was discussed exhaustively.