CH_3NO_2和CH_3ONO分解反应的量子化学和电子密度拓扑分析

Topological Study on Quantum Chemistry and Electronic Density Decomposition Reaction of CH_3NO_2 and CH_3ONO

采用B3LYP,MP2(full)和CCSD(T)方法在6-311G(d,p)水平上对三线态CH3NO2和异构体CH3ONO分解反应的微观机理进行了理论研究.优化得到了反应势能面上各驻点的几何构型,振动频率分析证实了过渡态的真实性,内禀反应坐标跟踪验证了过渡态与反应物和产物的连接关系.研究表明:CH3ONO通过TS1反应通道分解CH3和NO2,通过TS2通道生成CH3O和NO;CH3NO2通过TS3反应通道生成CH3和NO2.3个分解反应都是自然条件下较容易发生的分解反应.电子密度拓扑研究表明:TS1分解反应过程中存在一个三元环.

The decomposition mechanism of CH3NO2 and CH3ONO has been investigated by using B3LYP,MP2（full） and CCSD（T） methods at 6-311G（d,p） level.Geometries of stationary points on reaction potential surfaces were optimized by three methods mentioned above.Transition states were confirmed by vibration analysis.The connecting relationship of the transition states with the reactants and products are confirmed by the intrinsic reaction coordinates calculation.It was found that TS1 channel was that CH3ONO decomposed into CH3 and NO2,TS2 channel was that CH3ONO decomposed into CH3O and NO,TS3 channel was that CH3NO2 decomposed into CH3 and NO2.They can decompose under natural conditions.Topological analysis of electronic density was demonstrated that there appeared a three-membered ring during TS1 channel.