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采用密度泛函理论的B3LYP方法,在6-311++G(d,p)基组水平上研究了CH?3自由基与HNCO的微观反应机理,优化了反应过程中的反应物、中间体、过渡态和产物,为了获得更精确的能量信息,还计算了体系在反应途径上各驻点的能量.振动分析和IRC分析结果证实了中间体和过渡态的真实性,计算所得的键鞍点电荷密度的变化情况也确认了反应过程.对于CH?3自由基与HNCO反应,找到了七条可行的反应通道,对结果的分析表明:通道CH?3+HNCO→TS7→IM4→TS9→IM5,控制步骤活化能最低,是该反应的主要通道.在该反应体系中质子迁移过程反应活化能不高,也是能发生的.
The B3LYP method of density functional theory (DFT) was used to study the microscopic reaction mechanism of CH? 3 radical with HNCO on the 6-311 ++ G (d, p) basis set. The reaction products, intermediates , Transition states and products, in order to obtain more accurate energy information, the energies of the stagnation points in the reaction pathway are also calculated.The vibration analysis and IRC analysis results confirm the authenticity of the intermediates and transition states, the calculated bond saddle point The reaction process was also confirmed by the change of charge density.For the reaction of CH 3 with HNCO, seven feasible reaction channels were found, and the results showed that CH 3 + HNCO → TS 7 → IM 4 → TS 9 → IM 5, The control step has the lowest activation energy and is the main channel for the reaction, and it is also possible that the reaction activation energy of the proton migration process in the reaction system is not high.