CF3O2自由基和NO反应机理的理论研究

用密度泛函理论(DFT)的B3LYP方法, 分别在6-31G、6-311G、6-311+G(d)基组水平上研究了CF3O2自由基和NO反应机理. 研究结果表明, CF3O2自由基和NO反应存在三条可行的反应通道, 优化得到了相应的中间体和过渡态. 从活化能看, 通道CH3O2+NO→IM1→TS1→IM2→TS2→CF3O+ONO的活化能最低, 仅为70.86 kJ•mol-1, 是主要反应通道, 主要产物是CF3O和NO2. 而通道CH3O2+NO→IM1→TS3→CF3ONO2和CH3O2+NO→TS4→IM3→TS5→IM4→TS6→CF3O+NOO的活化能较高, 故该反应难以进行.

Theoretical Study on the Mechanism of the Reaction of CF3O2 with NO

Density Function Theory (DFT) B3LYP method was employed to study the mechanism of the reaction of CF3O2 radical and NO with the 6-31G、6-311G、6-311+G(d) basis sets. The study results indicate that there are three reaction pathways in this reaction. The main reaction pathway is CF3O2+NO→IM1→TS1→IM2→TS2→CF3O+NO2, the corresponding activation energy is 70.86 kJ•mol-1. The other reaction pathways are CF3O2+NO→ IM1→TS3→ CF3ONO2 and CF3O2+NO→TS4→IM3→TS5→IM4→TS6→CF3O+NOO, the corresponding activation energies are 258.71 kJ•mol-1 and 278.60 kJ•mol-1, and these reaction pathways are difficult to carry out. The results show that the main products are CF3O and NO2, which is in agreement with the results in literatures.