【摘要】 用密度泛函理论(DFT)的B3LYP方法,在6-311G、6-311+G(d)、6-311++G(d,p)基组水平上研究了CH3CF2O2与HO2自由基反应机理.结果表明,CH3CF2O2与HO2自由基反应存在两条可行的通道.通道CH3CF2O2+HO2邛IM1邛TS1邛CH3CF2OOH+O2的活化能为77.21kJ·mol-1,活化能较低,为主要反应通道,其产物是O2和CH3CF2OOH.这与实验结果是一致的;而通道CH3CF2O2+HO2邛IM2邛TS2邛IM3邛TS3邛IM4+IM5邛IM4+TS4邛IM4+OH+O2邛TS5+OH+O2邛CH3+CF2O+OH+O2邛CH3OH+CF2O+O2的控制步骤活化能为93.42kJ·mol-1,其产物是CH3OH、CF2O和O2.结果表明这条通道也能发生,这与前人的实验结果一致.更多还原

【Abstract】 Density functional theory (DFT) B3LYP method was employed to study the mechanism of the reac- tion of CH3CF2O2 radical and HO2 radical at the 6-311G?6-311+G(d)?6-311++G(d, p) levels. The results indi-cate that there are two reaction pathways in this reaction. The main reaction pathway is CH3CF2O2 +HO2→IM1→TS1→CH3CF2OOH+O2, the corresponding activation energy is 77.21 kJ·mol-1, and the main products are O2 and CH3CF2OOH. They are in good agreement with the experimental results. The other reaction pathway is CH3CF2O2+ HO2→IM2→TS2→IM3→TS3→IM4+ IM5→IM4+ TS4→IM4+OH+O2→TS5+OH+O2→CH3+CF2O+OH+O2→CH3OH+CF2O+O2, and the corresponding activation energy is 93.42 kJ·mol-1. The results show that this reaction pathway can also occur, and it is in agreement with the results in literatures.更多还原