CH3CF2O2与HO2自由基反应机理的理论研究

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→IM1→TS1→CH₃CF₂OOH＋O₂的活化能为77.21 kJ•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→IM2→TS2→IM3→TS3→IM4＋IM5→IM4＋TS4→IM4＋OH＋O₂→TS5＋OH＋O₂→CH₃＋CF₂O＋OH＋O₂→CH₃OH＋CF₂O＋O₂的控制步骤活化能为93.42 kJ•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.

Theoretical Study on the Mechanism of the Reaction of CH3CF2O2 with HO2Radical

Density functional theory (DFT) B3LYP method was employed to study the mechanism of the reaction of CH₃CF₂O₂ radical and HO₂ radical at the 6-311G、6-311+G(d)、6-311++G(d, p) levels. The results indicate 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 CH₃CF₂O + 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.