物理化学学报 >> 2005, Vol. 21 >> Issue (05): 490-493.doi: 10.3866/PKU.WHXB20050506

研究论文 上一篇    下一篇

CH3CF2O2与HO2自由基反应机理的理论研究

李来才; 朱元强; 查东; 田安民   

  1. 四川师范大学化学学院, 成都    610066;    四川大学化学学院, 成都    610064
  • 收稿日期:2004-09-22 修回日期:2004-11-29 发布日期:2005-05-15
  • 通讯作者: 李来才 E-mail:liline33@sohu.com

Theoretical Study on the Mechanism of the Reaction of CH3CF2O2 with HO2 Radical

LI Lai-Cai; ZHU Yuan-Qiang; ZHA Dong; TIAN An-Min   

  1. College of Chemistry, Sichuan Normal University, Chengdu 610066; College of Chemistry, Sichuan University, Chengdu 610064
  • Received:2004-09-22 Revised:2004-11-29 Published:2005-05-15
  • Contact: LI Lai-Cai E-mail:liline33@sohu.com

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→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.

关键词: 反应通道, 过渡态, 活化能, CH3CF2O2

Abstract: 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.

Key words: Reaction pathway, Transition state, Activation energy, CH3CF2O2