CF_3O_2自由基和NO反应机理的理论研究  

Theoretical Study on the Mechanism of the Reaction of CF_3O_2 with NO

作　　者：郑妍[1] 查东[1] 李来才[1] 

机构地区：[1]四川师范大学化学与材料科学学院,成都610066

出　　处：《物理化学学报》2006年第2期156-160,共5页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20277014);四川省自然科学基金(05JY029-038);四川省青年基金(04ZO026-043)资助

摘　　要：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70.86kJ·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.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 am 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.

关 键 词：反应通道 过渡态 活化能 CF3O2由基 

分 类 号：O621.25[理学—有机化学]