关键词: 自由基, 从头算方法, 反应机理

Abstract:

The mechanisms of the CH2＋ O2→ H2O＋ CO and CH2＋ O2→ H2＋ CO2 reactions have been studied by performing ab initio CAS(8,8)/6-31G(d,p) calculations, and five intermediates(IMn) and eight transitions(TSn) have been located along the reaction paths. The predicted path for the CH2＋ O2→ H2O＋ CO is: CH2＋ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS4→ IM4a→ TS5→ H2O＋ CO. For the CH2＋ O2→ H2＋ CO2 reaction, there are two paths: (i) CH2＋ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS6→ H2＋ CO2 and (ii) CH2＋ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS4→ IM4a→ TS7→ IM4b→ TS8→ H2＋ CO2, with the latter path more favorable energetically.

Key words: Radical, Ab initio study, Reaction mechanism