CH_3O_2+CH_3反应机理的理论计算研究(英文)

Theoretical investigation on the mechanisms of the CH_3O_2 plus CH_3 reaction

在CCSD(T)//B3LYP/6-311++G(3df,2pd)水平上对CH_3O_2+CH_3反应机理进行研究,在单重态和三重态势能面上探索了一些放热反应通道。计算结果显示反应主要发生在单重态势能面上,1im2无势垒解离产生CH3O+CH3O是最可能的反应途径。但是在三重态势能面上,CH_4+CH_2OO可能是主要的产物,其产生需要克服67.6 k J·mol^(-1)的势垒。

Mechanisms of the CH3O2 ＋ CH3 reaction have been studied theoretically at the CCSD （T）//B3LYP/6-311＋＋G （3dr, 2pd） level. Some exothermic pathways were explored on the singlet and triplet potential surfaces. DFT calculations indicate that the reaction should be occurring mainly on the singlet rather than triplet potential surface. On the singlet potential surface, the barrierless dissociation of 1im2 is the most feasible pathways to lead the products ofCH3O ＋ CH3O. But CH4＋CH2OO should be the major products by overcoming a modest barrier of 67.6 kJ.mol-1 on the triplet surface.