气相中VO_2^++CH_4反应的理论研究

Theoretical Study of the Reaction of VO_2^++CH_4 in the Gas Phase

运用密度泛函B3LYP/6-311++G(3df,3pd)//6-311G(2d,p)法研究了VO2+(1A1/3A')+CH4生成P1[V(OCH2)++H2O]和P2[(OCH2)++H2]的气相反应,揭示了VO2+活化甲烷的微观机理,研究结果表明生成P2的反应是主反应通道,并对影响反应机理和反应速率的势能面交叉现象进行了讨论。

The gas-phase reaction of VO2＋ （1A1/3A＇） ＋ CH4 generated P1 [ V （OCH：） ＋ ＋ H20] and P2 [ （OCH2 ）＋ ＋ H2 ] has been studied by using density functional theory （DFT） at the B3LYP/6-311 ＋ ＋ G （3df, 3pd）//6-311G（2d,p） level, which reveals the reaction mechanism of activation of C-H bond of CH4by VO2＋. The research results show that the re- action channel of forming P2 is the dominant one. The potential energy surface-crossing phenomenon is also discussed which dramatically affects reaction mechanism and reaction rate.