气相中二氧化钒活化甲烷C-H键的理论研究

Theoretical study of the C- H bond of methane activation by VO_2^+ in the gas phase

运用密度泛函B3LYP/6-311++G(3df,3pd)//6-311G(2d,p)法研究了VO+2(1A1/3A')+CH4生成P1[V(OCH2)++H2O]和P2[(OCH2)++H2]的气相反应,揭示了VO+2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+( 1 A1/3 A′) +CH4 to yield P1 [ V ( OCH2 ) + +H2 O ] and P2 [ ( OCH2 ) ++H2 ] has been studied using density functional theory ( DFT) at the B3LYP/6-311++G (3df, 3pd)//6-311G(2d,p) level.And the reaction mechanism of activation of C-H bond of CH4 by VO2+has been investigated.The computational results manifest that the reaction channel of forming H2 is the dominant one.The potential energy curve-crossing dramatically affecting reaction mechanism and reaction rate has been discussed.