Singlet and Triplet Reaction Paths for Gas-Phase Zr + C2H4 by Density Functional Theory

摘要: We use the B3LYP density functional theory with a large basis set to characterize stationary points on both triplet and singlet potential energy surfaces for gas-phase reaction Zr + C2H4 → ZrC2H2 H2. The previously described stepwise rearrangement path occurs surface, requiring passage over substantial exit channel barrier. A new, lower involves concerted of HZrC2H3 insertion intermediate directly weakly bound, product-like complex no barrier products. new low-energy from strongly bound dihydrido species H2ZrC2H2, which then dissociates products small 4 kcal/mol. argue that is more consistent than either experimental product kinetic distribution, peaks at 3−5 This in turn suggests access surface via fast intersystem crossing f...