Full dimensional time-dependent quantum dynamics study of the H+NH3 - H-2+NH2 reaction

摘要

A rigorous full dimensional time-dependent wave packet method has been developed for the reactive scattering between an atom and a tetra-atomic molecule. The method has been applied to the hydrogen abstraction reaction H+NH3 -> H-2+NH2. Initial state-selected total reaction probabilities are investigated for the reactions from the ground vibrational state and from four excited vibrational states of ammonia. The total reaction probabilities from two lowest "tunneling doublets" due to the inversion barrier for the umbrella bending motion of NH3 and from two pairs of doubly degenerate vibrational states of NH3 are also inspected. Integral cross sections and rate constants are calculated for the reaction from the ground state with the centrifugal-sudden approximation. The calculated results are compared with those from the previous seven dimensional calculations [M. Yang and J. C. Corchado, J. Chem. Phys. 126, 214312 (2007)]. This work shows that the full dimensional rate constants are a factor of 3 larger than the corresponding seven dimensional calculated values at T=200 K and are overall smaller than those obtained from the variational transition state theory in the whole temperature region. The work also reveals that nonreactive NH bonds of NH3 cannot be treated as spectators due to the fact that three NH bonds are coupled with each other during the reaction process.