An eight-dimensional quantum mechanical Hamiltonian for X+YCZ3 system and its applications to H+CH4 reaction

An eight-dimensional quantum mechanical Hamiltonian has been proposed based on Palma and Clary's model in which the non-reacting CZ(3) group keeps a C-3v symmetry in the X + YCZ(3) <-> XY + CZ(3) reaction J. Palma and D. C. Clary [J. Chem. Phys. 112, 1859 (2000)]. By transforming the original Cartesian coordinate system (x, s) into a scaled polar coordinate system (q, gamma), the vibrational Hamiltonian of CZ(3) group is expressed in a simple form with a clear physical picture. This Hamiltonian is used to investigate the H + CH4 -> H-2 + CH3 reaction on the Jordan-Gilbert potential energy surface. The total reaction probabilities are calculated for the initial ground state, and umbrella, bending, symmetric, and asymmetric stretching excited states of CH4 with total angular momentum J = 0. The integral cross sections for the reaction are also studied for these initial vibrational states with a centrifugal-sudden approximation. The total integral cross sections for the asymmetric stretching vibrational excited state are in good agreement with the experimental observations. The results also showed the difference of dynamical behavior between reactions from symmetric and asymmetric stretching excited states. The thermal rate constants are calculated for the temperature range T = 250-2000 K and compared with the experimental and other theoretical results. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4764358]