Nonadiabatic time-dependent wave packet study of the D++H2 reaction system

A theoretical investigation on the nonadiabatic processes of the D+ + H-2 reaction system has been carried out by means of exact three-dimensional nonadiabatic time-dependent wave packet calculations with an extended split operator scheme (XSOS). The diabatic potential energy surface newly constructed by Kamisaka et al. (J. Chem. Phys. 2002, 116, 654) was employed in the calculations. This study provided quantum cross sections for three competing channels of the reactive charge transfer, the nonreactive charge transfer, and the reactive noncharge transfer, which contrasted markedly to many previous quantum theoretical reports on the (DH2)(+) system restricted to the total angular momentum J = 0. These quantum theoretical cross sections derived from the ground rovibrational state of H-2 show wiggling structures and an increasing trend for both the reactive charge transfer and the nonreactive charge transfer but a decreasing trend for the reactive noncharge transfer throughout the investigated collision energy range 1.7-2.5 eV. The results also show that the channel of the reactive noncharge transfer with the largest cross section is the dominant one. A further investigation of the v-dependent behavior of the probabilities for the three channels revealed an interesting dominant trend for the reactive charge transfer and the nonreactive charge transfer at vibrational excitation v = 4 of H-2. In addition, the comparison between the centrifugal sudden (CS) and exact calculations showed the importance of the Coriolis coupling for the reactive system. The computed quantum cross sections are also compared with the experimental measurement results.