Coriolis-coupled wave packet dynamics of H + HLi reaction

Abstract

We investigated the effect of Coriolis coupling (CC) on the initial state-selected dynamics of H + HLi reaction by a time-dependent wave packet (WP) approach. Exact quantum scattering calculations were obtained by a WP propagation method based on the Chebyshev polynomial scheme and ab initio potential energy surface of the reacting system. Partial wave contributions up to the total angular momentum J = 30 were found to be necessary for the scattering of HLi in its vibrational and rotational ground state up to a collision energy ∼0.75 eV. For each J value, the projection quantum number K was varied from 0 to min (J, Kmax), with Kmax = 8 until J = 20 and Kmax = 4 for further higher J values. This is because further higher values of K do not have much effect on the dynamics and also because one wishes to maintain the large computational overhead for each calculation within the affordable limit. The initial state-selected integral reaction cross sections and thermal rate constants were calculated by summing up the contributions from all partial waves. These were compared with our previous results on the title system, obtained within the centrifugal sudden and J-shifting approximations, to demonstrate the impact of CC on the dynamics of this system. © 2006 American Chemical Society.