Semiclassical Nonadiabatic Dynamics Based on Quantum Trajectories for the O(\u3csup\u3e3\u3c/sup\u3eP,\u3csup\u3e1\u3c/sup\u3eD)+H\u3csub\u3e2\u3c/sub\u3e System

Abstract

The O(3P,1D)+H2→OH+H reaction is studied using trajectory dynamics within the approximate quantum potential approach. Calculations of the wave-packet reaction probabilities are performed for four coupled electronic states for total angular momentum J = 0 using a mixed coordinate/polar representation of the wave function. Semiclassical dynamics is based on a single set of trajectories evolving on an effective potential-energy surface and in the presence of the approximate quantum potential. Population functions associated with each trajectory are computed for each electronic state. The effective surface is a linear combination of the electronic states with the contributions of individual components defined by their time-dependent average populations. The wave-packet reaction probabilities are in good agreement with the quantum-mechanical results. Intersystem crossing is found to have negligible effect on reaction probabilities summed over final electronic states