The influence of potential energy surface topologies on the dissociation of H2

Abstract

In this work we present a theoretical study of the dissociative adsorption of hydrogen molecules from a series of model potential energy surfaces. The aim is to discover those particular topological features in the potential surface which are responsible for determining the vibrational state‐to‐state cross sections in both the dissociated and the scattered flux. The potential energy surface is two‐dimensional, and is chosen to be deliberately simple; a combination of Morse potentials and a Gaussian barrier. A quantum wave packet is chosen to represent the molecule and the dynamics are solved by a spectral grid method. Results show that the location of the barrier influences the scattering cross sections markedly. Early barriers result in vibrationally excited adsorbed species while late barriers produce translationally hot atoms. The individual state distributions resulting from the two model potentials are quite different. In addition, results are given for a potential where the activation barrier is deep in the exit channel. For this case, results show that molecules can trap near the barrier for significant times without invoking substrate degrees of freedom. This is explained in terms of trapping in dynamic wells. Finally, we assess the effect on dissociation probability following vibrational excitation of the hydrogen molecule.