Origin of Steric Effects in Methane Dissociative Chemisorption

Abstract

Steric effects in chemical reactions, namely, the dependence of reactivity on reactant spatial orientation and/or alignment, provide valuable information on the anisotropic potential energy surface and access to the transition state. However, a theoretical interpretation of steric effect is often not straightforward because of convolution of the dynamics by many other factors. Here, we present a theoretical study on the dissociative chemisorption of methane using a quasi-classical trajectory method on a density functional theory based global potential energy surface and offer a theoretical interpretation of the interesting but surprising steric effect in this prototypical and industrially relevant gas–surface reaction.