Dynamics of dissociative chemisorption Cl2/Si(111)-2 × 1

Abstract

We present a new theoretical methodology for investigating the process of dissociative chemisorption which consists of performing fully ab initio dynamical simulations of the dissociation process. The advantages of the new methodology are: the inclusion of the degrees of freedom of both the incident molecule and the atoms in the surface; an extremely accurate representation of the interatomic potentials over the relevant regions of configuration space and the absence of any assumptions about the nature of the dissociation process. The limitations of the technique are: the restriction of ground-state electronic configurations; the use of classical dynamics to evolve the ionic trajectories and inadequate statistics. It is shown that this final limitation is already being overcome by the continuing increase in the power of modern computers.