D2 dissociative adsorption on and associative desorption from Si(100): Dynamic consequences of an ab initio potential energy surface

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Abstract
Dynamical calculations are reported for D2dissociativechemisorption on and associative desorption from a Si(100) surface. These calculations use the dynamically relevant effective potential which is based on an ab initiopotential energy surface for the ‘‘pre‐paired’’ species. Three coordinates are included dynamically; the distance to the surface, the D–D bond length and a Si phonon coordinate. Other coordinates (multidimensionality) have been included via a static approximation. Both an asymmetric and symmetric reaction paths are considered. While energetics favors the asymmetric path, phase space favors the symmetric one. Under the conditions of many experiments, either could dominate. The calculations show quite weak dynamic coupling to the Si lattice for both paths, i.e., weak surface temperature dependences to dissociation and small energy loss to the lattice upon desorption. These calculations do not support previous suggestions that either a strong coupling to the lattice or ‘‘entropic’’ effects can reconcile the apparent violation of detailed balance obtained by comparing experimental dissociation to desorption barriers. In fact, the results reported here do not agree with several experimental findings. We discuss several possibilities for this disagreement, including experimental artifact, limitations in the dynamical model and even the possibility that electronically adiabatic dynamics involving the ‘‘pre‐paired’’ species is not relevant to experiments on real systems.

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