Hydrogen dissociation dynamics on precovered Pd surfaces: Langmuir is still right.

A recent scanning tunneling microscopy study by Mitsui et al. [Nature (London) 422, 705 (2003)] challenged the well-accepted picture based on early studies of Langmuir that an ensemble of at least two empty, catalytically active sites is required for the dissociative adsorption; instead, aggregates of three or more vacancies should be necessary. We have performed the first ab initio molecular dynamics study of the adsorption dynamics on a precovered surface providing detailed insights into the coverage dependence of the adsorption probability. The simulations show that there is no need to refine the Langmuirian picture: A dimer vacancy is still sufficient to dissociate hydrogen provided the kinetic energy of the molecules is large enough to overcome the relatively small adsorption barrier. In addition, we elucidate further aspects of the dissociation dynamics at precovered surfaces.