Dynamics of water dissociative chemisorption on Ni(111): effects of impact sites and incident angles.

Abstract

The dissociative chemisorption of water on rigid Ni(111) is investigated using a quasiclassical trajectory method on a nine-dimensional global potential energy surface based on a faithful permutation invariant fit of ∼25 000 density functional theory points. This full-dimensional model not only confirms the validity of our earlier reduced-dimensional model with 6 degrees of freedom, but also allows the examination of the influence of impact sites and incident angles. It is shown that the reactivity depends on the site of impact in a complex fashion controlled by the topography of the potential energy surface rather than the barrier height alone. In addition, the reaction is promoted by momenta both parallel and perpendicular to the surface, as predicted by the recently proposed sudden vector projection model.