Six-dimensional quantum dynamics for the dissociative chemisorption of HCl on rigid Ag(111) on three potential energy surfaces with different density functionals

We carried out six-dimensional quantum dynamics calculations for the dissociative chemisorption of HCl on a rigid Ag(111) surface, employing three potential energy surfaces (PESs) which were recently constructed using the neural network approach based on extensive density functional theory calculations with Perdew-Burke-Ernzerhof, Perdew-Wang91, and revised Perdew-Burke-Ernzerhof functionals, respectively. The vibrational excitation of HCl enhances the reactivity substantially, and the dissociation is most favored for HCl molecules colliding with rotation in a plane parallel to the Ag(111) surface (helicopter alignment). The influence of rotational excitation on the dissociation probability is much more complicated, with different trends at high and at low kinetic energies. The usage of three different PESs does not change the effects of vibrational excitation, rotational excitation, and rotational-alignment qualitatively, but it does change the magnitude of dissociation probabilities quantitatively due to the different barrier heights. Published by AIP Publishing