The quantum dynamics of interfacial hydrogen: Path integral maximum entropy calculation of adsorbate vibrational line shapes for the H/Ni(111) system

Abstract

Vibrational line shapes for a hydrogen atom on an embedded atom model (EAM) of the Ni(111) surface are extracted from path integral Monte Carlo data. Maximum entropy methods are utilized to stabilize this inversion. Our results indicate that anharmonic effects are significant, particularly for vibrational motion parallel to the surface. Unlike their normal mode analogs, calculated quantum line shapes for the EAM potential predict the correct ordering of vibrational features corresponding to parallel and perpendicular adsorbate motion. (C) 1997 American Institute of Physics.