Quantum nuclear effects on the location of hydrogen above and below the palladium (100) surface

Abstract

We report ab initio path integral molecular dynamics simulations of hydrogen and deuterium adsorbed on and absorbed in the Pd(100) surface at 100 K. Significant quantum nuclear effects are found by comparing with conventional ab initio molecular dynamics simulations with classical nuclei. For on-surface adsorption, hydrogen resides higher above the surface when quantum nuclear effects are included, an effect which brings the computed height into better agreement with experimental measurements. For sub-surface absorption, the classical and quantum simulations differ in an even more significant manner: the classically stable subsurface tetrahedral position is unstable when quantum nuclear effects are accounted for. This study provides insight that aids in the interpretation of experimental results and, more generally, underscores that despite the computational cost ab initio path integral molecular dynamics simulations of surface and subsurface adsorption are now feasible.