Nonadiabatic dynamics at metal surfaces: Independent-electron surface hopping

Abstract

Recent experiments have shown convincing evidence for nonadiabatic energy transfer from adsorbate degrees of freedom to surface electrons during the interaction of molecules with metal surfaces. In this paper, we propose an independent-electron surface hopping algorithm for the simulation of nonadiabatic gas-surface dynamics. The transfer of energy to electron-hole pair excitations of the metal is successfully captured by hops between electronic adiabats. The algorithm is able to account for the creation of multiple electron-hole pairs in the metal due to nonadiabatic transitions. Detailed simulations of the vibrational relaxation of nitric oxide on a gold surface, employing a multistate potential energy surface fit to density functional theory calculations, confirm that our algorithm can capture the underlying physics of the inelastic scattering process.