Nonadiabatic Dynamics at Metal Surfaces: Fewest Switches Surface Hopping with Electronic Relaxation

摘要

A new scheme is proposed for modeling molecular nonadiabatic dynamics near metal surfaces. The charge-transfer character of such dynamics is exploited to construct an efficient reduced representation for the electronic structure. In this representation, the fewest switches surface hopping (FSSH) approach can be naturally modified to include electronic relaxation (ER). The resulting FSSH-ER method is valid across a wide range of coupling strengths as supported by tests applied to the Anderson–Holstein model for electron transfer. Future work will combine this scheme with ab initio electronic structure calculations.