Nonadiabatic dynamics at metal surfaces: fewest switches surface hopping with electronic relaxation

TL;DR

This paper introduces a modified surface hopping method, FSSH-ER, for modeling nonadiabatic molecular dynamics at metal surfaces, effectively incorporating electronic relaxation and validated on the Anderson-Holstein model.

Contribution

A novel FSSH-ER scheme that integrates electronic relaxation into surface hopping for metal surface dynamics, enabling accurate simulations across various coupling strengths.

Findings

Validated on Anderson-Holstein model

Effective across a wide range of coupling strengths

Supports future integration with ab initio calculations

Abstract

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 strength 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.