Efficient implementation and performance analysis of the independent electron surface hopping method for dynamics at metal surfaces

TL;DR

This paper presents an efficient implementation of the independent electron surface hopping (IESH) method, demonstrating its accuracy and applicability for simulating nonadiabatic electron-nuclear dynamics at metal surfaces, including under external bias conditions.

Contribution

The authors develop a transparent and reliable implementation of IESH, extending its capabilities to include external bias potentials and validating its performance against quantum master equation results.

Findings

IESH accurately predicts scattering and desorption probabilities.

The method effectively models nonadiabatic effects at metal surfaces.

External bias can be incorporated with maintained accuracy.

Abstract

Independent electron surface hopping (IESH) is a computational algorithm for simulating the mixed quantum-classical molecular dynamics of adsorbate atoms and molecules interacting with metal surfaces. It is capable of modelling the nonadiabatic effects of electron-hole pair excitations on molecular dynamics. Here we present a transparent, reliable, and efficient implementation of IESH, demonstrating its ability to predict scattering and desorption probabilities across a variety of systems, ranging from model Hamiltonians to full dimensional atomistic systems. We further show how the algorithm can be modified to account for the application of an external bias potential, comparing its accuracy to results obtained using the hierarchical quantum master equation. Our results show that IESH is a practical method for modelling coupled electron-nuclear dynamics at metal surfaces, especially for highly energetic scattering events.