Orbital Surface Hopping from Orbital Quantum-Classical Liouville Equation for Nonadiabatic Dynamics of Many-electron Systems

TL;DR

This paper introduces an orbital surface hopping (OSH) algorithm derived from the orbital quantum classical Liouville equation, effectively modeling many-electron nonadiabatic dynamics at metal surfaces with high accuracy and efficiency.

Contribution

The paper develops a new OSH algorithm based on the orbital QCLE, connecting it with existing IESH methods and benchmarking its performance against FCI-SH for the first time.

Findings

OSH agrees well with IESH and FCI-SH in key dynamics metrics.

The method accurately captures orbital populations and energy relaxation.

It demonstrates high computational efficiency.

Abstract

Accurate simulation the many-electronic nonadiabatic dynamics process at metal surfaces remains as a significant task. In this work, we present an orbital surface hopping (OSH) algorithm rigorously derived from the orbital quantum classical Liouville equation (o-QCLE) to deal with nonadiabatic dynamics for many-electron systems. This OSH algorithm closely connects with the popular Independent Electron Surface Hopping (IESH) method, which has shown remarkable success in addressing these nonadiabatic phenomena, except that electrons hop between orbitals. We compare OSH with IESH approach and benchmark these two algorithms against the surface hopping method with a full Configuration Interaction (FCI) wavefunction. Our approach shows strong agreement with IESH and FCI-SH results for molecular orbital populations and kinetic energy relaxation and in high efficiency, demonstrating the ability of the new OSH method in capturing key aspects of many-electronic nonadiabatic dynamics.