Exact-Factorization-Based Surface-Hopping for Multi-State Dynamics

TL;DR

This paper introduces an improved surface-hopping algorithm based on the exact factorization approach, which accurately captures multi-state non-adiabatic dynamics and decoherence effects, outperforming traditional methods.

Contribution

The paper demonstrates that including the quantum momentum term from the exact factorization approach is essential for accurate multi-state non-adiabatic dynamics modeling.

Findings

SHXF accurately predicts three-state intersection dynamics.

Traditional surface-hopping methods fail without the quantum momentum term.

SHXF matches multi-configuration time-dependent Hartree benchmark results.

Abstract

A surface-hopping algorithm recently derived from the exact factorization approach, SHXF, [Ha, Lee, Min, J. Phys. Chem. Lett. 9, 1097 (2018)] introduces an additional term in the electronic equation of surface-hopping, which couples electronic states through the quantum momentum. This term not only provides a first-principles description of decoherence but here we show it is crucial to accurately capture non-adiabatic dynamics when more than two states are occupied at any given time. Using a vibronic coupling model of the uracil cation, we show that the lack of this term in traditional surface-hopping methods, including those with decoherence-corrections, leads to failure to predict the dynamics through a three-state intersection, while SHXF performs similarly to the multi-configuration time-dependent Hartree quantum dynamics benchmark.