A study of the decoherence correction derived from the exact factorization approach for non-adiabatic dynamics

TL;DR

This paper investigates a decoherence correction method derived from the exact factorization approach for non-adiabatic dynamics, comparing it with existing methods through ab initio simulations of photo-excited molecules.

Contribution

It introduces and evaluates a new decoherence correction based on the exact factorization approach, comparing its performance with established methods in non-adiabatic molecular dynamics.

Findings

Decoherence-corrected methods behave differently on individual trajectories.

Results averaged over trajectories are similar across methods.

The new correction provides a qualitatively different trajectory behavior.

Abstract

We present a detailed study of the decoherence correction to surface-hopping that was recently derived from the exact factorization approach. Ab initio multiple spawning calculations that use the same initial conditions and same electronic structure method are used as a reference for three molecules: ethylene, methaniminium cation, and fulvene, for which non-adiabatic dynamics follows a photo-excitation. A comparison with the Granucci-Persico energy-based decoherence correction, and the augmented fewest-switches surface-hopping scheme shows that the three decoherence-corrected methods operate on individual trajectories in a qualitatively different way, but results averaged over trajectories are similar for these systems.