Towards a correct description of initial electronic coherence in nonadiabatic dynamics simulations

TL;DR

This paper demonstrates that initial electronic coherence in nonadiabatic dynamics can be accurately modeled using ensemble-based methods with proper initial sampling and observable measures, improving upon traditional surface hopping techniques.

Contribution

It introduces a semiclassical mapping approach with initial electronic phase space sampling to correctly describe initial electronic coherence in nonadiabatic simulations.

Findings

Ensemble-based methods can accurately capture initial electronic coherence.

Proper initial sampling and observable measures are crucial for correct dynamics.

Traditional surface hopping methods fail to describe initial electronic coherence.

Abstract

The recent improvement in experimental capabilities for interrogating and controlling molecular systems with ultrafast coherent light sources calls for the development of theoretical approaches that can accurately and efficiently treat electronic coherence. However, the most popular and practical nonadiabatic molecular dynamics techniques, Tully's fewest-switches surface hopping and Ehrenfest mean-field dynamics, are unable to describe the dynamics proceeding from an initial electronic coherence. While such issues are not encountered with the analogous coupled-trajectory algorithms or numerically exact quantum dynamics methods, applying such methods necessarily comes with a higher computational cost. Here we show that a correct description of initial electronic coherence can indeed be achieved using methods that are based on an ensemble of independent trajectories. The key is the introduction of an initial sampling over the electronic phase space and the use of the correct observable measures, both of which are naturally achieved when working within the semiclassical mapping framework.