A First Principles Derivation of Energy Conserving Momentum Jumps in Surface Hopping Simulations

TL;DR

This paper provides a first-principles derivation of the energy-conserving momentum jumps in the surface hopping method, connecting it to quantum trajectory surface hopping and avoiding artificial rescaling.

Contribution

It offers a rigorous derivation of FSSH momentum jumps from quantum trajectory surface hopping, enhancing theoretical understanding and accuracy.

Findings

Derivation of FSSH momentum jumps from first principles.

Quantum forces in QTSH yield accurate nonadiabatic dynamics.

Energy conservation is rigorously maintained without artificial rescaling.

Abstract

The fewest switches surface hopping (FSSH) method proposed by Tully in 1990 [J. C Tully, J. Chem. Phys. 93, 1061 (1990)] -- along with its many later variations -- is basis for most practical simulations of molecular dynamics with electronic transitions in realistic systems. Despite its popularity, a rigorous formal derivation of the algorithm has yet to be achieved. In this paper, we derive the energy conserving momentum jumps characterizing FSSH from the perspective of quantum trajectory surface hopping (QTSH [C. C. Martens, J. Phys. Chem. A 123, 1110 (2019)]. In the limit of localized nonadiabatic transitions, simple mathematical and physical arguments allow the FSSH algorithm to be derived from first principles. For general processes, the quantum forces characterizing the QTSH method provides accurate results for nonadiabatic dynamics with rigorous energy conservation at the ensemble level within the consistency of the underlying stochastic surface hopping without resorting to the artificial momentum rescaling of FSSH.