The Coupled-Trajectory Mixed Quantum-Classical Algorithm: A Deconstruction

TL;DR

This paper critically analyzes a mixed quantum-classical algorithm based on exact factorization, highlighting the roles of different terms in decoherence and wavepacket branching, and comparing its decoherence times with surface-hopping methods.

Contribution

It provides a detailed deconstruction of the coupled-trajectory mixed quantum-classical algorithm, clarifying the importance of various terms in the equations for accurate non-adiabatic dynamics.

Findings

Coupled-trajectory term in electronic equations is crucial for accuracy.

Nuclear equation's coupled-trajectory term has minimal impact.

Decoherence times are comparable to those from surface-hopping methods.

Abstract

We analyze a mixed quantum-classical algorithm recently derived from the exact factorization equations [Min, Agostini, Gross, PRL {\bf 115}, 073001 (2015)] to show the role of the different terms in the algorithm in bringing about decoherence and wavepacket branching. The algorithm has the structure of Ehrenfest equations plus a "coupled-trajectory" term for both the electronic and nuclear equations, and we analyze the relative roles played by the different non-adiabatic terms in these equations, including how they are computed in practise. In particular, we show that while the coupled-trajectory term in the electronic equation is essential in yielding accurate dynamics, that in the nuclear equation has a much smaller effect. A decoherence time is extracted from the electronic equations and compared with that of augmented fewest-switches surface-hopping. We revisit a series of non-adiabatic Tully model systems to illustrate our analysis.