A coherent state approach to semiclassical nonadiabatic dynamics

The Journal of Chemical Physics
XiaoGeng Song, Troy Van Voorhis

Abstract

A semiclassical (SC) approximation to the quantum mechanical propagator for nonadiabatic systems is derived. Our derivation starts with an exact path integral expression that uses canonical coherent states for the nuclear degrees of freedom and spin coherent states for the electronic degrees of freedom. A stationary path approximation (SPA) is then applied to the path integral to obtain the SC approximation. The SPA results in complex classical trajectories of both nuclear and electronic degrees of freedom and a double ended boundary condition. The root search problem is solved using the previously proposed "real trajectory local search" algorithm. The SC approximation is tested on three simple one dimensional two-state systems proposed by Tully [J. Chem. Phys. 93, 1061 (1990)], and the SC results are compared to Ehrenfest and surface hopping predictions. Excellent agreement with quantum results is reached when the SC trajectory is far away from caustics. We discuss the origin of caustics in this SC formalism and the strengths and weaknesses of this approach.

References

Dec 15, 1989·Physical Review A: General Physics·J KurchanM Saraceno
Sep 13, 2002·Physical Review Letters·M PletyukhovM Brack
Jul 23, 2004·The Journal of Chemical Physics·Troy Van Voorhis, David R Reichman
Apr 20, 2005·The Journal of Chemical Physics·Priya V Parandekar, John C Tully
Sep 16, 2005·The Journal of Chemical Physics·S Bonella, D F Coker
Sep 17, 2005·The Journal of Chemical Physics·Xiaosong LiMichael J Frisch

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Citations

Dec 3, 2008·The Journal of Chemical Physics·XiaoGeng SongTroy Van Voorhis
Aug 3, 2019·The Journal of Chemical Physics·Johan E Runeson, Jeremy O Richardson
Jul 10, 2021·The Journal of Chemical Physics·Duncan BossionPengfei Huo

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