Nonadiabatic Dynamics with Coupled Trajectories

J Chem Theory Comput. 2021 Oct 12;17(10):5969-5991. doi: 10.1021/acs.jctc.1c00438. Epub 2021 Sep 10.

Abstract

In this paper, we discuss coupled-trajectory schemes for molecular-dynamics simulations of excited-state processes. New coupled-trajectory strategies to capture decoherence effects, revival of coherence and nonadiabatic interferences in long-time dynamics are proposed, and compared to independent-trajectory schemes. The working framework is provided by the exact factorization of the electron-nuclear wave function, and it exploits ideas emanating from various surface-hopping schemes. The new coupled-trajectory algorithms are tested on a one-dimensional two-state system using different model parameters which allow one to induce different dynamics. The benchmark is provided by the numerically exact solution of the time-dependent Schrödinger equation.