Studying rare nonadiabatic dynamics with transition path sampling quantum jump trajectories

TL;DR

This paper introduces a novel method combining transition path sampling with quantum jump trajectories to study rare nonadiabatic quantum dynamics without prior knowledge of transition states, enabling detailed mechanistic insights.

Contribution

The paper develops a quantum path ensemble approach using unravelled quantum master equations, allowing unbiased calculation of rates and yields in complex quantum systems.

Findings

Successfully applied to energy transfer, proton-coupled electron transfer, and electron transfer models.

Demonstrates unbiased rate calculations from reversible work in quantum path ensembles.

Shows effectiveness of path ensemble methods in complex quantum reactive dynamics.

Abstract

We present a method to study rare nonadiabatic dynamics in open quantum systems using transition path sampling and quantum jump trajectories. As with applications of transition path sampling to classical dynamics, the method does not rely on prior knowledge of transition states or reactive pathways, and thus can provide mechanistic insight into ultrafast relaxation processes in addition to their associated rates. In particular, we formulate a quantum path ensemble using the stochastic realizations of an unravelled quantum master equation, which results in trajectories that can be conditioned on starting and ending in particular quantum states. Because the dynamics rigorously obeys detailed balance, rate constants can be evaluated from reversible work calculations in this conditioned ensemble, allowing for branching ratios and yields to be computed in an unbiased manner. We illustrate the utility of this method with three examples: energy transfer in a donor-bridge-acceptor model, and models of photo-induced proton-coupled electron transfer and thermally activated electron transfer. These examples demonstrate the efficacy of path ensemble methods and pave the way for their use in studying of complex reactive quantum dynamics.