Efficient and Deterministic Propagation of Mixed Quantum-Classical Liouville Dynamics

TL;DR

This paper introduces an efficient, deterministic mixed quantum-classical dynamics method based on the quantum-classical Liouville equation, demonstrating high accuracy and reduced computational cost across various complex systems.

Contribution

It presents a novel deterministic propagation scheme for QCLE that requires fewer trajectories, improving efficiency and accuracy in simulating quantum-classical systems.

Findings

Accurately models spin-boson, electron transfer, and FMO complex dynamics.

Achieves long-time agreement with exact results using fewer trajectories.

Offers a promising tool for studying complex quantum-classical phenomena.

Abstract

We propose a highly efficient mixed quantum-classical molecular dynamics scheme based on a solution of the quantum-classical Liouville equation (QCLE). By casting the equations of motion for the quantum subsystem and classical bath degrees of freedom onto an approximate set of coupled first-order differential equations for c-numbers, this scheme propagates the composite system in time deterministically in terms of independent classical-like trajectories. To demonstrate its performance, we apply the method to the spin-boson model, a photo-induced electron transfer model, and a Fenna-Matthews-Olsen complex model, and find excellent agreement out to long times with the numerically exact results, using several orders of magnitude fewer trajectories than surface-hopping solutions of the QCLE. Owing to its accuracy and efficiency, this method promises to be very useful for studying the dynamics of mixed quantum-classical systems.