Stochastic Quantum Molecular Dynamics

TL;DR

This paper introduces stochastic quantum molecular dynamics, a first-principles method for simulating correlated electron-nuclear systems interacting with environments, enabling analysis of phenomena like relaxation and dissipation.

Contribution

It establishes a theoretical framework linking ensemble-averaged current densities to external potentials, expanding quantum molecular dynamics capabilities.

Findings

Demonstrated rotational relaxation of a molecule in a bath

Theoretical foundation for electron-ion relaxation processes

Potential to simulate dissipative quantum dynamics

Abstract

An approach to correlated dynamics of quantum nuclei and electrons both in dynamical interaction with external environments is presented. This stochastic quantum molecular dynamics rests on a theorem that establishes a one-to-one correspondence between the total ensemble-averaged current density of interacting nuclei and electrons and a given external vector potential. The theory allows for a first-principles description of phenomena previously inaccessible via standard quantum molecular dynamics such as electronic and nuclear relaxation in photochemistry, dissipative correlated electron-ion dynamics in intense laser fields, nuclear dephasing, etc. As a demonstration of the approach, we discuss the rotational relaxation of 4-(N,N-dimethylamino)benzonitrile in a uniform bath in the limit of classical nuclei.