On the electronic path integral normal modes of the Meyer-Miller-Stock-Thoss representation of nonadiabatic dynamics

TL;DR

This paper investigates the electronic normal modes in the Meyer-Miller-Stock-Thoss representation for nonadiabatic dynamics, revealing that truncating these modes does not reliably conserve the Quantum Boltzmann Distribution and affects accuracy.

Contribution

First study of electronic normal modes in MMST representation showing limitations in mode truncation for accurate, QBD-conserving nonadiabatic simulations.

Findings

Higher normal modes are not constrained by the distribution.

Truncating in MMST modes leads to inaccurate correlation functions.

QBD appears conserved for ensembles but not for individual trajectories.

Abstract

Accurate and efficient simulation of nonadiabatic dynamics is highly desirable for understanding charge and energy transfer in complex systems. A key criterion for obtaining an accurate method is conservation of the Quantum Boltzmann Distribution (QBD). For a single surface, Matsubara dynamics is known to conserve the QBD, as a consequence of truncating the dynamics in the higher normal modes of the imaginary-time path integral. Recently, a nonadiabatic Matsubara (NA-Mats) dynamics has been proposed (J. Chem. Phys., 2021, 154, 124124) which truncates in the normal modes of the nuclear variables but not in the electronic variables, which are described with the Meyer-Miller-Stock-Thoss (MMST) representation. Surprisingly, this NA-Mats method does not appear to conserve the QBD for a general system. This poses the question of the effect of truncating the higher path integral normal modes of the electronic variables in the MMST representation. In this article, we present what we believe is the first study of electronic normal modes of the MMST representation. We find that observables are not usually a function of a finite number of normal modes and that the higher normal modes are not constrained by the distribution, unlike in conventional nuclear normal modes. Furthermore, truncating the dynamics in MMST normal modes leads to inaccurate correlation functions and while the QBD appears conserved for an ensemble of trajectories, it is not for a single trajectory. Overall, this suggests that MMST path integral normal modes are not optimal for obtaining an accurate, QBD conserving nonadiabatic dynamics method.