Unified Formulation of Phase Space Mapping Approaches for Nonadiabatic Quantum Dynamics

TL;DR

This paper reviews recent advances in phase space mapping theories for nonadiabatic quantum dynamics, providing a unified framework that enhances the understanding and modeling of complex molecular systems involving electronic state couplings.

Contribution

It introduces a unified phase space mapping framework for nonadiabatic systems, generalizes the Meyer-Miller Hamiltonian, and links quantum dynamics with electron transport processes.

Findings

Unified phase space mapping framework developed.

Generalized Hamiltonian encompassing Meyer-Miller model.

Established connection between quantum dynamics and electron transport.

Abstract

Nonadiabatic dynamical processes are one of the most important quantum mechanical phenomena in chemical, materials, biological, and environmental molecular systems, where the coupling between different electronic states is either inherent in the molecular structure or induced by the (intense) external field. The curse of dimensionality indicates the intractable exponential scaling of calculation effort with system size and restricts the implementation of numerically exact approaches for realistic large systems. The phase space formulation of quantum mechanics offers an important theoretical framework for constructing practical approximate trajectory-based methods for quantum dynamics. This Account reviews our recent progress in phase space mapping theory: a unified framework for constructing the mapping Hamiltonian on phase space for coupled F-state systems where the renowned Meyer-Miller Hamiltonian model is a special case, a general phase space formulation of quantum mechanics for nonadiabatic systems where the electronic degrees of freedom are mapped onto constraint space and the nuclear degrees of freedom are mapped onto infinite space, and an isomorphism between the mapping phase space approach for nonadiabatic systems and that for nonequilibrium electron transport processes.