Mapping variable ring polymer molecular dynamics (MV-RPMD) is a previously proven method used to model the charge or energy dynamics of nonadiabatic systems, but while it can preserve its initial distribution, the electronic dynamics are not exact. Compared to adiabatic systems where species only exist on one potential energy surface (typically in the ground state), nonadiabatic systems allow the species to explore multiple potential surfaces or energy levels. Understanding the mechanism of nonadiabatic processes is a critical step towards applications in solar cells, transition metal catalysis, and photosynthesis. Our work aims to develop a modified MV-RPMD (mod-MV-RPMD) method that will preserve the system's initial distribution (Boltzmann distribution) while also accurately modeling the electronic dynamics. The method is based on a path-integral description for the nuclei and the Meyer-Miller-Stock-Thoss mapping representation for the electronic states. This combination allows both nuclear and electronic degrees of freedom to be treated on the same dynamical footing in terms of continuous classical variables. The mod-MV-RPMD method provides an efficient simulation method to obtain accurate nonadiabatic dynamics that rigorously preserve the quantum Boltzmann distribution.

Nonadiabatic dynamics while preserving the Boltzmann distribution: Modified mapping-variable ring polymer molecular dynamics

ACS Spring Meeting 2021

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