Flux-correlation approach to characterizing reaction pathways in quantum systems: A study of condensed-phase proton-coupled electron transfer

TL;DR

This paper presents a new flux-correlation method for analyzing reaction pathways in quantum systems, demonstrated on condensed-phase proton-coupled electron transfer reactions, revealing the significance of different pathways through exact quantum dynamics simulations.

Contribution

The paper introduces a flux-correlation approach to characterize quantum reaction pathways, applicable to both approximate and exact quantum dynamics simulations.

Findings

Quantitative measure of dynamical coupling in quantum transitions

Application to condensed-phase PCET reactions

Identification of dominant reaction pathways

Abstract

We introduce a simple method for characterizing reactive pathways in quantum systems. Flux auto- correlation and cross-correlation functions are employed to develop a quantitative measure of dynamical coupling in quantum transition events, such as reactive tunneling and resonant energy transfer. We utilize the method to study condensed-phase proton-coupled electron transfer (PCET) reactions and to determine the relative importance of competing concerted and sequential reaction pathways. Results presented here include numerically exact quantum dynamics simulations for model condensed-phase PCET reactions. This work demonstrates the applicability of the new method for the analysis of both approximate and exact quantum dynamics simulations.