2021/02/26 by Britta Johnson, Johnson, Britta Ann, Nandini Ananth +1
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Advanced NMR Techniques and Applications #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Spectroscopy and Quantum Chemical Studies
paper · pdf · doi:10.48550/arxiv.2103.00059
openalex publication_date 2021/02/26 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
Mean-Field Ring Polymer Molecular Dynamics (MF-RPMD) is a powerful, efficient, and accurate method for approximate quantum dynamic simulations of multi-level system dynamics. Initial efforts to compute nonadiabatic reaction rates using MF-RPMD were not successful; recent work showed that this can be remedied by including a simple, if adhoc, correction term that accounts for the formation of `kinked' or mixed electronic state ring polymer configurations. Here, we build on this idea, introducing a electronic state population based reaction coordinate and novel skew dividing surface that constrains nuclear positions to configurations where the reactant and product state potentials are near-degenerate and that samples kinked electronic state configurations. We then demonstrate the numerical accuracy of this method in computing rates for a series of nonadiabatic model systems.