Real-Time Dynamics and Detailed Balance in Ring Polymer Surface Hopping: The Impact of Frustrated Hops

Document Type

Article

Publication Date

9-28-2023

Abstract

Ring polymer surface hopping (RPSH) has been recently introduced as a well-tailored method for incorporating nuclear quantum effects, such as zero-point energy and tunneling, into nonadiabatic molecular dynamics simulations. The practical widespread usage of RPSH demands a comprehensive benchmarking of different reaction regimes and conditions with equal emphasis on demonstrating both the cons and the pros of the method. Here, we investigate the fundamental questions related to the conservation of energy and detailed balance in the context of RPSH. Using Tully’s avoided crossing model as well as a 2-state quantum system coupled to a classical bath undergoing Langevin dynamics, we probe the critical problem of the proper treatment of the classically forbidden transitions stemming from the surface hopping algorithm. We show that proper treatment of these frustrated hops is key to the accurate description of real-time dynamics as well as reproducing the correct quantum Boltzmann populations.

Identifier

85172739935 (Scopus)

Publication Title

Journal of Physical Chemistry Letters

External Full Text Location

https://doi.org/10.1021/acs.jpclett.3c02085

e-ISSN

19487185

PubMed ID

37732811

First Page

8658

Last Page

8666

Issue

38

Volume

14

Grant

CHE200007

Fund Ref

National Science Foundation

This document is currently not available here.

Share

COinS