Path Integrals for Nonadiabatic Dynamics: Multistate Ring Polymer Molecular Dynamics

Annu Rev Phys Chem. 2022 Jan 26. doi: 10.1146/annurev-physchem-082620-021809. Online ahead of print.ABSTRACTThis review focuses on a recent class of path-integral-based methods that simulate nonadiabatic dynamics in the condensed phase using only classical molecular dynamics trajectories in an extended phase space. Specifically, a semiclassical mapping protocol is used to derive an exact, continuous, Cartesian variable path-integral representation for the canonical partition function of a system in which multiple electronic states are coupled to nuclear degrees of freedom. Building on this exact statistical foundation, multistate ring polymer molecular dynamics methods are developed for the approximate calculation of real-time thermal correlation functions. The remarkable promise of these multistate ring polymer methods, their successful applications, and their limitations are discussed in detail.Expected final online publication date for the Annual Review of Physical Chemistry, Volume 73 is April 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.PMID:35081325 | DOI:10.1146/annurev-physchem-082620-021809

Source: Annual Review of Physical Chemistry - January 26, 2022 Category: Chemistry Authors: Nandini Ananth Source Type: research