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Reactive path ensembles within nonequilibrium steady states

Aditya N. Singh1,2 and David T. Limmer1,2,3,4,*

  • *Contact author: dlimmer@berkeley.edu
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Phys. Rev. Research 7, 043222 – Published 26 November, 2025

DOI: https://doi.org/10.1103/rngb-46dt

Abstract

The modern theory of rare events is grounded in near-equilibrium ideas, however, many systems of modern interest are sufficiently far from equilibrium that traditional approaches do not apply. Using the recently developed variational path sampling methodology, we study systems evolving within nonequilibrium steady states to elucidate how reactive processes are altered away from equilibrium. Variational path sampling provides access to ensembles of reactive events and a means of quantifying the relative importance of each dynamical degree of freedom in such processes. With it, we have studied the conformational change of a solute in an active bath. We illustrate how energy injection generically enhances the rates of rare events, even when energy is not directed into specific reactive modes. By studying the folding and unfolding transitions of a grafted polymer under shear, we illustrate how nonequilibrium reactive processes do not follow gradient paths due to the emergence of persistent currents. The breaking of detailed balance allows for the mechanisms of forward and backward reactions to be distinct, enabling unconventional pathways to be explored and designed, and states unstable in equilibrium to become stabilized kinetically away from it. The analysis presented in this work establishes some basic principles for understanding the mechanism through which rates are perturbed by nonconservative forces, and how probability currents can stabilize thermodynamically unfavorable states, and is made possible by the use of a numerical method that does not invoke proximity to equilibrium.

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Phys. Rev. Research 7, 043222– Published 26 November, 2025
  • Received 15 February 2025
  • Accepted 27 October 2025
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