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Transient probability currents provide upper and lower bounds on non-equilibrium steady-state currents in the Smoluchowski picture
Journal article   Open access   Peer reviewed

Transient probability currents provide upper and lower bounds on non-equilibrium steady-state currents in the Smoluchowski picture

Jeremy Copperman, David Aristoff, Dmitrii E. Makarov, Gideon Simpson and Daniel M. Zuckerman
The Journal of chemical physics, v 151(17), pp 174108-174108
07 Nov 2019
PMID: 31703496
url
https://doi.org/10.1063/1.5120511View
Published, Version of Record (VoR) Open

Abstract

Chemistry Chemistry, Physical Physical Sciences Physics Physics, Atomic, Molecular & Chemical Science & Technology
Probability currents are fundamental in characterizing the kinetics of nonequilibrium processes. Notably, the steady-state current J(ss) for a source-sink system can provide the exact mean-first-passage time (MFPT) for the transition from the source to sink. Because transient nonequilibrium behavior is quantified in some modern path sampling approaches, such as the "weighted ensemble" strategy, there is strong motivation to determine bounds on J(ss)-and hence on the MFPT-as the system evolves in time. Here, we show that J(ss) is bounded from above and below by the maximum and minimum, respectively, of the current as a function of the spatial coordinate at any time t for one-dimensional systems undergoing overdamped Langevin (i.e., Smoluchowski) dynamics and for higher-dimensional Smoluchowski systems satisfying certain assumptions when projected onto a single dimension. These bounds become tighter with time, making them of potential practical utility in a scheme for estimating J(ss) and the long time scale kinetics of complex systems. Conceptually, the bounds result from the fact that extrema of the transient currents relax toward the steady-state current.

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Collaboration types
Domestic collaboration
Web of Science research areas
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
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