English

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

Statistical Mechanics 2020-01-08 v5 Biological Physics Chemical Physics Computational Physics

Abstract

Probability currents are fundamental in characterizing the kinetics of non-equilibrium processes. Notably, the steady-state current JssJ_{ss} for a source-sink system can provide the exact mean-first-passage time (MFPT) for the transition from source to sink. Because transient non-equilibrium behavior is quantified in some modern path sampling approaches, such as the "weighted ensemble" strategy, there is strong motivation to determine bounds on JssJ_{ss} -- and hence on the MFPT -- as the system evolves in time. Here we show that JssJ_{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 tt for one-dimensional systems undergoing over-damped 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 JssJ_{ss} and the long-timescale kinetics of complex systems. Conceptually, the bounds result from the fact that extrema of the transient currents relax toward the steady-state current.

Keywords

Cite

@article{arxiv.1810.09964,
  title  = {Transient probability currents provide upper and lower bounds on non-equilibrium steady-state currents in the Smoluchowski picture},
  author = {Jeremy Copperman and David Aristoff and Dmitrii E. Makarov and Gideon Simpson and Daniel M. Zuckerman},
  journal= {arXiv preprint arXiv:1810.09964},
  year   = {2020}
}