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

在斯莫卢霍夫斯基图景中,瞬态概率流为非平衡稳态流提供了上下界。

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Abstract

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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