Kinetics of rare events for non-Markovian stationary processes and application to polymer dynamics

Abstract

How much time does it take for a fluctuating system, such as a polymer chain, to reach a target configuration that is rarely visited—typically because of a high energy cost? This question generally amounts to the determination of the first-passage time statistics to a target zone in phase space with lower occupation probability. Here, we present an analytical method to determine the mean first-passage time of a generic non-Markovian random walker to a rarely visited threshold, which goes beyond existing weak-noise theories. We apply our method to polymer systems, to determine (i) the first time for a flexible polymer to reach a large extension, and (ii) the first closure time of a stiff inextensible wormlike chain. Our results are in excellent agreement with numerical simulations and provide explicit asymptotic laws for the mean first-passage times to rarely visited configurations.