We develop a theory for inferring equilibrium transition rates from trajectories driven by a time-dependent force using results from stochastic thermodynamics. Applying the Kawasaki relation to approximate the nonequilibrium distribution function in terms of the equilibrium distribution function and the excess dissipation, we formulate a nonequilibrium transition state theory to estimate the rate enhancement over the equilibrium rate due to the nonequilibrium protocol. We demonstrate the utility of our theory in examples of pulling of harmonically trapped particles in one and two dimensions, as well as a semiflexible polymer with a reactive linker in three dimensions.
View Article and Find Full Text PDFActive matter represents a broad class of systems that evolve far from equilibrium due to the local injection of energy. Like their passive analogs, transformations between distinct metastable states in active matter proceed through rare fluctuations; however, their detailed balance violating dynamics renders these events difficult to study. Here, we present a simulation method for evaluating the rate and mechanism of rare events in generic nonequilibrium systems and apply it to study the conformational changes of a passive solute in an active fluid.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
February 2021
Complex systems can convert energy imparted by nonequilibrium forces to regulate how quickly they transition between long-lived states. While such behavior is ubiquitous in natural and synthetic systems, currently there is no general framework to relate the enhancement of a transition rate to the energy dissipated or to bound the enhancement achievable for a given energy expenditure. We employ recent advances in stochastic thermodynamics to build such a framework, which can be used to gain mechanistic insight into transitions far from equilibrium.
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