A general framework for microscopically reversible processes with memory

TL;DR

This paper develops a comprehensive theoretical framework for reversible stochastic processes with memory, unifying equilibrium statistics with non-Markovian dynamics and applicable to single-molecule experiments and nanoscience.

Contribution

It introduces a novel approach to describe reversible processes with memory, bridging equilibrium and non-equilibrium physics through pathway characterization.

Findings

States depend on history, establishing a one-to-one pathway-state correspondence.

Equilibrium arises from exploring all connecting pathways between states.

Framework applies to single-molecule experiments and nanoscience, offering a general theory of irreversible processes.

Abstract

Statistical Mechanics deals with ensembles of microstates that are compatible with fixed constraints and that on average define a thermodynamic macrostate. The evolution of a small system is normally subjected to changing constraints and involve a stochastic dependence on previous events. Here, we develop a theory for reversible processes with memory that comprises equilibrium statistics and that converges to the same physics in the limit of independent events. This framework is based on the characterization of single phase-space pathways and is used to derive ensemble-average dynamics in stochastic systems driven by a protocol in the limit of no friction. We show that the state of a system depends on its history to the extent of attaining a one-to-one correspondence between states and pathways when memory covers all the previous events. Equilibrium appears as the consequence of exploring all pathways that connect two states by all procedures. This theory is useful to interpret single-molecule experiments in Biophysics and other fields in Nanoscience and an adequate platform for a general theory of irreversible processes.