Exact fluctuation relation for open systems beyond the Jarzynski equality

TL;DR

This paper derives exact fluctuation relations for open systems that extend the Jarzynski equality, expressing free energy differences through ensemble averages involving the Hamiltonian of mean force and divergence measures, validated on complex driven systems.

Contribution

It introduces a new fluctuation relation for open systems that generalizes the Jarzynski equality beyond Hamiltonian dynamics and arbitrary coupling regimes.

Findings

The relation recovers free energy differences in complex driven systems.

It reduces to the Jarzynski equality under Hamiltonian dynamics.

The theory is validated on dissipative, phase-space-compressing drives.

Abstract

We derive exact fluctuation equalities for open systems that recover free energy differences between two equilibrium endpoints connected by nonequilibrium processes with arbitrary dynamics and coupling. The exponential of the free energy difference is expressed in terms of ensemble averages of the Hamiltonian of mean force (HMF) shift and the chi-squared divergence between the initial and final marginal probability distribution of the open system. A trajectory counterpart of this relation follows from an asymptotic equilibration postulate, which treats relaxation to the final stationary canonical state as a boundary condition rather than as a consequence of constraints on the driven dynamics. In the frozen-coupling regime, the HMF shift reduces to the bare-system Hamiltonian shift, yielding a clear heat-work decomposition. The Jarzynski equality (JE) is recovered under the assumption of Hamiltonian dynamics for the combined system. We validate the theory on a dissipative, phase-space-compressing drive followed by an underdamped Langevin relaxation, where the assumptions underlying the JE break down, whereas our equality reproduces the exact free energy differences.