Finite-time fluctuation theorem for diffusion-influenced surface reactions

TL;DR

This paper proves a finite-time fluctuation theorem for diffusion-influenced surface reactions, linking stochastic reaction dynamics with deterministic diffusion equations, applicable to any geometry.

Contribution

It introduces a finite-time fluctuation theorem for surface reactions with a novel thermodynamic affinity linked to fluctuation symmetry, expressed analytically via diffusion equations.

Findings

Finite-time fluctuation theorem established for surface reactions.

Analytical expressions derived for reaction rates and affinity.

Applicable to arbitrary geometries with diffusion boundary conditions.

Abstract

A finite-time fluctuation theorem is proved for the diffusion-influenced surface reaction A<->B in a domain with any geometry where the species A and B undergo diffusive transport between the reservoir and the catalytic surface. A corresponding finite-time thermodynamic force or affinity is associated with the symmetry of the fluctuation theorem. The time dependence of the affinity and the reaction rates characterizing the stochastic process can be expressed analytically in terms of the solution of deterministic diffusion equations with specific boundary conditions.