A theory for diffusion-controlled reactions within nonequilibrium steady states

TL;DR

This paper develops a theoretical framework for understanding diffusion-controlled reactions in nonequilibrium steady states, extending rate theory and analyzing how work influences reaction rates with an illustrative ion pairing model.

Contribution

It introduces a generalized relation between reactive fluxes and reaction rates in nonequilibrium conditions using transition path theory.

Findings

Generalized rate relations for nonequilibrium steady states

Work constrains reaction rate enhancements

Validated theory with an analytically solvable ion model

Abstract

We study diffusion-controlled processes in nonequilibrium steady states, where standard rate theory assumptions break down. Using transition path theory, we generalize the relations between reactive probability fluxes and measures of the rate of the reaction. Stochastic thermodynamics analysis reveals how work constrains the enhancement of rates relative to their equilibrium values. An analytically solvable ion pairing model under a strong electric field illustrates and validates our approach and theory. These findings provide deeper insights into diffusion-controlled reaction dynamics beyond equilibrium.