A theory for diffusion-controlled reactions within nonequilibrium steady states

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.

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Publication Details

Journal
The Journal of Chemical Physics
Published
2025-10-13
DOI
https://doi.org/10.1063/5.0284657
Primary Topic
Advanced Thermodynamics and Statistical Mechanics
Type
article
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article

A theory for diffusion-controlled reactions within nonequilibrium steady states

Seokjin Moon, David T. Limmer
The Journal of Chemical Physics
Advanced Thermodynamics and Statistical Mechanics
article

A theory for diffusion-controlled reactions within nonequilibrium steady states

Seokjin Moon, David T. Limmer
article en

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.

The Journal of Chemical PhysicsVol. 163(14)
Lawrence Berkeley National Laboratory (US), Kavli Energy NanoScience Institute (US), University of California, Berkeley (US)
Openalex Percentile: Top 77%
Advanced Thermodynamics and Statistical Mechanics
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A theory for diffusion-controlled reactions within nonequilibrium steady states — Seokjin Moon, David T. Limmer · The Journal of Chemical Physics (2025) | TGRS Research Map | TGRS