A theory for diffusion-controlled reactions within nonequilibrium steady states.

Area of Science:

• Physical Chemistry
• Chemical Physics
• Theoretical Chemistry

Background:

• Standard rate theory assumptions fail in nonequilibrium steady states.
• Understanding diffusion-controlled processes is crucial for complex chemical reactions.

Purpose of the Study:

• To generalize rate theory for diffusion-controlled processes in nonequilibrium steady states.
• To investigate the role of work in modulating reaction rates.
• To provide a theoretical framework for reactions beyond equilibrium.

Main Methods:

• Utilizing transition path theory to generalize flux-rate relations.
• Applying stochastic thermodynamics to analyze work's effect on rates.
• Developing and validating an analytically solvable ion pairing model.

Main Results:

• Established generalized relations between reactive probability fluxes and reaction rates.
• Demonstrated how applied work constrains rate enhancement compared to equilibrium.
• Validated the theoretical approach with an ion pairing model under an electric field.

Conclusions:

• The study provides a robust theoretical framework for diffusion-controlled reactions in nonequilibrium steady states.
• Findings deepen the understanding of reaction dynamics by considering external work.
• The developed methods and insights are applicable to various complex chemical systems.