Dissipation-Driven Selection under Finite Diffusion: Hints from Equilibrium and Separation of Time Scales

Area of Science:

• Chemical kinetics
• Non-equilibrium thermodynamics
• Complex systems

Background:

• Reaction networks can convert thermal energy into non-equilibrium chemical states.
• Kinetics and energy dissipation are crucial for dictating non-equilibrium state populations.
• Previous theoretical exploration focused mainly on the infinite diffusion limit.

Purpose of the Study:

• Investigate the impact of finite diffusion rates on non-equilibrium reaction networks.
• Explore phenomena like selection maximization and state switching under specific kinetic regimes.
• Develop an intuitive, equilibrium-based framework for understanding complex non-isothermal reaction networks.

Main Methods:

• Time-scale separation analysis to capture leading non-equilibrium features.
• Identification of fast-dissipation sub-networks within the larger reaction network.
• Utilizing equilibrium arguments under well-defined conditions to analyze non-equilibrium behavior.

Main Results:

• Finite diffusion rates, slower than some reactions, can lead to maximized chemical selection or switched selected states at stationarity.
• Fast-dissipation sub-networks' Boltzmann equilibrium can dominate the steady-state of the entire system.
• Dissipated heat and entropy production can be estimated using the heat capacity of fast-dissipation sub-networks.

Conclusions:

• A novel framework allows for an equilibrium-based understanding of complex non-isothermal reaction networks.
• This approach simplifies the analysis of systems crucial for understanding the emergence of complex structures.
• The findings provide tools for analyzing how thermal gradients drive chemical selection in complex systems.