Thermodynamic Relations between Free Energy and Mobility

TL;DR

This paper uncovers fundamental thermodynamic relations linking free energy and mobility, valid even in hydrodynamic limits, for systems obeying detailed balance and Boltzmann distribution, with implications for inhomogeneous equilibrium states.

Contribution

It establishes a new class of relations between kinetic and thermodynamic factors that hold universally for systems satisfying detailed balance, including those with inhomogeneous states.

Findings

Derived thermodynamic relations between free energy and mobility.

Identified consistency conditions for self-diffusivities in inhomogeneous systems.

Provided mathematical framework ensuring thermodynamic-kinetic consistency.

Abstract

Stochastic and dynamical processes lie at the heart of all physical, chemical, and biological systems. However, kinetic and thermodynamic properties which characterize these processes have largely been treated separately as they can be obtained independently for many systems at thermodynamic equilibrium. In this work we demonstrate the existence of a class of relations between kinetic and thermodynamic factors which holds even in the hydrodynamic limit, and which must be satisfied for all systems that satisfy detailed balance and Boltzmann distribution at equilibrium. We achieve this by proving that for systems with inhomogeneous equilibrium states governed by dynamics such as the Cahn-Hilliard (CH) dynamics, the chemical potential and self-diffusivity must mutually constrain each other. We discuss common issues in the literature which result in inconsistent formulations, construct the consistency requirement mathematically, develop a class of self-diffusivities that guarantee consistency, and discuss how the requirement originates from detailed balance and Boltzmann distribution, and is therefore applicable to both conserved and non-conserved dynamics.