A Unified Theory of Free Energy Functionals and Applications to Diffusion

TL;DR

This paper develops a rigorous, unified framework for constructing free energy functionals in continuum models, clarifying their physical interpretation and broadening their applicability beyond traditional gradient-based forms.

Contribution

It introduces a generalized formalism for free energy functionals that unifies existing models and provides a clear physical interpretation of key parameters.

Findings

Unified free energy framework applicable beyond Ginzburg-Landau models

Derived physical meaning for the gradient energy parameter in Cahn-Hilliard

Validated approach using silicon-germanium alloy system

Abstract

Free energy functionals of Ginzburg-Landau type lie at the heart of a broad class of continuum dynamical models, such as the Cahn-Hilliard and Swift-Hohenberg equations. Despite the wide use of such models, the assumptions embodied in the free energy functionals are frequently either poorly justified or lead to physically opaque parameters. Here, we introduce a mathematically rigorous pathway for constructing free energy functionals that generalizes beyond the constraints of Ginzburg-Landau gradient expansions. We show that the new formalism unifies existing free energetic descriptions under a single umbrella by establishing the criteria under which the generalized free energy reduces to gradient-based representations. Consequently, we derive a precise physical interpretation of the gradient energy parameter in the Cahn-Hilliard model as the product of an interaction length scale and the free energy curvature. The practical impact of our approach is demonstrated using both a model free energy function and the silicon-germanium alloy system.