The exact solution of the Koga-Widom-Indekeu model and related models of wetting in fluid mixtures

TL;DR

This paper provides an exact analytical solution for a class of models describing wetting phenomena in fluid mixtures, clarifying the conditions under which critical point wetting occurs or is absent.

Contribution

It derives exact density profiles and surface tensions for the Koga-Widom-Indekeu model, confirming the absence of critical point wetting and proposing a universality principle based on symmetry.

Findings

Exact solutions for surface tensions and density profiles in the KWI model.

Critical point wetting is absent in models with XY symmetry.

Universality principle links wetting behavior to symmetry of the order parameter.

Abstract

We show how a broad class of two-component square-gradient models of wetting may be solved exactly for the surface tensions and density profile paths, and clarify how the presence or absence of critical point wetting, in binary and ternary mixtures, is related to universality and symmetry principles at critical end points. We begin by solving a model of fluid interfaces, first introduced by Koga and Widom, in ternary mixtures showing three phase coexistence. Numerical studies had revealed interesting wetting transitions, as well as curious geometrical properties of the profile paths in the density plane, and led these authors to conjecture expressions for the surface tensions. These conjectures were extended by Koga and Indekeu and predicted that partial wetting may persist up to the line of critical end points, i.e. critical point wetting was absent. Here, we obtain the exact density profiles and surface tensions for the Koga-Widom-Indekeu (KWI) model using complex analysis and drawing on the theory of algebraic curves. The exact solution determines the location and order of wetting transitions in the surface phase diagram, confirming that critical point wetting is absent. The model also displays the remarkable property that microscopic density profiles are mapped, by a conformal transform, onto the shape of a macroscopic drop near the contact line whose tensions satisfy the Neumann triangle. Two related models, which illustrate the role of the component isotropy, are also discussed. These models suggest that a universality principle governs wetting in fluid mixtures, resolving contradicting results from earlier studies: Critical point wetting is present if the order-parameter components of the mixture describe Ising-like criticality, but is absent if there is a local XY symmetry. Implications for wetting transitions in more microscopic models and in experiments are discussed.