The Casimir effect in wetting layers

TL;DR

This paper reveals that an entropic Casimir effect, previously overlooked, significantly influences 3D wetting transitions by altering phase diagrams and critical singularities, emphasizing the importance of interfacial fluctuations.

Contribution

It identifies and quantifies the entropic Casimir contribution in 3D wetting, showing its impact on phase behavior and critical phenomena, which was neglected in prior models.

Findings

Casimir term increases adsorption near first-order wetting transitions

It does not change the Nakanishi-Fisher phase diagram

It alters the critical singularities of tricritical wetting

Abstract

For a long time, the study of thermal effects at three-dimensional (3D) short-ranged wetting transitions considered only the effect of interfacial fluctuations. We show that an entropic Casimir contribution, missed in previous treatments, produces significant effects when it is included; in particular, mean-field predictions are no longer obtained when interfacial fluctuations are ignored. The Casimir term arises from the many different microscopic configurations that correspond to a given interfacial one. By employing a coarse-graining procedure, starting from a microscopic Landau-Ginzburg-Wilson Hamiltonian, we identify the interfacial model for 3D wetting and the exact form of the Casimir term. The Casimir contribution does not alter the Nakanishi-Fisher surface phase diagram; it significantly increases the adsorption near a first-order wetting transition and completely changes the predicted critical singularities of tricritical wetting, including the nonuniversality occurring in 3D arising from interfacial fluctuations. We illustrate how the Casimir term leads to a reappraisal of the critical singularities at wetting transitions.