The Influence of Intermolecular Forces at Critical Point Wedge Filling

TL;DR

This study uses microscopic density functional theory to analyze how intermolecular forces influence the nature of filling transitions in wedge geometries, revealing a change from first-order to continuous transitions near the critical point.

Contribution

It demonstrates the transition from first-order to continuous filling transitions near the critical point, aligning with effective Hamiltonian theory predictions.

Findings

Both wetting and filling transitions are first-order at low temperatures.

Near the critical point, filling transitions become continuous while wetting remains first-order.

Critical singularities depend on the nature of wall-fluid forces and match theoretical predictions.

Abstract

We use microscopic density functional theory to study filling transitions in systems with long-ranged wall-fluid and short-ranged fluid-fluid forces occurring in a right-angle wedge. By changing the strength of the wall-fluid interaction we can induce both wetting and filling transitions over a wide range of temperatures and study the order of these transitions. At low temperatures we find that both wetting and filling transitions are first-order in keeping with predictions of simple local effective Hamiltonian models. However close to the bulk critical point the filling transition is observed to be continuous even though the wetting transition remains first-order and the wetting binding potential still exhibits a small activation barrier. The critical singularities for adsorption for the continuous filling transitions depend on whether retarded or non-retarded wall-fluid forces are present and are in excellent agreement with predictions of effective Hamiltonian theory even though the change in the order of the transition was not anticipated.