Crystallisation of soft matter under confinement at interfaces and in wedges

TL;DR

This study uses density functional theory to explore how soft matter systems exhibit surface freezing or melting under confinement, revealing the conditions for prefreezing, premelting, and their phase transitions at interfaces and wedges.

Contribution

It provides a theoretical framework for understanding surface phase transitions in soft matter under confinement, highlighting the roles of wall potential range and strength.

Findings

Surface freezing occurs with weak wall repulsion, with a frozen layer growing logarithmically.

Prefreezing is a first-order transition involving a free energy barrier.

Surface melting can occur with strong, long-range wall repulsion, leading to wetting by liquid.

Abstract

The surface freezing and surface melting transitions exhibited by a model two-dimensional soft matter system is studied. The behaviour when confined within a wedge is also considered. The system consists of particles interacting via a soft purely repulsive pair potential. Density functional theory (DFT) is used to calculate density profiles and thermodynamic quantities. The external potential due to the confining walls is modelled via a hard-wall with an additional repulsive Yukawa potential. The surface phase behaviour depends on the range and strength of this repulsion: When the repulsion strength is weak, the wall promotes freezing at the surface of the wall. The thickness of this frozen layer grows logarithmically as the bulk liquid-solid phase coexistence is approached. Our mean-field DFT predicts that this crystalline layer at the wall must be nucleated (i.e. there is a free energy barrier) and its formation is necessarily a first-order transition, referred to as `prefreezing', by analogy with the prewetting transition. However, in contrast to the latter, prefreezing cannot terminate in a critical point, since the phase transition involves a change in symmetry. If the wall-fluid interaction is sufficiently long ranged and the repulsion is strong enough, surface melting can instead occur. Then the interface between the wall and the bulk crystalline solid becomes wet by the liquid phase as the chemical potential is decreased towards the value at liquid-solid coexistence. It is observed that the finite thickness fluid film at the wall has a broken translational symmetry due to its proximity to the bulk crystal and so the nucleation of the wetting film can be either first-order or continuous. Our mean-field theory predicts that for certain wall potentials there is a premelting critical point analogous to the surface critical point for the prewetting transition. In a wedge...