Highly confined mixtures of parallel hard squares: A Density Functional Theory study

TL;DR

This study uses Density Functional Theory to explore the phase behavior of highly confined mixtures of parallel hard squares, revealing first-order transitions, asymmetric packings, and demixing phenomena in slit geometries.

Contribution

It provides a theoretical analysis of phase transitions and packing behavior of confined square mixtures, highlighting the effectiveness of DFT in such low-dimensional systems.

Findings

First-order transitions between symmetric and asymmetric packings.

Observation of strong demixing between different species.

Comparison of confined system behavior with periodic boundary conditions.

Abstract

Using the Fundamental-Measure Density Functional Theory, we have studied theoretically the phase behavior of extremely confined mixtures of parallel hard squares in slit geometry. The pore width is chosen such that configurations consisting of two consecutive big squares, or three small squares, in the transverse direction, perpendicular to the walls, are forbidden. We analyzed two different mixtures with edge-lengths of species selected so as to allow or forbid one big plus one small square to fit into the channel. For the first mixture we obtained first-order transitions between symmetric and asymmetric packings of particles: small and big squares are preferentially adsorbed at different walls. Asymmetric configurations are shown to lead to more efficient packing at finite pressures. We argue that the stability region of the asymmetric phase in the pressure-composition plane is bounded so that the symmetric phase is stable at low and very high pressure. For the second mixture, we observe strong demixing between phases which are rich in different species. Demixing occurs in the transverse direction, i.e. the dividing interface is perpendicular to the walls, and phases exhibit symmetric density profiles. The possible experimental realization of this behaviour (which in practical terms is precluded by jamming) in strictly two-dimensional systems is discussed. Finally the phase behavior of a mixture with periodic boundary conditions is analyzed and the differences and similarities between the latter and the confined system are discussed. We claim that, although exact calculations discard the existence of true phase transitions in $1+\epsilon$-dimensional systems, Density Functional Theory is still successful to describe packing properties of large clusters of particles.