Phase behaviour and correlations of parallel hard squares: From highly confined to bulk systems

TL;DR

This study evaluates the performance of Fundamental-Measure Theory (FMT) in predicting phase behaviour and correlations of parallel hard squares in bulk and confined systems, comparing with simulations and other theories.

Contribution

It provides a comprehensive assessment of FMT's accuracy for bulk and confined parallel hard squares, highlighting its strengths and limitations.

Findings

FMT overestimates bulk correlations and predicts a columnar phase absent in simulations.

The equation of state from FMT aligns well with simulations, with PY approach sometimes better.

FMT accurately predicts structure, correlations, and density profiles in confined systems.

Abstract

We study a fluid of two-dimensional parallel hard squares in bulk and under confinement in channels, with the aim of evaluating the performance of Fundamental-Measure Theory (FMT). To this purpose, we first analyse the phase behaviour of the bulk system using FMT and Percus-Yevick theory, and compare the results with MD and MC simulations. In a second step, we study the confined system and check the results against those obtained from Transfer Matrix Method and from our own Monte Carlo simulations. Squares are confined to channels with parallel walls at angles of 0$^{\circ}$ or 45$^{\circ}$ relative to the diagonals of the parallel hard squares, respectively, which allows for an assessment of the effect of the external-potential symmetry on the fluid structural properties. In general FMT overestimates bulk correlations, predicting the existence of a columnar phase (absent in simulations) prior to crystallisation. The equation of state predicted by FMT compares well with simulations, although the PY approach with the virial route is better in some range of packing fractions. The FMT is highly accurate for the structure and correlations of the confined fluid due to the dimensional crossover property fulfilled by the theory. Both density profiles and equations of state of the confined system are accurately predicted by the theory. The highly non-uniform pair correlations inside the channel are also very well described by FMT.