Correlation functions in liquids and crystals : Free energy functional and liquid - crystal transition

TL;DR

This paper develops a free energy functional approach to study the liquid-crystal transition in three-dimensional fluids, accurately predicting freezing parameters and crystal structures for various potentials, aligning well with simulations.

Contribution

It introduces a method incorporating symmetry broken parts of the correlation function to precisely describe freezing transitions in 3D fluids.

Findings

Accurate prediction of freezing parameters for inverse power potentials.

Identification of the preferred crystal structure (bcc or fcc) based on potential exponent.

Determination of the fluid-bcc-fcc triple point at 1/n = 0.158.

Abstract

A free energy functional for a crystal that contains both the symmetry conserved and symmetry broken parts of the direct pair correlation function has been used to investigate the crystallization of fluids in three-dimensions. The symmetry broken part of the direct pair correlation function has been calculated using a series in ascending powers of the order parameters and which contains three- and higher-bodies direct correlation functions of the isotropic phase. It is shown that a very accurate description of freezing transitions for a wide class of potentials is found by considering the first two terms of this series. The results found for freezing parameters including structure of the frozen phase for fluids interacting via the inverse power potential u(r) = \epsilon (\sigma/r)^{n} for n ranging from 4 to \infty are in very good agreement with simulation results. It is found that for n > 6.5 the fluid freezes into a face centred cubic (fcc) structure while for n \leq 6 the body centred cubic (bcc) structure is preferred. The fluid-bcc-fcc triple point is found to be at 1/n = 0.158 which is in good agreement with simulation result.