Ordering, correlation functions and phase transitions in molecular systems

TL;DR

This paper reviews recent methods for calculating pair correlation functions in broken symmetry phases of molecular systems within density functional theory, enabling more accurate predictions of phase stability and transitions.

Contribution

It introduces an exact DFT formulation incorporating correlation functions of broken symmetry phases, improving phase transition analysis.

Findings

Accurate calculation of PCFs in broken symmetry phases.

Comparison shows improved accuracy over previous methods.

Application to various fluid freezing transitions.

Abstract

Although the classical density functional theory (DFT) of inhomogeneous fluids was formulated more than four decades ago, its application to broken symmetry phases of molecular systems remained a challenge. Approximate free energy functionals proposed in the past failed to give accurate description of relative stability of phases, phase transitions, and of properties arising due to broken symmetry. In a DFT pair correlation functions (PCFs) play a fundamental role. While in the case of homogeneous fluids, PCFs are routinely determined using experimental, theoretical or simulation methods, determination of PCFs of broken symmetry phases remained a problem. Breaking of symmetry at the transition point gives rise a new contribution to correlation functions which may differ significantly from that of the coexisting higher symmetry phase. We review methods which have been developed in the last few years to calculate PCFs of broken symmetry phases and their inclusion in the expressions of the grand potential and the intrinsic free-energy. This leads to formulation of an exact DFT. We describe application of the theory to freezing of variety of fluids into ordered phases and transition from an ordered phase of higher symmetry to a phase of lower symmetry. Comparison of results found from different versions of DFT and simulations reveal their accuracy. A brief description of basics of statistical mechanics is included to make the article self-contained.