Classical Density Functional Theory applied to the solid state

TL;DR

This paper introduces a stable and consistent implementation of classical Density Functional Theory for solid state phase diagrams, demonstrating robustness and semi-quantitative accuracy across various potentials.

Contribution

A new stable implementation of classical DFT that avoids numerical instabilities and does not rely on approximate spherical integration schemes.

Findings

Successfully computes phase diagrams for Lennard-Jones and Wang et al. potentials.

Semi-quantitative agreement with known phase diagrams.

Gaussian approximations are nearly as accurate as full minimization.

Abstract

The standard model of classical Density Functional Theory for pair potentials consists of a hard-sphere functional plus a mean-field term accounting for long ranged attraction. However, most implementations using sophisticated Fundamental Measure hard-sphere functionals suffer from potential numerical instabilities either due to possible instabilities in the functionals themselves or due to implementations that mix real- and Fourier-space components inconsistently. Here, we present a new implementation based on a demonstrably stable hard-sphere functional that is implemented in a completely consistent manner. The present work does not depend on approximate spherical integration schemes and so is much more robust than previous algorithms. The methods are illustrated by calculating phase diagrams for the solid state using the standard Lennard-Jones potential as well as a new class of potentials recently proposed by Wang et al (Phys. Chem. Chem. Phys. 22, 10624 (2020)). The latter span the range from potentials for small molecules to those appropriate to colloidal systems simply by varying a parameter. We verify that cDFT is able to semi-quantitatively reproduce the phase diagram in all cases. We also show that for these problems computationally cheap Gaussian approximations are nearly as good as full minimization based on finite differences.