# Deriving phase field crystal theory from dynamical density functional theory: consequences of the approximations

## TL;DR

This paper critically examines the derivation of phase field crystal (PFC) theory from dynamical density functional theory (DDFT), highlighting the impact of common approximations on the accuracy of phase diagrams and crystal stability predictions.

## Contribution

The authors identify key approximations in deriving PFC from DDFT that lead to significant inaccuracies, and suggest that deriving PFC models for the logarithm of the density may improve accuracy.

## Key findings

- Neglecting certain terms affects crystal stability predictions.
- Standard polynomial approximations introduce spurious phase behavior.
- A one-mode approximation for log density yields surprisingly accurate results.

## Abstract

Phase field crystal (PFC) theory, extensively used for modelling the structure of solids, can be derived from dynamical density functional theory (DDFT) via a sequence of approximations. Standard derivations neglect a term of form $\nabla\cdot[n\nabla L n]$, where $n$ is the scaled density profile and $L$ is a linear operator. We show that this term makes a significant contribution to the stability of the crystal, and dropping this term from the theory forces another approximation, that of replacing the logarithmic term from the ideal gas contribution to the free energy with its truncated Taylor expansion, to yield a polynomial in $n$. However, the consequences of doing this are the presence of an additional spinodal in the phase diagram, so the liquid is predicted first to freeze and then to melt again as the density is increased; and other periodic structures are erroneously predicted to be thermodynamic equilibria. A second approximation is to replace $L$ by a gradient expansion. This leads to the possibility of solutions failing to exist above a certain value of the average density. We illustrate these conclusions with a simple model two-dimensional fluid. The consequences of the PFC approximations are that the phase diagram is both qualitatively incorrect, in that it has a stripe phase, and quantitatively incorrect (by orders of magnitude) regarding the properties of the crystal. Thus, although PFC models are successful as phenomenological models of crystallisation, we find it impossible to derive the PFC model as an accurate approximation to DDFT, without introducing spurious artefacts. However, making a simple one-mode approximation for the logarithm of the density distribution is surprisingly accurate, which gives a tantalising hint that accurate PFC-type theories may instead be derived for the field $\log(\rho(x))$, rather than for the density profile itself.