Classical density functional theory, unconstrained crystallization, and polymorphic behavior

TL;DR

This paper investigates the challenges of applying finite temperature density functional theory (ftDFT) to crystallization, identifies numerical instabilities in current models, and demonstrates the method's ability to predict polymorphic behavior in Lennard-Jones systems.

Contribution

It reveals the instability of tensor functionals in ftDFT and shows that reverting to an older model enables successful simulation of crystallization and polymorphism.

Findings

ftDFT can describe crystallization in inhomogeneous systems

Crystallization depends on boundary conditions and protocol

Energy barriers exist between different structural states

Abstract

While in principle, finite temperature density functional theory (ftDFT) should be a powerful tool for the study of crystallization, in practice this has not so far been the case. Progress has been hampered by technical problems which have plagued the study of the crystalline systems using the most sophisticated Fundamental Measure Theory models. In this paper, the reasons for the difficulties are examined and it is proposed that the tensor functionals currently favored are in fact numerically unstable. By reverting to an older, more heuristic model it is shown that all of the technical difficulties are eliminated. Application to a Lennard-Jones fluid results in a demonstration of power of ftDFT to describe crystallization in a highly inhomogeneous system. First, we show that droplets attached to a slightly hydrophobic wall crystallize spontaneously upon being quenched. The resulting crystallites are clearly faceted structures and are predominantly HCP structures. In contrast, droplets in a fully periodic calculational cell remain stable to lower temperatures and eventually show the same spontaneous localization of the density into 'atoms' but in an amorphous structure having many of the structural charactersitics of a glass. A small change of the protocol leads, at the same temperature, to the formation of crystals, this time with the FCC structure typical of bulk Lennard-Jones solids. The FCC crystals have lower free energy than the amorphous structures which in turn are more stable than the liquid droplets. It is demonstrated that as the temperature is raised, the free energy differences between the structures decreases until the solid clusters become less stable than the liquid droplets and spontaneously melt. The presence of energy barriers separating the various structures is therefore clearly demonstrated.