Phase field theory of crystal nucleation in hard sphere liquid

TL;DR

This paper applies phase field theory to model crystal nucleation in hard-sphere liquids, using molecular dynamics data to accurately predict interface properties and nucleation barriers, improving upon classical models.

Contribution

The study integrates molecular dynamics data into phase field modeling for hard-sphere liquids, accurately predicting nucleation barriers and interface properties without adjustable parameters.

Findings

Predicted interface properties match molecular dynamics data.

Nucleation barrier heights align with Monte Carlo results.

Tolman length decreases with increasing cluster size.

Abstract

The phase field theory of crystal nucleation described in [L. Granasy, T. Borzsonyi, T. Pusztai, Phys. Rev. Lett. 88, 206105 (2002)] is applied for nucleation in hard--sphere liquids. The exact thermodynamics from molecular dynamics is used. The interface thickness for phase field is evaluated from the cross--interfacial variation of the height of the singlet density peaks. The model parameters are fixed in equilibrium so that the free energy and thickness of the (111), (110), and (100) interfaces from molecular dynamics are recovered. The density profiles predicted without adjustable parameters are in a good agreement with the filtered densities from the simulations. Assuming spherical symmetry, we evaluate the height of the nucleation barrier and the Tolman length without adjustable parameters. The barrier heights calculated with the properties of the (111) and (110) interfaces envelope the Monte Carlo results, while those obtained with the average interface properties fall very close to the exact values. In contrast, the classical sharp interface model considerably underestimates the height of the nucleation barrier. We find that the Tolman length is positive for small clusters and decreases with increasing size, a trend consistent with computer simulations.