Crystal nuclei in melts: A Monte Carlo simulation of a model for attractive colloids

TL;DR

This study uses Monte Carlo simulations to investigate crystal nucleation in a colloidal melt model with attractive interactions, demonstrating the applicability of classical nucleation theory and providing detailed insights into nucleus properties.

Contribution

Introduces a continuous potential model for colloid-polymer systems and applies advanced simulation techniques to analyze nucleation and phase transition properties.

Findings

Classical nucleation theory accurately describes the nucleation barrier.

Surface excess free energy of nuclei can be quantitatively determined.

Anisotropy of interface free energy has minimal impact on nucleation barrier.

Abstract

As a model for a suspension of hard-sphere like colloidal particles where small nonadsorbing dissolved polymers create a depletion attraction, we introduce an effective colloid-colloid potential closely related to the Asakura-Oosawa model but that does not have any discontinuities. In simulations, this model straightforwardly allows the calculation of the pressure from the Virial formula, and the phase transition in the bulk from the liquid to crystalline solid can be accurately located from a study where a stable coexistence of a crystalline slab with a surrounding liquid phase occurs. For this model, crystalline nuclei surrounded by fluid are studied both by identifying the crystal-fluid interface on the particle level (using suitable bond orientational order parameters to distinguish the phases) and by "thermodynamic" means. I.e., the latter method amounts to compute the enhancement of chemical potential and pressure relative to their coexistence values. We show that the chemical potential can be obtained from simulating thick films, where one wall with a rather long range repulsion is present, since near this wall the Widom particle insertion method works, exploiting the fact that the chemical potential in the system is homogeneous. Finally, the surface excess free energy of the nucleus is obtained, for a wide range of nuclei volumes. From this method, it is established that classical nucleation theory works, showing that for the present model the anisotropy of the interface excess free energy of crystals and their resulting nonspherical shape has only a very small effect on the barrier.