Monte Carlo Tests of Nucleation Concepts in the Lattice Gas Model

TL;DR

This paper tests classical nucleation theory using Monte Carlo simulations of the lattice gas model, examining cluster growth, nucleation barriers, and the validity of different cluster definitions across temperatures.

Contribution

It provides a detailed comparison of nucleation kinetics and cluster definitions in the lattice gas model, validating theoretical predictions and introducing methods to estimate nucleation barriers.

Findings

Physical clusters match volume estimates from the lever rule for large droplets.

Geometrical clusters are valid only below 60% of the critical temperature.

Chemical potential can be used to estimate nucleation barriers for non-spherical clusters.

Abstract

The conventional theory of homogeneous and heterogeneous nucleation in a supersaturated vapor is tested by Monte Carlo simulations of the lattice gas (Ising) model with nearest-neighbor attractive interactions on the simple cubic lattice. The theory considers the nucleation process as a slow (quasi-static) cluster (droplet) growth over a free energy barrier $\Delta F^*$, constructed in terms of a balance of surface and bulk term of a "critical droplet" of radius $R^*$, implying that the rates of droplet growth and shrinking essentially balance each other for droplet radius $R=R^*$. For heterogeneous nucleation at surfaces, the barrier is reduced by a factor depending on the contact angle. Using the definition of "physical" clusters based on the Fortuin-Kasteleyn mapping, the time-dependence of the cluster size distribution is studied for "quenching experiments" in the kinetic Ising model, and the cluster size $\ell ^*$ where the cluster growth rate changes sign is estimated. These studies of nucleation kinetics are compared to studies where the relation between cluster size and supersaturation is estimated from equilibrium simulations of phase coexistence between droplet and vapor in the canonical ensemble. The chemical potential is estimated from a lattice version of the Widom particle insertion method. For large droplets it is shown that the "physical clusters" have a volume consistent with the estimates from the lever rule. "Geometrical clusters" (defined such that each site belonging to the cluster is occupied and has at least one occupied neighbor site) yield valid results only for temperatures less than 60% of the critical temperature, where the cluster shape is non-spherical. We show how the chemical potential can be used to numerically estimate $\Delta F^*$ also for non-spherical cluster shapes.