Two-step nucleation in confined geometry: Phase diagram of finite particles on a lattice gas model

Abstract

We use a degenerated Ising model to describe nucleation and crystallization from solution in a confined two-component system. The free energy is calculated using metadynamics simulation with coordination numbers as the reaction coordinates. We deploy nudged elastic band simulation to determine the minimum energy path and give properties of the crystallization path. In this confined system, depletion effects, which could also be caused by slow material transport in the solution, prevent the post-critical cluster from further growth, and the crystalline state would only be stable at larger cluster sizes. Fluctuation of the higher coupling strength of the crystalline state enables further growth until the crystalline cluster is in equilibrium with the solvent, and this way, a second barrier is crossed. From the parameters and setup, we find necessary conditions for the occurrence of two-step nucleation in our system. These findings can be adapted to real systems as biomineralization, colloidal crystallization, and the solidification of metals.