The Influence on Crystal Nucleation of an Order-Disorder Transition among the Subcritical Clusters

TL;DR

This paper develops a thermodynamic model to study how the degree of order in pre-critical clusters influences crystal nucleation, revealing an order-disorder transition that affects nucleation rates and pathways.

Contribution

It introduces a novel model linking cluster size and order, demonstrating how disorder impacts nucleation dynamics independently of critical cluster properties.

Findings

Disordered pre-critical clusters reduce nucleation rate.

An order-disorder transition occurs among pre-critical clusters.

Three distinct nucleation pathways are identified.

Abstract

Studies of nucleation generally focus on the properties of the critical cluster, but the presence of defects within the crystal lattice means that the population of nuclei necessarily evolve through a distribution of pre-critical clusters with varying degrees of structural disorder on their way to forming a growing stable crystal. To investigate the role pre-critical clusters play in nucleation, we develop a simple thermodynamic model for crystal nucleation in terms of cluster size and the degree of cluster order that allows us to alter the work of forming the pre-critical clusters without effecting the properties of the critical cluster. The steady state and transient nucleation behaviour of the system are then studied numerically, for different microscopic ordering kinetics. We find that the models exhibits a generic order-disorder transition in the pre-critical clusters. Independent of the type of ordering kinetics, increasing the accessibility of disordered pre-critical clusters decreases both the steady state nucleation rate and the nucleation lag time. Furthermore, the interplay between the free energy surface and the microscopic ordering kinetics leads to three distinct nucleation pathways.