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Influence on crystal nucleation of an order-disorder transition among the subcritical clusters

Richard K. Bowles1,2,* and Peter Harrowell3,†

  • 1Department of Chemistry, University of Saskatchewan, Saskatoon, SK, Canada S7H 0H1
  • 2Centre for Quantum Topology and its Applications (quanTA), University of Saskatchewan, SK, Canada S7N 5E6
  • 3School of Chemistry, University of Sydney, New South Wales 2006, Australia

  • *richard.bowles@usask.ca
  • †peter.harrowell@sydney.edu.au

Phys. Rev. E 105, L062602 – Published 17 June, 2022

DOI: https://doi.org/10.1103/PhysRevE.105.L062602

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 precritical clusters with varying degrees of structural disorder on their way to forming a growing stable crystal. To investigate the role precritical 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 precritical clusters without affecting the properties of the critical cluster. The steady state and transient nucleation behavior of the system are then studied numerically, for different microscopic ordering kinetics. We find that the model exhibits a generic order-disorder transition in the precritical clusters. Independent of the types of ordering kinetics, increasing the accessibility of disordered precritical 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.

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