Limit of validity of Ostwald's rule of stages in a statistical mechanical model of crystallization

Abstract

We have only rules of thumb with which to predict how a material will crystallize, chief among which is Ostwald's rule of stages. It states that the first phase to appear upon transformation of a parent phase is the one closest to it in free energy. Although sometimes upheld, the rule is without theoretical foundation and is not universally obeyed, highlighting the need for microscopic understanding of crystallization controls. Here we study in detail the crystallization pathways of a prototypical model of patchy particles. The range of crystallization pathways it exhibits is richer than can be predicted by Ostwald's rule, but a combination of simulation and analytic theory reveals clearly how these pathways are selected by microscopic parameters. Our results suggest strategies for controlling self-assembly pathways in simulation and experiment.

8 pages, 8 figures

References in corpus (7)

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• Competitive nucleation and the Ostwald rule in a generalized Potts model with multiple metastable phases

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• Freezing of soft-core bosons at zero temperature: A variational theory
• Correlation between thermodynamic anomalies and pathways of ice nucleation in supercooled water
• Kinetic phase diagram for nucleation and growth of competing crystal polymorphs in charged colloidal suspensions
• Nucleation of colloids and macromolecules: does the nucleation pathway matter?
• Kinetic phase diagram for two-step nucleation in colloid-polymer mixtures
• Competitive Heterogeneous Nucleation onto a Microscopic Impurity in a Potts Model
• Shape-Determined Kinetic Pathways in 2D Solid-Solid Phase Transitions