Spontaneous Crystallization in Systems of Binary Hard Sphere Colloids

Abstract

Computer simulations of the fluid-to-solid phase transition in the hard sphere system were instrumental for our understanding of crystallization processes. But while colloid experiments and theory have been predicting the stability of several binary hard sphere crystals for many years, simulations were not successful to confirm this phenomenon. Here, we report the growth of binary hard sphere crystals isostructural to Laves phases, AlB${}_2$, and NaZn${}_{13}$ in simulation directly from the fluid. We analyze particle kinetics during Laves phase growth using event-driven molecular dynamics simulations with and without swap moves that speed up diffusion. The crystallization process transitions from nucleation and growth to spinodal decomposition already deep within the fluid-solid coexistence regime. Finally, we present packing fraction-size ratio state diagrams in the vicinity of the stability regions of three binary crystals.

9 pages, 11 figures

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Cited by in corpus (9)

• Colloidal Hard Spheres: Triumphs, Challenges and Mysteries
• Crystallization of Binary Nanocrystal Superlattices and the Relevance of Short-Range Attraction
• Irreversible swap algorithms for soft sphere glasses
• Freezing line of polydisperse hard spheres via direct-coexistence simulations
• Decoupling of rotation and translation at the colloidal glass transition
• Entropic Trapping of Hard Spheres in Spherical Confinement
• Fast event-driven simulations for soft spheres: from dynamics to Laves phase nucleation
• Molecular Dynamics Simulations of Binary Sphere Mixtures
• Tuning Stoichiometry to Promote Formation of Binary Colloidal Superlattices