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February 21, 2026AIChE Journal2 citations

The elusive fluid‐and‐crystal coexistence state in simulations of monodisperse, hard‐sphere colloids

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JWJ. Galen WangUDUmesh DhumalMZMonica E. A. Zakhari

Key Points

  • The research aims to understand the challenges in realizing spontaneous fluid-crystal coexistence in monodisperse hard-sphere colloids.
  • Review of existing simulations and their findings on phase behavior.
  • Discussion of biases introduced in previous studies to achieve coexistence.
  • Analysis of Frenkel's entropy-exchange mechanism and its implications.
  • Spontaneous, long-lived fluid-crystal coexistence has not been observed in unbiased simulations.
  • Coexistence typically occurs only with physical or algorithmic bias.
  • The difficulty in achieving coexistence supports Frenkel's view on entropy in hard-sphere crystallization.

Abstract

Abstract Monodisperse, purely repulsive hard spheres (MPRHS) are a canonical model for fluid–solid phase behavior in atomic and colloidal systems. Liquid‐state theory, free‐energy calculations, simulations, and experiments establish a first‐order fluid–solid transition in this model, a thermodynamic picture we take as given. Following Alder and Wainwright, we treat explicit fluid–crystal phase separation—coexistence of fluid‐and‐crystal domains—as an important benchmark for confirming first‐order behavior, complementary to demonstrating phase transition between single phases. Against this backdrop, we highlight a specific gap. Decades of simulations have mapped equations of state, coexistence properties, and nucleation rates, forming a foundational body of results, yet spontaneous, long‐lived fluid–crystal coexistence has not been reported in unbiased MPRHS simulations. Instead, coexistence appears either when physical/model‐level bias is introduced (e.g., seeding, gravity) or under algorithmic bias designed to accelerate barrier crossing. Studies that avoid bias typically observe transient mixed states ultimately overtaken by a single metastable phase, consistent with Frenkel's estimate that a spontaneous coexistence state in even large simulations would require years of sampling. In this Perspective, we focus on why such coexistence is so difficult to realize under pristine conditions, and what that means for testing Frenkel's entropy‐exchange mechanism in simulation. We argue that this kinetic difficulty is precisely what one expects from Frenkel's picture of competing vibrational and configurational entropy in hard‐sphere crystallization, and that minimal, controlled “hardness” perturbations that directly enhance in‐cage vibrational entropy provide the most direct route to making that entropic mechanism dynamically accessible and quantifiable.

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Cite This Study

Wang et al. (2026) studied this question.

synapsesocial.com/papers/69994cdf873532290d021c1chttps://doi.org/10.1002/aic.70275
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