Transformations of body-centered cubic crystals composed of hard or soft spheres to liquids or face-centered cubic crystals

F Wang and YL Han, JOURNAL OF CHEMICAL PHYSICS, 150, 014504 (2019).

DOI: 10.1063/1.5059358

The monodispersed hard-sphere system is one of the simplest models for the study of phase transitions. Despite intensive studies of crystallization and melting of hard-sphere face-centered cubic (FCC) crystals, the phase transformations of hard-sphere body-centered cubic (BCC) crystals have not been explored because hard spheres cannot form a stable BCC lattice. In fact, unstable BCC hard-sphere crystals and their related phase transformations can be experimentally achieved. Here, we measured the kinetics of the melting and solid-solid transformations of BCC hard-sphere crystals at various volume fractions via molecular dynamics simulations. When the volume fraction phi < 0.494, the system melts catastrophically. At phi > 0.545, the BCC crystal transforms to a metastable polycrystal consisting of FCC and hexagonal close-packed (HCP) domains, which is different from those crystallized from supercooled liquids, and then slowly equilibrates toward the FCC crystal. At 0.494 < phi < 0.545, the BCC crystal transforms to an intermediate-order metastable state consisting of BCC and non-crystal particles without FCC and HCP symmetries and then equilibrates toward the coexistence of the FCC crystal and liquid. We further studied the melting and BCC-FCC transitions of crystals composed of soft spheres with potential u(r) = epsilon(r/sigma)(-n). The unstable BCC crystals at n = 12, 9, 8 exhibit similar melting and BCC-FCC transitions as hard- sphere BCC crystals, while the metastable BCC crystals at n = 5, 6, 7 melt quickly at low densities but take very long time for the BCC-FCC transition at high densities. We also estimate the BCC-FCC interfacial energy and critical nucleus size. These results cast light on the melting and solid-solid transformations of atomic BCC crystals, which exist widely in nature. Published under license by AIP Publishing.

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