Properties of non-FCC hard-sphere solids predicted by density functional theory

Physics – Condensed Matter – Statistical Mechanics

Scientific paper

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Scientific paper

10.1103/PhysRevE.74.021121

The free energies of the FCC, BCC, HCP and Simple Cubic phases for hard spheres are calculated as a function of density using the Fundamental Measure Theory models of Rosenfeld et al (PRE 55, 4245 (1997)), Tarazona (PRL 84, 694 (2001)) and Roth et al (J. Phys.: Cond. Matt. 14, 12063 (2002)) in the Gaussian approximation. For the FCC phase, the present work confirms the vanishing of the Lindemann parameter (i.e. vanishing of the width of the Gaussians) near close packing for all three models and the results for the HCP phase are nearly identical. For the BCC phase and for packing fractions above $\eta \sim 0.56$, all three theories show multiple solid structures differing in the widths of the Gaussians. In all three cases, one of these structures shows the expected vanishing of the Lindemann parameter at close packing, but this physical structure is only thermodynamically favored over the unphysical structures in the Tarazona theory and even then, some unphysical behavior persists at lower densities. The simple cubic phase is stabilized in the model of Rosenfeld et al. for a range of densities and in the Tarazona model only very near close-packing.

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