Stable and metastable hard sphere crystals in Fundamental Measure Theory

Abstract: Using fully minimized fundamental measure functionals, we investigate free energies, vacancy concentrations and density distributions for bcc, fcc and hcp hard-sphere crystals. Results are complemented by an approach due to Stillinger which is based on expanding the crystal partition function in terms of the number n of free particles while the remaining particles are frozen at their ideal lattice positions. The free energies of fcc/hcp and one branch of bcc agree well with Stillinger's approach truncated at n=2. A second branch of bcc solutions features rather spread-out density distributions around lattice sites and large equilibrium vacancy concentrations and is presumably linked to the shear instability of the bcc phase. Within fundamental measure theory and the Stillinger approach (n=2), hcp is more stable than fcc by a free energy per particle of about 0.001 k_{B}T. In previous simulation work, the reverse situation has been found which can be rationalized in terms of effects due to a correlated motion of at least 5 particles in the Stillinger picture.