Phonon contribution to the entropy of hard sphere crystals

Abstract

Comparing the entropies of hard spheres in the limit of close packing, for different stacking sequences of the hexagonal layers, has been a challenge because the differences are so small. Here we present a new method based on a "sticky-sphere" model by which the system interpolates between hard spheres in one limit and a harmonic crystal in the other. For the fcc and hcp stackings we have calculated the entropy difference in the harmonic (sticky) limit, as well as the differences in the free energy change upon removing the stickiness in the model. The former, or phonon entropy, accounts for most of the entropy difference. Our value for the net entropy difference, 0.001164(8) k_B per sphere, is in excellent agreement with the best previous estimate by Mau and Huse [Phys. Rev. E 59, 4396 (1999)].