Estimation of the free energy of hard-sphere crystals via a free-volume approach

Abstract

The free energies of the face-centred (FCC) and base-centred cubic (BCC) hard-sphere (HS) crystals have been estimated via the free-volume approach. We present two free-volume equations for the FCC and BCC HS crystals, which are different from those predicted by Velasco et al. [Langmuir 14(19) (1998), 5652–5655], and the equations exhibit more accuracy than Velasco et al.'s equations. The limitation of using the free-volume approach was assessed by comparing with true free energies obtained by other well-known methods, and possible improvement and application are discussed.

Keywords:

• free volume
• hard sphere
• free energy
• molecular dynamics

Acknowledgements

This study was supported by Nanyang Technological University (NTU) under grant Nos M58120005 and M52120043, and computational resources were been provided by the School of Chemical and Biomedical Engineering at NTU.