Empirical bond-order potential description of thermodynamic properties of crystalline silicon

Thermodynamic properties of silicon (diamond cubic phase) are calculated using an empirical many-body potential developed by Tersoff [Phys. Rev. Lett. 56, 632 (1986)] based on the concept of bond order. It is shown that this model gives predictions in good agreement with experiment for those properties governed by energetics (free energy, entropy, and heat capacity). The thermal expansion coefficient is less well described, which is traced to the fact that the model potential, in its present version, is overly stiff and therefore unable to account properly for the volume dependence of the transverse acoustic modes. Furthermore, sensitivity of the potential to whether each atom remains bonded to only four neighbors indicates that the short-range nature of the potential may necessitate model improvement before it is suitable for studies of thermomechanical properties at elevated temperatures or large deformations.