Study of melting of molecular crystals by a modified Pople–Karasz model

A new modified model that combines the modified models of Chandrasekhar et al. with those of Keskin and Özgan, which are based on the Pople–Karasz theory, is applied to study the thermodynamics of melting and solid–solid transitions of molecular crystals. The thermodynamic properties of the disordered system are evaluated relative to those of the perfectly ordered one using the lowest approximation of the cluster-variation method, which is identical to the mean-field approximation. A good agreement is found between the present modified theory and the available experimental data. For melting transitions the agreement is excellent and much better than with the calculations of the Pople–Karasz theory and its previous modified theories. Approximate agreement is obtained for the solid–solid transitions. However, for these transition the experimental agreement with the present modified theory is still better than previous modified theories except at zero and low pressures.