The global phase diagram of the Gay–Berne model

Abstract

The phase diagram of the Gay–Berne model with anisotropy parameters k53, k 855 has been evaluated by means of computer simulations. For a number of temperatures, NPT simulations were performed for the solid phase leading to the determination of the free energy of the solid at a reference density. Using the equation of state and free energies of the isotropic and nematic phases available in the existing literature the fluid–solid equilibrium was calculated for the temperatures selected. Taking these fluid–solid equilibrium results as the starting points, the fluid–solid equilibrium curve was determined for a wide range of temperatures using Gibbs–Duhem integration. At high temperatures the sequence of phases encountered on compression is isotropic to nematic, and then nematic to solid. For reduced temperatures below T50.85 the sequence is from the isotropic phase directly to the solid state. In view of this we locate the isotropic–nematic–solid triple point at TINS50.85. The present results suggest that the high-density phase designated smectic B in previous simulations of the model is in fact a molecular solid and not a smectic liquid crystal. It seems that no thermodynamically stable smectic phase appears for the Gay–Berne model with the choice of parameters used in this work. We locate the vapor–isotropic liquid–solid triple point at a temperature TVIS50.445. Considering that the critical temperatures is Tc50.473, the Gay–Berne model used in this work presents vapor–liquid separation over a rather narrow range of temperatures. It is suggested that the strong lateral attractive interactions present in the Gay–Berne model stabilizes the layers found in the solid phase. The large stability of the solid phase, particularly at low temperatures, would explain the unexpectedly small liquid range observed in the vapor–liquid region.