Evaluation of the grand-canonical partition function using expanded Wang-Landau simulations. I. Thermodynamic properties in the bulk and at the liquid-vapor phase boundary

The Wang-Landau sampling is a powerful method that allows for a direct determination of the density of states. However, applications to the calculation of the thermodynamic properties of realistic fluids have been limited so far. By combining the Wang-Landau method with expanded grand-canonical simulations, we obtain a high-accuracy estimate for the grand-canonical partition function for atomic and molecular fluids. Then, using the formalism of statistical thermodynamics, we are able to calculate the thermodynamic properties of these systems, for a wide range of conditions spanning the single-phase regions as well as the vapor-liquid phase boundary. Excellent agreement with prior simulation work and with the available experimental data is obtained for argon and CO2, thereby establishing the accuracy of the method for the calculation of thermodynamic properties such as free energies and entropies. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4712023]