Thermodynamic properties of a hard-core Lennard-Jones fluid from computer simulation and the coupling parameter series expansion.

The thermodynamic properties of a fluid with an interaction potential consisting in a hard-sphere core plus a Lennard-Jones tail have been obtained by Monte Carlo (MC) NVT simulation as a function of the density along several isotherms. In addition, the liquid–vapour coexistence has been determined by means of histogram-reweighting MC. These data have been used to analyse the performance of perturbation theory. To this end, the first three perturbation terms of the inverse temperature expansion of the Helmholtz free energy have been obtained by means of MC NVT simulations to test the convergence of the perturbation series and to compare with the predictions of the coupling parameter series expansion. Then, the predictions of the latter theory for the thermodynamic properties have been compared with the simulations, revealing the overall excellent performance of this perturbation theory for this model fluid, except in the vicinity of the critical point. [ABSTRACT FROM PUBLISHER]