Theory and Computer Simulation of the First- and Second-order Perturbative Contributions to the Free Energy of Square-well Fluids

Abstract

We have performed extensive MC simulations in the NVT ensemble of the first- and second-order perturbative contributions, F 1 and F 2 , to the free energy of square-well (SW) fluids for wide ranges of densities and potential widths. These data are used to test the accuracy of theoretical calculations performed within the framework of the Barker-Henderson perturbation theory. For F 2 the performance of several approximations is analyzed.