Third-order thermodynamic perturbation theory for effective potentials that model complex fluids

Abstract

We have performed Monte Carlo simulations to obtain the thermodynamic properties of fluids with two kinds of hard-core plus attractive-tail or oscillatory potentials. One of them is the square-well potential with small well width. The other is a model potential with oscillatory and decaying tail. Both model potentials are suitable for modeling the effective potential arising in complex fluids and fluid mixtures with extremely-large-size asymmetry, as is the case of the solvent-induced depletion interactions in colloidal dispersions. For the former potential, the compressibility factor, the excess energy, the constant-volume excess heat capacity, and the chemical potential have been obtained. For the second model potential only the first two of these quantities have been obtained. The simulations cover the whole density range for the fluid phase and several temperatures. These simulation data have been used to test the performance of a third-order thermodynamic perturbation theory (TPT) recently developed by one of us [ S. Zhou Phys. Rev. E 74 031119 (2006)] as compared with the well-known second-order TPT based on the macroscopic compressibility approximation due to Barker and Henderson. It is found that the first of these theories provides much better accuracy than the second one for all thermodynamic properties analyzed for the two effective potential models.