Application of renormalization group corrected coupling parameter expansion method to square well fluids

Abstract

In this paper, we have applied the seventh order version of coupling parameter expansion (CPE) method combined with global renormalization group theory (GRGT) to square well fluids of various ranges and have performed the following studies. Firstly, the convergence of the GRGT iteration scheme has been studied. It is observed that the point-wise convergence is non-uniform and slow in the coexistence region away from the critical point. However, the point-wise convergence improved as the critical temperature is approached. Secondly, we have obtained the liquid–vapor phase diagrams (LVPDs) for the square well fluids. The LVPDs obtained using GRGT corrected seventh order CPE are significantly accurate over those obtained from GRGT corrected 1-order thermodynamic perturbation theory (TPT). Also, excessive flatness of LVPDs close to the critical region as observed in GRGT corrected 1-order TPT has not been seen in the LVPDs of present method. Thirdly, the critical exponents have been obtained using present method. The exponents are seen to be of Ising universality class and follow the Rushbrooke and Griffiths equalities qualitatively. Finally, a study of Yang–Yang anomaly has been done using our method. It has been observed that the method predicts the existence of the anomaly but the predictions of the strength of anomaly differed from those of simulations. The reasons for the differences are analyzed.