Coupling parameter series expansion for fluid with square-well plus repulsive-square-barrier potential

Abstract

Monte Carlo simulations in the canonical ensemble are performed for fluid with potential consisting of a square-well plus a square-barrier to obtain thermodynamic properties such as pressure, excess energy, constant volume excess heat capacity, and excess chemical potential, and structural property such as radial distribution function. The simulations cover a wide density range for the fluid phase, several temperatures, and different combinations of the parameters defining the potential. These simulation data have been used to test performances of a coupling parameter series expansion (CPSE) recently proposed by one of the authors [S. Zhou, Phys. Rev. E 74, 031119 (2006)], and a traditional 2nd-order high temperature series expansion (HTSE) based on a macroscopic compressibility approximation (MAC) used with confidence since its introduction in 1967. It is found that (i) the MCA-based 2nd-order HTSE unexpectedly and depressingly fails for most situations investigated, and the present simulation results can serve well as strict criteria for testing liquid state theories. (ii) The CPSE perturbation scheme is shown to be capable of predicting very accurately most of the thermodynamic properties simulated, but the most appropriate level of truncating the CPSE differs and depends on the range of the potential to be calculated; in particular, the shorter the potential range is, the higher the most appropriate truncating level can be, and along with rising of the potential range the performance of the CPSE perturbation scheme will decrease at higher truncating level. (iii) The CPSE perturbation scheme can calculate satisfactorily bulk fluid rdf, and such calculations can be done for all fluid states of the whole phase diagram. (iv) The CPSE is a convergent series at higher temperatures, but show attribute of asymptotic series at lower temperatures, and as a result, the surest asymptotic value occurs at lower-order truncation.