Convergence and low temperature adaptability analysis of the high temperature series expansion of the free energy

Abstract

By appealing to the coupling parameter series expansion to calculate the first seven perturbation coefficients of the high temperature series expansion (HTSE) of the free energy, analysis of convergence and low temperature adaptability of the HTSE in calculating fluid thermodynamic properties is performed for the first time; the fluid thermodynamic properties considered include critical parameters, vapor-liquid coexistence curve, thermodynamic characteristic functions, chemical potential, pressure, and constant volume excess heat capacity. To proceed with the analysis, a well known square well model is used as sample; the well widths considered range over a wide interval, and the relevant temperatures amenable to simulation calculations (used as "exact" results to analyze the HTSE) can be both very high and very low. The main discoveries reached are summarized as follows: (1) The HTSE usually converges at the 4th-order truncation, but with decrease of the temperature considered, the lowest truncation order, which makes the HTSE to converge, tends to rise. As a conservative estimate, it is considered that the HTSE always converges for reduced temperature T* higher than 0.25, whereas for T* < 0.25 there appear signs indicating that the HTSE may diverge from the 7th-order truncation. (2) Within the temperature interval with T* ≥ 0.5, the HTSE converges approximately to the correct solution, and the HTSE can be reliably used to calculate the fluid thermodynamic properties, and within this temperature interval, the 4th-order truncation is enough; whereas for T* < 0.5, such as within the temperature interval with 0.275 ≤ T* ≤ 0.355, although the HTSE does converge, it does not converge to the correct solution, and the deviations between the HTSE calculations and MC simulations become an ever-prominent issue with the rising of the density, and the slopes of the thermodynamic properties over density are not satisfactorily represented. As a result, the HTSE is not suited for calculations for temperature interval T* < 0.5.