On the accuracy of the liquid theory approximate methods for the description of liquid metal thermodynamics

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Abstract
The accuracy of the various liquid theory methods for calculating the thermodynamic properties of liquid metals is investigated. The calculations have been made for liquid Na, Rb, Mg and Al over wide ranges of temperature T and density n using (i) the variational method and hard-sphere reference system (the HSV method), (ii) the Barker-Henderson (BH) method, (iii) the Weeks-Chandler-Andersen (WCA) method and (iv) the expressions for energy and pressure in terms of the radial distribution function found in the Percus-Yevick approximation (the PYEP method). The results of the calculations are compared with each other and with experiment. The pseudopotential model is used which describes all the atomic properties of the alkali metals to a high precision, those of Mg rather well, and of Al fairly well. It has been shown that the simple HSV approximation suitable for a semi-quantitative description of the liquid metal properties is insufficient for quantitative calculations of differential characteristics, such as melting temperatures, entropies of fusion, entropies of liquid alloy mixing, etc. The PYEP and BH methods allow the authors to calculate some thermodynamic potentials rather precisely but the computational difficulties prevent them from being used for calculating other thermodynamic properties. The WCA method has been found to combine high accuracy with sufficient simplicity of calculations and seems, therefore, to be the most promising one for quantitative calculations of liquid metal thermodynamics. They also discuss the problems of applicability of the methods considered at various T and n (particularly in the vicinity of the critical point), of the dependence of their accuracy on the metal valency and the sensitivity of the results to the type of pseudopotential model used.