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Class of consistent fundamental-measure free energies for hard-sphere mixtures

Andrés Santos*

  • Departamento de Física, Universidad de Extremadura, E-06071 Badajoz, Spain

  • *andres@unex.es; http://www.unex.es/eweb/fisteor/andres/

Phys. Rev. E 86, 040102(R) – Published 5 October, 2012

DOI: https://doi.org/10.1103/PhysRevE.86.040102

Abstract

In fundamental-measure theories the bulk excess free-energy density of a hard-sphere fluid mixture is assumed to depend on the partial number densities {ρi} only through the four scaled-particle-theory variables {ξα}, i.e., Φ({ρi})Φ({ξα}). By imposing consistency conditions, it is proven here that such a dependence must necessarily have the form Φ({ξα})=ξ0ln(1ξ3)+Ψ(y)ξ1ξ2/(1ξ3), where yξ22/12πξ1(1ξ3) is a scaled variable and Ψ(y) is an arbitrary dimensionless scaling function which can be determined from the free-energy density of the one-component system. Extension to the inhomogeneous case is achieved by standard replacements of the variables {ξα} by the fundamental-measure (scalar, vector, and tensor) weighted densities {nα(r)}. Comparison with computer simulations shows the superiority of this bulk free energy over the White Bear one.

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