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

Soft Condensed Matter 2012-10-08 v2 Statistical Mechanics Chemical Physics

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{\rho_i} only through the four scaled-particle-theory variables ξα{\xi_\alpha}, i.e., Φ(ρi)Φ(ξα)\Phi({\rho_i})\to\Phi({\xi_\alpha}). 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)\Phi({\xi_\alpha})=-\xi_0\ln(1-\xi_3)+\Psi(y)\xi_1\xi_2/(1-\xi_3), where yξ22/12πξ1(1ξ3)y\equiv {\xi_2^2}/{12\pi \xi_1 (1-\xi_3)} is a scaled variable and Ψ(y)\Psi(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{\xi_\alpha} by the fundamental-measure (scalar, vector, and tensor) weighted densities nα(r){n_\alpha(\mathbf{r})}. Comparison with computer simulations shows the superiority of this bulk free energy over the White Bear one.

Keywords

Cite

@article{arxiv.1208.3089,
  title  = {Class of consistent fundamental-measure free energies for hard-sphere mixtures},
  author = {Andrés Santos},
  journal= {arXiv preprint arXiv:1208.3089},
  year   = {2012}
}

Comments

5 pages; v2: substantial additions