Abstract
We generalize a variational principle for the mean spherical approximation for a system of charged hard spheres in 3D to arbitrary dimensions. We first construct a free energy variational trial function from the Debye-Hückel excess charging internal energy at a finite concentration and an entropy obtained at the zero-concentration limit by thermodynamic integration. In three dimensions the minimization of this expression with respect to the screening parameter leads to the mean spherical approximation, usually obtained by solution of the Ornstein-Zernike equation. This procedure, which interpolates naturally between the zero concentration/coupling limit and the high-concentration/ coupling limit, is extended to arbitrary dimensions. We conjecture that this result is also equivalent to the MSA as originally defined, although a technical proof of this point is left for the future. The Onsager limitT ΔS MSA/ΔE MSA → 0 for infinite concentration/coupling is satisfied for all d ≠ 2, while ford=2 this limit is 1.
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On leave from Department of Physics, University of Puerto Rico, Mayagüez Campus, Mayagüez, Puerto Rico, 00681.
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Velázquez, E.S., Blum, L. & Frisch, H.L. Variational extension of the mean spherical approximation to arbitrary dimensions. J Stat Phys 89, 203–214 (1997). https://doi.org/10.1007/BF02770761
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DOI: https://doi.org/10.1007/BF02770761