Density Fluctuations in an Electrolyte from Generalized Debye-Hueckel Theory

Abstract

Near-critical thermodynamics in the hard-sphere (1,1) electrolyte is well described, at a classical level, by Debye-Hueckel (DH) theory with (+,-) ion pairing and dipolar-pair-ionic-fluid coupling. But DH-based theories do not address density fluctuations. Here density correlations are obtained by functional differentiation of DH theory generalized to {\it non}-uniform densities of various species. The correlation length $\xi$ diverges universally at low density $\rho$ as $(T\rho {)}^{-1/4}$ (correcting GMSA theory). When $\rho ={\rho }_c$ one has $\xi \approx {\xi }_0^{+}/t^{1/2}$ as $t\equiv (T-T_c)/T_c\to 0+$ where the amplitudes ${\xi }_0^{+}$ compare informatively with experimental data.

5 pages, REVTeX, 1 ps figure included with epsf. Minor changes, references added. Accepted for publication in Phys. Rev. Lett

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