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 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.