Mesoscopic theory for size- and charge- asymmetric ionic systems. I. Case of extreme asymmetry

Abstract

A mesoscopic theory for the primitive model of ionic systems is developed for arbitrary size, $\lambda ={\sigma }_{+}/{\sigma }_{-}$, and charge, $Z=e_{+}/|e_{-}|$, asymmetry. Our theory is an extension of the theory we developed earlier for the restricted primitive model. The case of extreme asymmetries $\lambda \to \infty$ and $Z\to \infty$ is studied in some detail in a mean-field approximation. The phase diagram and correlation functions are obtained in the asymptotic regime $\lambda \to \infty$ and $Z\to \infty$, and for infinite dilution of the larger ions (volume fraction $n_p\sim 1/Z$ or less). We find a coexistence between a very dilute 'gas' phase and a crystalline phase in which the macroions form a bcc structure with the lattice constant $\approx 3.6{\sigma }_{+}$. Such coexistence was observed experimentally in deionized aqueous solutions of highly charged colloidal particles.