Field-Theoretic Approach to Ionic Systems: Criticality and Tricriticality

Abstract

A Landau-Ginzburg functional of two order parameters (charge-density $\varphi$ and mass-density deviation $\eta$) is developed in order to yield a field theory relevant to ionic lattice gases as well as a family of off-lattice models of ionic fluids that go beyond the restricted primitive model (RPM). In a mean-field (MF) approximation an instability of a uniform phase with respect to charge fluctuations with a wave-number $k\ne 0$ is found. This second-order transition to a charge-ordered phase terminates at a tricritical point (tcp). Beyond MF, a singularity of a mass correlation function for $k\to 0$ occurs at ion concentration lower than that of the MF tcp. An effective functional depending only on $\eta$ is constructed. For low ion concentration the usual Landau form of the simple-fluid (Ising) functional is obtained; hence in this theory the critical point is in the Ising universality class.

23 pages and 4 figures. Figure 4 has parts a and b, which are in separate figs. (i. e., the figures take 5 pages)