Journal of Chemical Physics, Vol.106, No.3, 1195-1209, 1997
A Percolation Theory of Ionic Clustering in Electrolytes
We use the methods of continuum percolation theory to develop a consistent, essentially analytic theory for the properties of the restricted primitive model (RPM) of electrolytes. Contributions to the thermodynamic properties of this system are divided into two types; those from pairs of ions in the same cluster, and those from pairs in different clusters (we call these IN and OUT contributions, respectively, for brevity). We give exact expressions for the IN contributions as weighted integrals over the ionic pair connectedness functions. We give an exact analytic solution for these functions in the generalized mean-spherical approximation. The OUT contributions are calculated by replacing the system of ionic clusters by a system of charged hard spheres having the same statistics, and using the analytic results available for the latter system. Because the method requires no input from simulations, it can be readily adapted to treat many different electrolyte systems. Our method closely models simulation data for the thermodynamic quantities of the RPM. An earlier note [J. Chem. Phys. 96, 9233 (1992)] sketched our theory and compared our results to electrolyte data. Here we present in detail the analytic basis for our method. In future papers we expect to present detailed numerical results.
Keywords:CHARGED HARD-SPHERES;MEAN SPHERICAL APPROXIMATION;RESTRICTED PRIMITIVE MODEL;HYPERNETTED-CHAIN EQUATION;CONTINUUM PERCOLATION;INTEGRAL-EQUATION;CRITICAL-POINT;FLUIDS;BEHAVIOR;MATRICES