treated dipolar spheres in the bulk [1] and near surfaces [2], and then extended their algorithms to more sophisticated
We have developed robust and efficient numerical methods for solving integral equation theories for electrolyte solutions. These models of spheres with embedded dipoles and quadrupoles methods are hybrids of Newton-Raphson and Picard iterations and [3]. The algorithm described in Ref. [2] has recently been have been obtained as extended versions of the previous methods applied to dipolar hard spheres near a metallic wall [4].
for pure solvents by solving nontrivial problems posed by the inclu-These studies, however, have never included ions (anions sion of ions. Bulk electrolytes and electrolytes near both inert and and cations) in the system. It is generally recognized that metallic surfaces are considered. The basic equations previously derived for a one-component fluid near a planar wall are extended a numerical method often becomes quite unstable once to a multicomponent fluid. Analytical expressions for elements of highly charged ions are included in the solvents [1, 2]. The the Jacobian matrices are arranged in compact form. A striking objective of the present article is to extend earlier methods feature of the method for surface problems is that the Jacobian is to electrolyte solutions, mixtures of solvent molecules and determined only from bulk properties. A discussion of some special treatments that need to be considered for asymmetric anions and ions, without deterioration in the convergence properties cations is included. These methods have been demonstrated using of the numerical methods. Although the basic equations the full reference hypernetted-chain theory for various sizes of ions are described for mixtures of dipolar hard spheres (solvent in a wide range of ionic concentrations. ᮊ 1996 Academic Press, Inc. molecules) and charged hard spheres (ions), they can readily be adapted to other related models.
Since the pair interactions are angle-dependent and the the last subject. lic surface or when the ion diameters differ, the wall-anion Robust and efficient algorithms were already developed and wall-cation density profiles differ. In the latter cases, by Kinoshita and Harada for pure solvents. They first special numerical considerations are required. The present article describes some details of the numerical methods used in a previous publication [5] in which theoretical re-1 Permanent address: Nuclear Chemical Engineering Research Section, sults for the structure of metal-electrolyte solution inter-