Two major contributions are devised for that theory of concentrated electrolytes which by convention regards the ions as completely paired into uncharged dipolar “molecules.” First, a more satisfactory expression is obtained for the wavelength‐dependent static dielectric “constant” ε(k). Second, a variational principle for Helmholtz free energy F is displayed whose minimization with respect to the ion‐pair size distribution p(1) serves to determine both F and p(1). In anticipation of future numerical applications, a binary collision approximation is specified for the short‐range interaction aspect of the functional F[p(1)].
F.H. Stillinger and R.J. White. Ion-pair theory of concentrated electrolytes: III. varia-tional principle. J. Chem. Phys. 54: 3395-3404, 1971.
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