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” . Second, a variational principle for Helmholtz free energy is displayed whose minimization with respect to the ion‐pair size distribution serves to determine both and . In anticipation of future numerical applications, a binary collision approximation is specified for the short‐range interaction aspect of the functional .
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Research Article| September 10 2003
Ion‐Pair Theory of Concentrated Electrolytes. III. Variational Principle
Frank H. Stillinger;
Frank H. Stillinger, Ronald J. White; Ion‐Pair Theory of Concentrated Electrolytes. III. Variational Principle. J. Chem. Phys. 15 April 1971; 54 (8): 3395–3404. https://doi.org/10.1063/1.1675356
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