The ionic correlation contribution to the free energy of spherical double layers

An estimate of the ion fluctuation contribution to the free energy for a dispersion of spherical macroions, without additional salt, is made using the cell model. The Poisson–Boltzmann approximation is used to estimate the linear response in a given cell, which together with second order perturbatio...

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Bibliographic Details
Published in:The Journal of chemical physics 1988-10, Vol.89 (8), p.5145-5152
Main Authors: WOODWARD, C. E, JÖNSSON, B, AKESSON, T
Format: Article
Language:English
Subjects:
Chemistry
Colloidal state and disperse state
Exact sciences and technology
General and physical chemistry
Physical and chemical studies. Granulometry. Electrokinetic phenomena
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Summary:An estimate of the ion fluctuation contribution to the free energy for a dispersion of spherical macroions, without additional salt, is made using the cell model. The Poisson–Boltzmann approximation is used to estimate the linear response in a given cell, which together with second order perturbation theory allow us to calculate the free energy of interaction between a pair of cells. As well, an infinite order theory is developed. We find excellent agreement with simulations for monovalent counterions, the comparison becoming poorer for more strongly coupled systems. A cubic lattice of cells is studied, modeling a macroionic dispersion. The fluctuation contribution is shown to be several orders of magnitude larger than the usual quantum dispersion forces. However, it plays a minor role in the thermodynamics of the lattice.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.455632