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Comput Methods Biomech Biomed Engin. 2013;16(5):463-80. doi: 10.1080/10255842.2011.624769. Epub 2012 Jan 23.

Spatial variation of permittivity of an electrolyte solution in contact with a charged metal surface: a mini review.

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Laboratory of Biophysics, Faculty of Electrical Engineering, University of Ljubljana, Ljubljana, Slovenia.


Contact between a charged metal surface and an electrolyte implies a particular ion distribution near the charged surface, i.e. the electrical double layer. In this mini review, different mean-field models of relative (effective) permittivity are described within a simple lattice model, where the orientational ordering of water dipoles in the saturation regime is taken into account. The Langevin-Poisson-Boltzmann (LPB) model of spatial variation of the relative permittivity for point-like ions is described and compared to a more general Langevin-Bikerman (LB) model of spatial variation of permittivity for finite-sized ions. The Bikerman model and the Poisson-Boltzmann model are derived as limiting cases. It is shown that near the charged surface, the relative permittivity decreases due to depletion of water molecules (volume-excluded effect) and orientational ordering of water dipoles (saturation effect). At the end, the LPB and LB models are generalised by also taking into account the cavity field.

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