Journal
NONLINEARITY
Volume 26, Issue 10, Pages 2899-2922Publisher
IOP PUBLISHING LTD
DOI: 10.1088/0951-7715/26/10/2899
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Funding
- National Science Foundation (NSF) [DMS-1319731]
- NSF Center for Theoretical Biological Physics (CTBP) [PHY-0822283]
- National Institutes of Health [R01GM096188]
- Natural Science Foundation of China [NSFC-11101276, NSFC-91130012]
- Alexander von Humboldt Foundation
- Direct For Mathematical & Physical Scien
- Division Of Physics [1308264] Funding Source: National Science Foundation
- Division Of Mathematical Sciences
- Direct For Mathematical & Physical Scien [1319731] Funding Source: National Science Foundation
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Near a charged surface, counterions of different valences and sizes cluster; and their concentration profiles stratify. At a distance from such a surface larger than the Debye length, the electric field is screened by counterions. Both recent studies using a variational mean-field approach that includes ionic size effects and Monte Carlo simulations suggest that counterion stratification is determined by the ionic valence-to-volume ratios. Central in the mean-field approach is a free-energy functional of ionic concentrations in which the ionic size effects are included through the entropic effect of solvent molecules. The corresponding equilibrium conditions define the generalized Boltzmann distributions relating the ionic concentrations to the electrostatic potential. This paper presents a detailed analysis and numerical calculations for such a free-energy functional to understand the dependence of the ionic charge density on the electrostatic potential through the generalized Boltzmann distributions, the role of ionic valence-to-volume ratios in the counterion stratification and the modification of Debye length due to the effect of ionic sizes.
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