Non-mean-field screening by multivalent counterions

Abstract

Screening of a strongly charged macroion by its multivalent counterions can not be described in the framework of mean field Poisson-Boltzmann (PB) theory because multivalent counterions form a strongly correlated liquid (SCL) on the surface of the macroion. It was predicted that a distant counterion polarizes the SCL as if it were a metallic surface and creates an electrostatic image. The attractive potential energy of the image is the reason why the charge density of counterions decreases faster with distance from the charged surface than in PB theory. Using the Monte Carlo method to find the equilibrium distribution of counterions around the macroion, we confirm the existence of the image potential energy. It is also shown that due to the negative screening length of the SCL, $-2\xi$, the effective metallic surface is actually above the SCL by $|\xi |$.

9 pages, 6 figures; v5: new section added to address bulk screening by monovalent salt

References in corpus (6)

• Electrostatic correlations: from Plasma to Biology
• Statics and Dynamics of Strongly Charged Soft Matter
• Simulation of charge reversal in salty environments: Giant overcharging?
• Test-charge theory for the electric double layer
• Colloidal charge reversal: Dependence on the ionic size and the electrolyte concentration
• Negative density of states: screening, Einstein relation, and negative diffusion

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