Screening of a macroion by multivalent ions: A new boundary condition for the Poisson-Boltzmann equation and charge inversion

V. I. Perel, B. I. Shklovskii

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Abstract

Screening of a macroion by multivalent counterions is considered. It is shown that ions form strongly correlated liquid at the macroion surface. Cohesive energy of this liquid leads to strong additional attraction of counterions to the surface. Away from the surface this attraction is taken into account by a new boundary condition for the Poisson-Boltzmann equation. This equation is solved with the new boundary condition for a charged flat surface and a long cylinder. For a cylinder Onsager-Manning theory looses its universality so that apparent charge of the cylinder is smaller than their theory predicts and depends on its bare charge. It can also vanish or change sign.

Original languageEnglish (US)
Pages (from-to)446-453
Number of pages8
JournalPhysica A: Statistical Mechanics and its Applications
Volume274
Issue number3
DOIs
StatePublished - Dec 15 1999

Bibliographical note

Funding Information:
We are grateful to V.A. Bloomfield, M.M. Fogler, A.Yu. Grosberg, R. Kjellander, S. Marcelja, R. Podgornik and I. Rouzina for valuable discussions. This work was supported by RFSF (V.P.) and by NSF DMR-9616880.

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