Dressed polyions, counterion condensation, and adsorption excess in polyelectrolyte solutions.
The phenomenon of Manning-Oosawa counterion condensation is given an explicit statistical mechanical and qualitative basis via a dressed polyelectrolyte formalism in connection with the topology of the electrostatic free-energy surface and is derived explicitly in terms of the adsorption excess of ions about the polyion via the nonlinear Poisson-Boltzmann equation. The approach is closely analogous to the theory of ion binding in micelles. Our results not only elucidate a Poisson-Boltzmann analysis, which shows that a fraction of the counterions lie within a finite volume around the polyion even if the volume of the system tends towards infinity, but also provide a direct link between Manning's theta-the number of condensed counterions for each polyion site-and a statistical thermodynamic quantity, namely, the adsorption excess per monomer.
Mohanty
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U
Eugene F. Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02167, USA.
Ninham
B W
BW
Oppenheim
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I
D000327:Adsorption; D004247:DNA / Q000737:chemistry*; D004563:Electrochemistry; D004573:Electrolytes; D007477:Ions; D008433:Mathematics; D008962:Models, Theoretical; D009838:Oligodeoxyribonucleotides / Q000737:chemistry; D011108:Polymers; D012996:Solutions
D004573:Electrolytes; D007477:Ions; D009838:Oligodeoxyribonucleotides; D011108:Polymers; D012996:Solutions; D004247:DNA