title: Counterion condensation revisited.
abstract: We review some of the characteristic properties of the structure of polyelectrolyte solutions: the condensed layer of counterions that forms abruptly at a critical threshold charge density on the polymer chain; the more diffuse Debye-Hückel cloud, which is spatially distinct from the condensed layer; and the entropic release of counterions from the condensed layer as a driving force for the binding of oppositely charged ligands. We present a reminder of the basis of our current understanding in a variety of experiments, simulations, and theories; and we attempt as well to clarify some misunderstandings. We present a new analysis of a lattice model that suggests why the limiting laws for polyelectrolyte thermodynamics have proved to be accurate despite the neglect of polymer-polymer interactions in their original derivation. We sketch recent progress in constructing a potential between counterion and polyion. A counterion located in the interface between condensed layer and Debye cloud is repelled from the polyion, creating a sharp boundary between the two counterion populations.
authors.affiliation: Department of Chemistry, Rutgers University, Piscataway, NJ 08854-8087, USA. gmanning@rutchem.rutgers.edu
authors.forename: G S
authors.initials: GS
authors.lastname: Manning
authors.forename: J
authors.initials: J
authors.lastname: Ray
mesh_terms: D004573:Electrolytes; D011108:Polymers / Q000737:chemistry*
chemical_list: D004573:Electrolytes; D011108:Polymers