title: Salt-induced collapse and reexpansion of highly charged flexible polyelectrolytes.
abstract: We study the salt-dependent conformations of dilute flexible polyelectrolytes in solution via computer simulations. Low concentrations of multivalent salt induce the known conformational collapse of individual polyelectrolyte chains, but as the salt concentration is increased further this is followed by a reexpansion. We explicitly demonstrate that multivalent counterions can overcompensate the bare charge of the chain in the reexpansion regime. Both the degree of reexpansion and the occurrence of overcharging sensitively depend on ion size. Our findings are relevant for a wide range of salt-induced complexation phenomena.
authors.affiliation: Department of Materials Science and Engineering and Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Pai-Yi
authors.initials: PY
authors.lastname: Hsiao
authors.forename: Erik
authors.initials: E
authors.lastname: Luijten
mesh_terms: D003198:Computer Simulation; D004573:Electrolytes / Q000737:chemistry*; D008968:Molecular Conformation; D012492:Salts / Q000737:chemistry*; D012996:Solutions
chemical_list: D004573:Electrolytes; D012492:Salts; D012996:Solutions