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Properties of polyelectrolytes in tetravalent salt solutions are intensivelyinvestigated by a coarse-grained model. The concentration of salt and the sizeof tetravalent counterions are found playing a decisive role on chainproperties. If the size of tetravalent counterions is compatible with the oneof monomers, the chains show extended structures at low and at high saltconcentrations, whereas at intermediate salt concentrations, they acquirecompact and prolate structures. The swelling exponent of a chain against saltconcentration behaves in an analogous way as the morphological quantities.Under certain condition, the electrostatics gives a negative contribution tothe persistence length, in companion with a salt-induced mechanical instabilityof polyelectrolytes. Nearly at the same moment, it appears like-chargeattraction between chains. The equal size of the tetravalent ions and themonomers is the optimal condition to attain the strongest attraction betweenchains and the most compact chain structure. Moreover, the ions form amulti-layer organization around a chain and, thus, the integrated chargedistribution reveals an oscillatory behavior. The results suggest that chargeinversion has no direct connection with redissolution of polyelectrolytes athigh salt concentrations.Comment: 34 pages, 12 figures; accepted for publicatio

macromolecules

Chain Morphology, Swelling Exponent, Persistence Length, Like-Charge Attraction, and Charge Distribution around a Chain in Polyelectrolyte Solutions: Effects of Salt Concentration and Ion Size Studied by Molecular Dynamics Simulations