Counterion-counterion correlation in the double layer around cylindrical polyions: Counterion size and valency effects

Abstract

Monte Carlo simulation and Poisson-Boltzmann results on some aspects of structure and thermodynamics of aqueous polyelectrolyte solutions are presented. The polyelectrolyte solution is described by an infinitely long cylindrical polyion surrounded by counterions modeled as rigid ions moving in a continuum dielectric. Ion-ion correlations in the form of volume average of the counterion-counterion distribution function in the double layer surrounding the polyion are reported for mono- and divalent counterions and for a range of polyion concentrations and charge density parameters in each case. These results confirm again strong influence of the charge density parameter of polyions on properties of polyelectrolyte solutions. The structural information is supplemented by the calculated thermodynamic properties such as osmotic coefficients and heats of dilutions; the latter quantity has not been examined yet in detail by computer simulations. The results are discussed in view of the existing experimental data from the literature for these properties.