Canonical Monte Carlo method is used to study a refined model of polyelectrolyte solution. The discrete charges on a polyion are located periodically along the helix. The ion‐ion and ion‐polyion interactions are described by a solvent‐averaged potential which accounts for the desolvation of ions. The major parameters of the short‐range potential function are Gurney coefficients for the counterion‐counterion (Acc) and the charged group‐counterion interaction (Apc). From simulations, the self‐diffusion coefficient for counterions, D/Do, was calculated. This quantity is rather sensitive to the value of Apc and much less to the choice of the counterion‐counterion coefficient. The refined model is used to analyze a fraction of apparently free counterions, α (≈D/D0), as obtained from recent measurements of transport properties in aqueous solutions of lithium and cesium poly(styrenesulfonate). The values of Gurney parameters, which fit experimental results, are determined: for a good agreement with experimental data an additional repulsive interaction Apc≈3900 J/mol is required for lithium poly(styrenesulfonate) at 5°C. This value is smaller (≈1500 J/mol) for lithium salt at 35°C, and negative, ≈−130 J/mol, for cesium salt of poly(styrenesulfonic) acid.
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