Approach to the limit of counterion condensation

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Abstract
According to counterion condensation theory, one of the contributions to the polyelectrolyte free energy is a pairwise sum of Debye–Hückel potentials between polymer charges that are reduced by condensed counterions. When the polyion model is taken as an infinitely long and uniformly spaced line of charges, a simple closed expression for the summation, combined with entropy‐derived mixing contributions, leads to the central result of the theory, a condensed fraction of counterions dependent only on the linear charge density of the polyion and the valence of the counterion, stable against increases of salt up to concentrations in excess of 0.1M. Here we evaluate the sum numerically for B‐DNA models other than the infinite line of B‐DNA charges. For a finite‐length line there are end effects at low salt. The condensation limit is reached as a flat plateau by increasing the salt concentration. At a fixed salt concentration the condensation limit is reached by increasing the length of the line. At moderate salt even very short B‐DNA line‐model oligomers have condensed fractions not far from the infinite polymer limit. For a long double‐helical array with charge coordinates at the phosphates of B‐DNA, the limiting condensed fraction appears to be approached at low salt. In contrast to the results for the line of charges, however, the computed condensed fraction varies strongly with salt in the range of experimentally typical concentrations. Salt invariance is restored, in agreement with both the line model and experimental data, when dielectric saturation is considered by means of a distance‐dependent dielectric function. For sufficiently long B‐DNA line and helical models, at typical salt concentrations, the counterion binding fraction approaches the polymer limit as a linear function of 1/P, where P is the number of phosphate groups of B‐DNA.

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