Monte Carlo electrostatic persistence lengths compared with experiment and theory

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Abstract
An off‐lattice rotational isomeric state model Monte Carlo algorithm for a polyelectrolyte with Debye–Hueckel screening and no hard core repulsion is used to generate short (up to 150 unit) chains at (1) different ionic strengths, (2) varying uniform charge densities, and (3) p H–p K 0 governed ionization. The mean square radii of gyration are related to the apparent total persistence lengths of the polyelectrolytes via the wormlike chain model. Near the random coil limit the apparent electrostatic persistence length varies approximately as the inverse square root of the ionic strength and linearly with charge density. The persistence length behavior is very similar in cases (2) and (3). These approximate power laws agree well with those found experimentally for hyaluronate and variably ionized polyacrylic acid. The original electrostatic persistence length theory, which does not contain excluded volume effects, predicts power law exponents which are twice these. Corrections due to polyelectrolyte excluded volume theories do not consistently yield good fits to the data, but do give ‘‘pseudo‐,’’ or weakly changing power laws similar to those obtained from the Monte Carlo and experimental data. The similarity between the Monte Carlo and experimental results may indicate that the Debye–Hueckel approximation is reasonable, and that the neglect of hard core repulsion (e.g., zero chain diameter) is insignificant compared to electrostatic effects. This lends strength to the interpretations that electrostatic excluded volume effects explain much of the apparent deviation from the electrostatic persistence length theory and that the approximation of a smeared out line charge works fairly well, even when the actual charges are irregularly spaced.