A grand canonical Monte Carlo simulation study of polyelectrolyte solutions

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Abstract
We present the results of grand canonical Monte Carlo simulations on a model of ‘‘rod-like’’ polyelectrolyte solutions. The model is approximate, but well studied by a variety of techniques. The parameters in the model are chosen to mimic DNA and polystyrenesulfonate solutions. We find that the Poisson–Boltzmann equation retains its semiquantitative utility in this model if 1:1 electrolyte is present, and that integral equation theories are measurably even more accurate. By comparison with experimental results, we argue that there are limitations in the present model. Finally, a simulation of polyions surrounded by divalent mobile ions provides additional evidence for charge inversion under certain thermodynamic conditions. This feature is not predicted by the Poisson–Boltzmann equation.