Macromolecules, Vol.36, No.20, 7824-7832, 2003
A modified random phase approximation of polyelectrolyte solutions
We compute the phase diagrams of salt-free polyelectrolyte solutions, using a modified Debye-Huckel approach. We introduce the chain connectivity via the random phase approximation with three modifications. First, we modify the electrostatic potential at short distances to include a boundary on the electrostatic attractions at the distance of closest approach between charges, which is important in semidilute solutions. This modification is shown to act as a hard core contribution in solutions of simple electrolytes. Second, we introduce a cutoff on the integration of the modes of wavelength smaller than the size over which the electrostatic attractions cannot be linearized and strongly perturbed chain are expected. A concentration-dependent cutoff is shown to be essential to predict physically reasonable phase diagrams. Third, ion condensation is included self-consistently. The modification does not give correct phase diagrams without the concentration-dependent cutoff. The combined modifications give phase diagrams in agreement with Monte Carlo simulations.