Polyelectrolyte solutions with multivalent salts

We investigate the thermodynamic properties of a polyelectrolyte solution in the presence of multivalent salts. The polyions are modeled as rigid cylinders with the charge distributed uniformly along the major axis. The solution, besides the polyions, contain monovalent and divalent counterions as well as monovalent coions. The strong electrostatic attraction existing between the polyions and the counterions results in formation of clusters consisting of one polyion and a number of associated monovalent and divalent counterions. The theory presented in the paper allows us to explicitly construct the Helmholtz free energy of a polyelectrolyte solution. The characteristic cluster size, as well as any other thermodynamic property can then be determined by an appropriate operation on the free energy.