Equilibrium studies on oppositely charged polyelectrolytes

Polyelectrolytes are well known to be strongly correlated even in extremely dilute solutions. At high concentrations especially, proper accountability of ionic specificity in terms of ion size and dielectric environment is essential. We present how such ionic specificities affect the equilibrium thermodynamics of various electrolytes/polyelectrolytes systems. By accounting for the ionization equilibrium between the oppositely charged groups, an approximate analytical formula for the intra-chain pair potential can be derived in terms of the charge and size of the chain. In the case of oppositely charged polyelectrolytes, the inter-chain pair potential can also be derived self-consistently by incorporating all monomer and counterion degrees of freedom.