Mean-field theory of the phase diagram of ultrasoft, oppositely charged polyions in solution

We investigate the phase separation of the “ultrasoft restricted primitive model” (URPM), a coarse-grained representation of oppositely charged, interpenetrating polyelectrolytes, within a mean-field description based on the “chemical picture.” The latter distinguishes between free ions and dimers of oppositely charged ions (Bjerrum pairs) which are in chemical equilibrium governed by a law of mass action. Interactions between ions, and between ions and dimers are treated within linearized Poisson-Boltzmann theory, at four levels of approximation corresponding to increasingly refined descriptions of the interactions. The URPM is found to phase separate into a dilute phase of dimers, and a concentrated phase of mostly free (unpaired) ions below a critical temperature T_c. The phase diagram differs, however, considerably from the predictions of recent simulations; T_c is about three times higher, and the critical density is much lower than the corresponding simulation data [D. Coslovich, J. P. Hansen, and G. Kahl, Soft Matter 7, 1690 (2011) https://doi.org/10.1039/c0sm01090a]. Possible reasons for this unexpected failure of mean-field theory are discussed. The Kirkwood line, separating the regimes of monotonically decaying and damped oscillatory decay of the charge-charge correlation function at large distances is determined within the random phase approximation.