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Dipolar origin of the gas-liquid coexistence of the hard-core 1:1 electrolyte model.

We present a systematic study of the effect of the ion pairing on the gas-liquid phase transition of hard-core 1:1 electrolyte models. We study a class of dipolar dimer models that depend on a parameter R(c), the maximum separation between the ions that compose the dimer. This parameter can vary from sigma(+/-) that corresponds to the tightly tethered dipolar dimer model to R(c)--> infinity that corresponds to the Stillinger-Lovett description of the free ion system. The coexistence curve and critical point parameters are obtained as a function of R(c) by grand-canonical Monte Carlo techniques. Our results show that this dependence is smooth but nonmonotonic and converges asymptotically towards the free ion case for relatively small values of R(c). This fact allows us to describe the gas-liquid transition in the free ion model as a transition between two dimerized fluid phases. The role of the unpaired ions can be considered as a perturbation of this picture.