Field-theoretic description of ionic crystallization in the restricted primitive model.
Effects of charge-density fluctuations on a phase behavior of the restricted primitive model are studied within a field-theoretic formalism. We focus on a lambda line of continuous transitions between charge-ordered and charge-disordered phases that is observed in several mean-field theories, but is absent in simulation results. In our study the RPM is reduced to a phi(6) theory, and a fluctuation contribution to a grand thermodynamic potential is obtained by generalizing the Brazovskii approach. We find that in a presence of fluctuations the lambda -line disappears. Instead, a fluctuation-induced first-order transition to a charge-ordered phase appears in the same region of a phase diagram, where the liquid-ionic-crystal transition is obtained in simulations. Our results indicate that the charge-ordered phase should be identified with an ionic crystal.
Ciach
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Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Poland.
Patsahan
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