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Field-theoretic description of ionic crystallization in the restricted primitive model

A. Ciach·O. Patsahan
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Abstract

Effects of charge-density fluctuations on a phase behavior of the restricted primitive model (RPM) are studied within a field-theoretic formalism. We focus on a $λ$-line of continuous transitions between charge-ordered and charge-disordered phases that is observed in several mean-field (MF) theories, but is absent in simulation results. In our study the RPM is reduced to a $ϕ^6$ 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 $λ$-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.

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A. Ciach, O. Patsahan. 2006-04-13. Field-theoretic description of ionic crystallization in the restricted primitive model. https://doi.org/10.1103/physreve.74.021508

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