Criticality, tricriticality, and crystallization in discretized models of electrolytes.
The Restricted Primitive Model of ionic systems is studied within a field-theoretic approach in order to provide a theoretic basis for the qualitative difference in the phase diagrams obtained in simulations for sigma/a=1,sigma/a=2, and sigma/a>/=3 ( a is the lattice constant and sigma is the ion diameter). The evolution of the phase diagrams from the case sigma/a=1 to the case sigma/a=square root[2] [nearest-neighbor ( NN ) occupancy excluded] is studied in the model with NN repulsion, 0</=J</= infinity, supplementing Coulomb forces. The boundary of stability of the charge-disordered phase with respect to short-wavelength charge fluctuations and the tricritical point are found in a mean-field ( MF ) approximation. Next, the effect of fluctuations is studied and we find that for J exceeding a particular value J0 a fluctuation-induced first-order phase transition should be expected instead of the continuous transition found in MF. At J= J0 the line of continuous transitions splits into two lines enclosing the two-phase region, whose thickness increases from zero when J>/= J0 increases. We argue that this transition corresponds to formation of a bcc ionic crystal. For high densities the ions form an fcc crystal, for which we find a fluctuation-induced first-order charge-ordered-charge-disordered transition, in agreement with recent simulation studies. Our results also shed light on the simulation results obtained for an off-lattice ionic system, for which a schematic phase diagram is constructed.
Institute of Physical Chemistry, Polish Academy of Sciences 01-224 Warszawa, Poland.
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