Cluster-variation approximation for a network-forming lattice-fluid model

We consider a three-dimensional lattice model of a network-forming fluid, which has been recently investigated by Girardi by means of Monte Carlo simulations [J. Chem. Phys. 126, 064503 (2007)], with the aim of describing water anomalies. We develop an approximate semianalytical calculation, based on a cluster-variation technique, which turns out to reproduce almost quantitatively different thermodynamic properties and phase transitions determined by the Monte Carlo method. Nevertheless, our calculation points out the existence of two different phases characterized by long-range orientational order, and of critical transitions between them and to a high-temperature orientationally disordered phase. Also, the existence of such critical lines allows us to explain certain 'kinks' in the isotherms and isobars determined by the Monte Carlo analysis. The picture of the phase diagram becomes much more complex and richer, though unfortunately less suitable to describe real water.