Compressible cell gas models for asymmetric fluid criticality.

We thoroughly describe a class of models recently presented by Fisher and coworkers [Phys. Rev. Lett. 116, 040601 (2016)]PRLTAO0031-900710.1103/PhysRevLett.116.040601. The crucial feature of such models, termed compressible cell gases (CCGs), is that the individual cell volumes of a lattice gas are allowed to fluctuate. They are studied via the seldom-used (μ, p, T) ensemble, which leads to their exact mapping onto the Ising model. Remarkably, CCGs obey complete scaling, a formulation for the thermodynamic behavior of fluids near the gas-liquid critical point that accommodates features inherent to the asymmetric nature of this phase transition like the Yang-Yang (YY) and singular coexistence-curve diameter anomalies. The CCG_{0} models generated when volumes vary freely reveal local free volume fluctuations as the origin of these phenomena. Local energy-volume coupling is found to be another relevant microscopic factor. Furthermore, the CCG class is greatly extended by using the decoration transformation, with an interesting example being the Sastry-Debenedetti-Sciortino-Stanley model for hydrogen bonding in low-temperature water. The magnitude of anomalies is characterized by a single parameter, the YY ratio, which for the models so far considered here ranges from -∞ to 1/2.