The phase diagram of ice: a quasi-harmonic study based on a flexible water model

Abstract: The phase diagram of ice is studied by a quasi-harmonic approximation. The free energy of all experimentally known ice phases has been calculated with the flexible q-TIP4P/F model of water. The only exception is the high pressure ice X, in which the presence of symmetric O-H-O bonds prevents its modeling with this empirical interatomic potential. The simplicity of our approach allows us to study ice phases at state points of the T-P plane that have been omitted in previous simulations using free energy methods based on thermodynamic integration. The effect in the phase diagram of averaging the proton disorder that appears in several ice phases has been studied. It is found particularly relevant for ice III, at least for cell sizes typically used in phase coexistence simulations. New insight into the capability of the employed water model to describe the coexistence of ice phases is presented. We find that the H-ordered ices IX and XIV, as well as the H-disordered ice XII, are particularly stable for this water model. This fact disagrees with experimental data. The unexpected large stability of ice IX is a property related to the TIP4P-character of the water model. Only after omission of these three stable ice phases, the calculated phase diagram becomes in reasonable qualitative agreement to the experimental one in the T-P region corresponding to ice Ih, II, III, V, and VI. The calculation of the phase diagram in the quantum and classical limits shows that the most important quantum effect is the stabilization of ice II due to its lower zero-point energy when compared to that one of ices Ih, III, and V.