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Liquid water and ices: understanding the structure and physical properties

A review of the structure and some properties of condensed phases of water is given. Since the discovery of the polymorphism of crystalline ice (beginning of the twentieth century), 15 ice modifications have been found and their structures have been determined. If we do not take into consideration proton ordering or disordering, nine distinct crystalline ice modifications in which water molecules retain their individuality are known. In the tenth, ice X, there are no H2O molecules. It contains ions (or atoms) of oxygen and hydrogen. The structure of all these modifications is described and information about their fields of stability and about the transition between them is given. It is emphasized that there are ice modifications which are metastable at any temperature and pressure (ices Ic, IV and XII), and many modifications can exist as metastable phases beyond their fields of stability. The ability of water to exist in metastable states is one of its remarkable properties. Several amorphous ice modifications (all of them are metastable) are known. Brief information about their properties and transitions between them is given. At the end of the 1960s the conception of the water structure as a three-dimensional hydrogen-bonded network was conclusively formed. Discovery of the polymorphism of amorphous ices awakened interest in the heterogeneity of the water network. Structural and dynamical heterogeneity of liquid water is discussed in detail. Computer simulation showed that the diffusion coefficient of water molecules in dense regions of the network is lower than in the loose regions, while an increase of density of the entire network gives rise to an increase of diffusion coefficient. This finding contradicts the conceptions associated with the primitive two-state models and can be explained from pressure dependences of melting temperature and of homogeneous nucleation temperature. A brief discussion of the picture of molecular motions in liquid water based on experiment and on computer simulation is given. This picture is still very incomplete. The most fascinating idea that was put forward during the last 20 years was the second critical point conjecture. It is still not clear whether this conjecture corresponds to reality.