Density and Phonon-Stiffness Anomalies of Water and Ice in the Full Temperature Range.

Abstract

The specific-heat difference between the O:H van der Waals bond and the H-O polar-covalent bond and the Coulomb repulsion between electron pairs on adjacent oxygen atoms determine the angle-length-stiffness relaxation dynamics of the hydrogen bond (O:H-O), which is responsible for the density and phonon-stiffness oscillation of water ice over the full temperature range. Cooling shortens and stiffens the part of relatively lower specific-heat, and meanwhile lengthens and softens the other part of the O:H-O bond via repulsion. Length contraction/elongation of a specific part always stiffens/softens its corresponding phonon. In the liquid and in the solid phase, the O:H bond contracts more than the H-O elongates, hence, an O:H-O cooling contraction and the seemingly "regular" process of cooling densification take place. During freezing, the H-O contracts less than the O:H elongates, leading to an O:H-O elongation and volume expansion. At extremely low temperatures, the O:H-O angle stretching lowers the density slightly as the O:H and the H-O lengths change insignificantly. In ice, the O-O distance is longer than it is in water, resulting in a lower density, so that ice floats.