The high-frequency dynamics of liquid water

This article is dedicated to reviewing the recent inelastic x-ray scattering (IXS) work on the high-frequency collective dynamics in liquid water. The results obtained with the IXS technique are directly compared with existing ones from inelastic neutron scattering (INS) and molecular dynamics simulation investigations that were carried out with the aim of achieving an understanding of the collective properties of water at the microscopic level. The IXS work has made it possible to demonstrate experimentally the existence, in the range of exchange momentum (Q) examined (1-10 nm-1), of two branches of collective modes: one linearly dispersing with Q (with the apparent sound velocity of 3200 m s-1) and the other at almost constant energy (5-7 meV). It has been possible to show that the dispersing branch originates from an upwards bend of the ordinary sound branch observed in low-frequency measurements. The study of this sound velocity dispersion, marking a transition from the ordinary sound, co, to the `fast' sound, c, as a function of temperature, has made it possible to relate the origin of this phenomenon to a structural relaxation process, which presents many analogies with those observed for glass-forming systems. The possibility of estimating from the IXS data the value of the relaxation time, , as a function of temperature leads to a relating of the relaxation process to the structural rearrangements induced by the making and breaking of hydrogen bonds. In this framework, it is then possible to recognize a hydrodynamical `normal' regime, i.e. one for which the density fluctuations have a period of oscillation that is on a timescale that is long with respect to , and a solid-like regime in the opposite limit. In the latter regime, the density fluctuations `feel' the liquid as frozen and the sound velocity is much higher: this is `fast' sound, whose velocity is equivalent to the sound velocity found in crystalline ice Ih.