title: Dynamical Crossover in Hot Dense Water: The Hydrogen Bond Role.
abstract: We investigate the terahertz dynamics of liquid H2O as a function of pressure along the 450 K isotherm, by coupled quasielastic neutron scattering and inelastic X-ray scattering experiments. The pressure dependence of the single-molecule dynamics is anomalous in terms of both microscopic translation and rotation. In particular, the Stokes-Einstein-Debye equations are shown to be violated in hot water compressed to the GPa regime. The dynamics of the hydrogen bond network is only weakly affected by the pressure variation. The time scale of the structural relaxation driving the collective dynamics increases by a mere factor of 2 along the investigated isotherm, and the structural relaxation strength turns out to be almost pressure independent. Our results point at the persistence of the hydrogen bond network in hot dense water up to ice VII crystallization, thus questioning the long-standing perception that hydrogen bonds are broken in liquid water under the effect of compression.
authors.affiliation: EPSL, ICMP, École polytechnique fédérale de Lausanne (EPFL), Station 3, CH-1015 Lausanne, Switzerland.|Institut Laue Langevin , 71, avenue des Martyrs, B.P. 156, 38042 Grenoble, Cedex 9, France.
authors.forename: Umbertoluca
authors.initials: U
authors.lastname: Ranieri
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, CNRS UMR 7590, Université Pierre et Marie Curie , 4 Place Jussieu, F-75252 Paris, France.
authors.forename: Paola
authors.initials: P
authors.lastname: Giura
authors.affiliation: Istituto Nazionale di Ottica, CNR-INO , via N. Carrara 1, 50019 Sesto Fiorentino, Italy.|European Laboratory for Non Linear Optics, LENS, via N. Carrara 1, 50019 Sesto Fiorentino, Italy.
authors.forename: Federico A
authors.initials: FA
authors.lastname: Gorelli
authors.affiliation: Istituto Nazionale di Ottica, CNR-INO , via N. Carrara 1, 50019 Sesto Fiorentino, Italy.|European Laboratory for Non Linear Optics, LENS, via N. Carrara 1, 50019 Sesto Fiorentino, Italy.
authors.forename: Mario
authors.initials: M
authors.lastname: Santoro
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, CNRS UMR 7590, Université Pierre et Marie Curie , 4 Place Jussieu, F-75252 Paris, France.
authors.forename: Stefan
authors.initials: S
authors.lastname: Klotz
authors.affiliation: EPSL, ICMP, École polytechnique fédérale de Lausanne (EPFL), Station 3, CH-1015 Lausanne, Switzerland.
authors.forename: Philippe
authors.initials: P
authors.lastname: Gillet
authors.affiliation: ESRF - The European Synchrotron , 71, avenue des Martyrs, CS 40220 38043 Grenoble Cedex 9, France.
authors.forename: Luigi
authors.initials: L
authors.lastname: Paolasini
authors.affiliation: Institut Laue Langevin , 71, avenue des Martyrs, B.P. 156, 38042 Grenoble, Cedex 9, France.
authors.forename: Michael Marek
authors.initials: MM
authors.lastname: Koza
authors.affiliation: EPSL, ICMP, École polytechnique fédérale de Lausanne (EPFL), Station 3, CH-1015 Lausanne, Switzerland.|Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, CNRS UMR 7590, Université Pierre et Marie Curie , 4 Place Jussieu, F-75252 Paris, France.
authors.forename: Livia E
authors.initials: LE
authors.lastname: Bove