title: Pressure dependence of viscosity in supercooled water and a unified approach for thermodynamic and dynamic anomalies of water.
abstract: The anomalous decrease of the viscosity of water with applied pressure has been known for over a century. It occurs concurrently with major structural changes: The second coordination shell around a molecule collapses onto the first shell. Viscosity is thus a macroscopic witness of the progressive breaking of the tetrahedral hydrogen bond network that makes water so peculiar. At low temperature, water at ambient pressure becomes more tetrahedral and the effect of pressure becomes stronger. However, surprisingly, no data are available for the viscosity of supercooled water under pressure, in which dramatic anomalies are expected based on interpolation between ambient pressure data for supercooled water and high pressure data for stable water. Here we report measurements with a time-of-flight viscometer down to [Formula: see text] and up to [Formula: see text], revealing a reduction of viscosity by pressure by as much as 42%. Inspired by a previous attempt [Tanaka H (2000)J Chem Phys112:799-809], we show that a remarkably simple extension of a two-state model [Holten V, Sengers JV, Anisimov MA (2014)J Phys Chem Ref Data43:043101], initially developed to reproduce thermodynamic properties, is able to accurately describe dynamic properties (viscosity, self-diffusion coefficient, and rotational correlation time) as well. Our results support the idea that water is a mixture of a high density, "fragile" liquid, and a low density, "strong" liquid, the varying proportion of which explains the anomalies and fragile-to-strong crossover in water.
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumiére Matiére and Institut Universitaire de France, F-69622 Villeurbanne, France.
authors.forename: Lokendra P
authors.initials: LP
authors.lastname: Singh
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumiére Matiére and Institut Universitaire de France, F-69622 Villeurbanne, France.
authors.forename: Bruno
authors.initials: B
authors.lastname: Issenmann
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumiére Matiére and Institut Universitaire de France, F-69622 Villeurbanne, France frederic.caupin@univ-lyon1.fr.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Caupin
keywords: dynamic crossover; supercooled water; two-state model; viscosity; water anomalies