Isotope effect on the anomalies of water: A corresponding states analysis.

Light and heavy water show similar anomalies in thermodynamic and dynamic properties, with a consistent trend of anomalies occurring at higher temperatures in heavy water. Viscosity also increases faster upon cooling in heavy water, causing a giant isotope effect, with a viscosity ratio near 2.4 at 244 K. While a simple temperature shift apparently helps in collapsing experimental data for both isotopes, it lacks a clear justification, changes value with the property considered, and requires additional ad hoc scaling factors. Here, we use a corresponding states analysis based on the possible existence of a liquid-liquid critical point in supercooled water. This provides a coherent framework that leads to the collapse of thermodynamic data. The ratio between the dynamic properties of the isotopes is strongly reduced. In particular, the decoupling between viscosity η and self-diffusion D, measured as a function of temperature T by the Stokes-Einstein ratio Dη/T, is found to collapse after applying the corresponding states analysis. Our results are consistent with simulations and suggest that the various isotope effects mirror the one on the liquid-liquid transition.

Viscosity and Stokes-Einstein relation in deeply supercooled water under pressure.

We report measurements of the shear viscosity η in water up to 150 MPa and down to 229.5 K. This corresponds to more than 30 K supercooling below the melting line. The temperature dependence is non-Arrhenius at all pressures, but its functional form at 0.1 MPa is qualitatively different from that at all pressures above 20 MPa. The pressure dependence is non-monotonic, with a pressure-induced decrease of viscosity by more than 50% at low temperature. Combining our data with literature data on the self-diffusion coefficient Ds of water, we check the Stokes-Einstein relation which, based on hydrodynamics, predicts constancy of Dsη/T, where T is the temperature. The observed temperature and pressure dependence of Dsη/T is analogous to that obtained in simulations of a realistic water model. This analogy suggests that our data are compatible with the existence of a liquid-liquid critical point at positive pressure in water.

Shear viscosity and Stokes-Einstein violation in supercooled light and heavy water.

We report shear viscosity of heavy water supercooled 33K below its melting point, revealing a 15-fold increase compared to room temperature. We also confirm our previous data for the viscosity of supercooled light water and reach a better accuracy. Our measurements, based on the spontaneous Brownian motion of 350nm spheres, disagree at the lowest temperature with the only other available data, based on Poiseuille flow in a narrow capillary, which may have been biased by electro-osmotic effects. Here we provide a detailed description of the experiment and its analysis. We review the literature data about dynamic properties of water (viscosity, self-diffusion coefficient, and rotational correlation time), discuss their temperature dependence, and compare their decoupling in the two isotopes.

Pressure dependence of viscosity in supercooled water and a unified approach for thermodynamic and dynamic anomalies of water.

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 Phys 112:799-809], we show that a remarkably simple extension of a two-state model [Holten V, Sengers JV, Anisimov MA (2014) J Phys Chem Ref Data 43:043101], 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.

Viscosity of deeply supercooled water and its coupling to molecular diffusion.

The viscosity of a liquid measures its resistance to flow, with consequences for hydraulic machinery, locomotion of microorganisms, and flow of blood in vessels and sap in trees. Viscosity increases dramatically upon cooling, until dynamical arrest when a glassy state is reached. Water is a notoriously poor glassformer, and the supercooled liquid crystallizes easily, making the measurement of its viscosity a challenging task. Here we report viscosity of water supercooled close to the limit of homogeneous crystallization. Our values contradict earlier data. A single power law reproduces the 50-fold variation of viscosity up to the boiling point. Our results allow us to test the Stokes-Einstein and Stokes-Einstein-Debye relations that link viscosity, a macroscopic property, to the molecular translational and rotational diffusion, respectively. In molecular glassformers or liquid metals, the violation of the Stokes-Einstein relation signals the onset of spatially heterogeneous dynamics and collective motions. Although the viscosity of water strongly decouples from translational motion, a scaling with rotational motion remains, similar to canonical glassformers.

Bistability of a compliant cavity induced by acoustic radiation pressure.

We report on the first observation of multiple-order bistability due to acoustic radiation pressure in a compliant acoustic cavity formed between a spherical ultrasonic transducer immersed in water and the free liquid surface located at its focus. The hysteretic behavior of the cavity length, observed both with amplitude ramps and frequency sweeps, is accurately described using a one-dimensional model of a compliant Fabry-Pérot resonator assuming the acoustic radiation pressure to be the only coupling between the cavity and the acoustic field.