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Pierre Ragueneau

Publications and source records attributed to Pierre Ragueneau.

2 recordsLinked to original sources

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 temperature 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 which leads to the collapse of thermodynamic data. The ratio between 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.

physics.chem-ph

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

We report shear viscosity of heavy water supercooled $33\,\mathrm{K}$ 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 $350\,\mathrm{nm}$ 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. The viscosity ratio between the two isotopes reaches 2.2 at the lowest temperature. A companion Letter [F. Caupin, P. Ragueneau, and B. Issenmann, arXiv:2112.09010] discusses this giant dynamic isotopic effect. 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.

physics.chem-ph