arXiv subjects

Frédéric Caupin

Publications and source records attributed to Frédéric Caupin.

24 records · Page 2Linked to original sources

arXiv2017

Compressibility anomalies in stretched water and their interplay with density anomalies

Water keeps puzzling scientists because of its numerous properties which behave oppositely to usual liquids: for instance, water expands upon cooling, and liquid water is denser than ice. To explain this anomalous behaviour, several theories have been proposed, with different predictions for the properties of supercooled water (liquid at conditions where ice is more stable). However, discriminating between those theories with experiments has remained elusive because of spontaneous ice nucleation. Here we measure the sound velocity in liquid water stretched to negative pressure, and derive an experimental equation of state, which reveals compressibility anomalies. We show by rigorous thermodynamic relations how these anomalies are intricately linked with the density anomaly. Some features we observe are necessary conditions for the validity of two theories of water.

physics.chem-ph↗

arXiv2016

Molecular mechanism for cavitation in water under tension

Despite its relevance in biology and engineering, the molecular mechanism driving cavitation in water remains unknown. Using computer simulations, we investigate the structure and dynamics of vapor bubbles emerging from metastable water at negative pressures. We find that in the early stages of cavitation, bubbles are irregularly shaped and become more spherical as they grow. Nevertheless, the free energy of bubble formation can be perfectly reproduced in the framework of classical nucleation theory (CNT) if the curvature dependence of the surface tension is taken into account. Comparison of the observed bubble dynamics to the predictions of the macroscopic Rayleigh--Plesset (RP) equation, augmented with thermal fluctuations, demonstrates that the growth of nanoscale bubbles is governed by viscous forces. Combining the dynamical prefactor determined from the RP equation with the free energy of CNT yields an analytical expression for the cavitation rate that reproduces the simulation results very well over a wide range of pressures. Furthermore, our theoretical predictions are in excellent agreement with cavitation rates obtained from inclusion experiments. This suggests that homogeneous nucleation is observed in inclusions, whereas only heterogeneous nucleation on impurities or defects occurs in other experiments.

physics.comp-ph↗

arXiv2016

An Equation of State For The TIP4P/2005 Model of Water Including Negative Pressures

One of the most promising frameworks for understanding the anomalies of cold and especially supercooled water is that of two-structure thermodynamics, in which water is viewed as a non-ideal mixture of two interconvertible local structures. The non-ideality of this mixture may give rise, at very low temperatures, to a liquid-liquid phase transition (LLPT) and a liquid-liquid critical point (LLCP), at which thermodynamic response functions diverge. Various versions of the "two-structure equation of state" (TSEOS) based on this concept have shown remarkable agreement with both experimental data in real water and simulation results. However, recent experiments probing supercooled water at negative pressures reveal the inadequacy of extrapolations of equations of state developed for positive pressures, and have begun to shed additional light on the source of the anomalies of supercooled water. We have analyzed simulation results for the TIP4P/2005 model over a broad range of positive and negative pressures from ambient temperature to deep supercooling. We find that by explicitly incorporating a liquid-vapor spinodal into a two-structure equation of state, we are able to match the simulation data in TIP4P/2005 with striking accuracy. In particular, our equation of state reproduces the observed lines of minima and maxima in the density, isothermal compressibility, and isobaric heat capacity. Contrary to scenarios in which a retracing spinodal accounts for the thermodynamic anomalies of water, we find that the liquid-vapor spinodal in this model continues monotonically to lower pressures as temperature is decreased, influencing but not giving rise to the locus of density maxima and other thermodynamic anomalies. We explain the behavior of TIP4P/2005 in terms of two phenomena: the competition between two local structures and a monotonic liquid-vapor spinodal.

cond-mat.stat-mech↗

arXiv2016

Curvature-dependence of the liquid-vapor surface tension beyond the Tolman approximation

Surface tension is a macroscopic manifestation of the cohesion of matter, and its value $σ_\infty$ is readily measured for a flat liquid-vapor interface. For interfaces with a small radius of curvature $R$, the surface tension might differ from $σ_\infty$. The Tolman equation, $σ(R) = σ_\infty / (1 + 2 δ/R)$, with $δ$ a constant length, is commonly used to describe nanoscale phenomena such as nucleation. Here we report experiments on nucleation of bubbles in ethanol and n-heptane, and their analysis in combination with their counterparts for the nucleation of droplets in supersaturated vapors, and with water data. We show that neither a constant surface tension nor the Tolman equation can consistently describe the data. We also investigate a model including $1/R$ and $1/R^2$ terms in $σ(R)$. We describe a general procedure to obtain the coefficients of these terms from detailed nucleation experiments. This work explains the conflicting values obtained for the Tolman length in previous analyses, and suggests directions for future work.

physics.chem-ph↗

arXiv2013

Anomalies in bulk supercooled water at negative pressure

Water is the most familiar liquid, and arguably the most complex. Anomalies of supercooled water have been measured during decades, and competing interpretations proposed. Yet, a decisive experiment remains elusive, because of unavoidable crystallization into ice. We investigate the state of water that is both supercooled and under mechanical tension, or negative pressure. Liquids under negative pressure can be found in plants or fluid inclusions in minerals. Using such water inclusions in quartz, we report the first measurements on doubly metastable water down to $-15^\circ\mathrm{C}$ and around $-100\,\mathrm{MPa}$. We observe sound velocity anomalies that can be reproduced quantitatively with molecular dynamics simulations. These results rule out one proposed scenario for water anomalies, and put further constraints on the remaining ones.

cond-mat.stat-mech↗

arXiv2010

Time-resolved quantitative multiphase interferometric imaging of a highly focused ultrasound pulse

Interferometric imaging is a well established method to image phase objects by mixing the image wavefront with a reference one on a CCD camera. It has also been applied to fast transient phenomena, mostly through the analysis of single interferograms. It is shown that for repetitive phenomena multiphase acquisition brings significant advantages. A 1 MHz focused sound field emitted by a hemispherical piezotransducer in water is imaged as an example. Quantitative image analysis provides high resolution sound field profiles. Pressure at focus determined by this method agrees with measurements from a fiber-optic probe hydrophone. This confirms that multiphase interferometric imaging can indeed provide quantitative measurements.

physics.optics↗