arXiv subjects

Frédéric Caupin

Publications and source records attributed to Frédéric Caupin.

At least 19 recordsLinked to original sources

arXiv2026

Effects of Interaction Range on Fluid Multicriticality: A Computational Study of an Interconverting Lattice Model

The range of intermolecular interactions plays a central role in determining the nature of phase behavior and critical phenomena. It is well established through studies of the Ising model that as interaction range increases, Monte Carlo simulations progressively approach meanfield predictions as the effects of critical fluctuations are suppressed. In this work, we investigate how varying interaction range influences fluid multicriticality using an interconverting lattice model that exhibits both Ising-like liquid-gas criticality and symmetric fluid tricriticality (similar to that in the superfluid $^4$He-$^3$He mixture). This minimal model serves as a representative system for exploring the evolution of competing critical points within a generic framework. We analyze the model using both meanfield theory and three-dimensional Monte Carlo simulations while systematically varying the number of interacting neighbors, $Z_n$, from 6 to 388. We find that the system with nearest-neighbor interactions ($Z_n=6$) reveals only two types of multicritical behavior, while for larger interaction ranges, four distinct archetypes emerge. We demonstrate the convergence of the simulation results to those of the meanfield theory as the number of interacting neighbors tends to infinity, and we discuss the results within the framework of crossover critical phenomena.

cond-mat.stat-mech↗

arXiv2026

Phase fluctuations in a confined fluid

Fluid phase equilibrium depends on the external constraints imposed on a system. In a closed system with fixed volume, depending on the average density, a vapor bubble may be stable, metastable, or unstable, with respect to the homogeneous liquid phase. In the case where the bubble is metastable, we study its lifetime, i.e. the average waiting time needed to observe bubble collapse, and the corresponding lifetime of the homogeneous liquid. For the smallest systems, we predict the possibility to observe phase flipping, when the fluid oscillates between states with and without bubble. We provide an example of phase flipping in a simulation of a Lennard-Jones fluid.

cond-mat.soft↗

arXiv2026

Shear and bulk viscosities of water up to 1.6 GPa and anomaly in the structural relaxation time

Deep in the Earth's crust, pressure exceeds one thousand times the atmospheric pressure. Water still flows under these conditions, but experiences dramatic changes in structure and fluidity. Using combined dynamic and inelastic light scattering techniques, we simultaneously measure the shear and bulk viscosities of water as a function of pressure. The former increases faster than the latter, so that their ratio shows a two-fold decrease from 0 to 1.6 GPa; we confirm this trend with simulations. We analyze our results in terms of the structural relaxation time $τ$. Contrary to other liquids, pressure initially accelerates relaxation in water. Our measurements reveal that $τ$ reaches a minimum close to 1 ps around 0.5 GPa. We interpret $τ$ as a the equilibration time of hydrogen bonds, and propose that the minimum in $τ$ arises from a structural anomaly which allows fastest interconversion between local structures in water, and generates a cascade of thermodynamic and dynamic anomalies.

cond-mat.soft↗

arXiv2026

Structural and dynamic anomalous properties of TIP4P/2005 water at extreme pressures

Water shows numerous thermodynamic, dynamic, and structural anomalies. Recent experiments [Eichler et al. Phys. Rev. Lett. 134, 134101 (2025)], based on measurements of shear and bulk viscosities of liquid water up to 1.6 GPa, have reported the existence of a minimum in the variation of the structural relaxation time τα with pressure at room temperature. Here we investigate this and related properties with molecular dynamics simulations of the TIP4P/2005 water model, performed at extreme pressures commensurate with the experiments. Specifically, we compute dynamic (self-diffusion, shear and bulk viscosities, and structural relaxation time) and structural (oxygen-oxygen radial distribution function and structure factor, translational order parameter) properties down to 220 K and up to 2.7 GPa. We find good agreement with the experimental observations, and confirm the existence of a minimum in τα . The microscopic information obtained from the simulations suggests that this anomaly is connected with the sudden reorganization of the hydrogen bond network induced by pressurization.

cond-mat.soft↗

arXiv2025

Degenerate Fluid Polyamorphism Induced by Symmetrical Molecular Interconversion

Fluid polyamorphism is the existence of multiple fluid-fluid phase transitions in a single-component substance. It can occur due to interconversion between two alternative molecular or supramolecular states. In this work, we investigate a special (``degenerate'') case of fluid polyamorphism, in which all three characteristic parameters of the interconversion equilibrium constant, i.e. the changes of energy, entropy, and volume, are zero. This feature of interconversion is typical for the Ising spin model of ferromagnets but is also observed in a polyamorphic chiral fluid mixture of interconverting enantiomers. To investigate the consequences of interconversion's degeneration for fluid polyamorphism, we have performed a meanfield analysis and 3D Monte Carlo simulations of a compressible binary lattice with interconverting species (referred to as the ``blinking-checkers model''), which generally demonstrates the existence of both liquid-gas and liquid-liquid transitions. By tuning the interaction parameters, we have demonstrated that, in the degenerate interconverting case, a coupling between the fraction of interconversion (a vector-like nonconserved order parameter) and the total density (a scalar conserved order parameter) may produce a symmetrical tricritical point. At this point, the line of second-order transitions between two fluids, ``disordered'' (with 50:50 interconversion) and ``ordered'' (with temperature and pressure dependent interconversion fraction), is terminated by first-order transitions between the fluid states. This point exhibits the typical features of symmetrical tricritical points as observed in a superfluid mixture of helium isotopes and in some magnetic materials. We also show that the transition between the ordered and disordered fluid could occur in either the liquid or the gaseous phase.

cond-mat.soft↗

arXiv2024

Anomalous behaviour of transport properties in a supercooled water-glycerol mixture

Glycerol acts as a natural cryoprotectant by depressing the temperature of ice nucleation and slowing down the dynamics of water mixtures. In this work we characterize dynamics -- diffusion, viscosity, and hydrogen-bond dynamics -- as well as density anomaly and structure of water mixtures with 1\% to 50\% w/w glycerol at low temperatures via molecular dynamics simulations using all-atom and coarse-grained models. Simulations reveal distinct violations of the Stokes-Einsten relation in the low temperature regime for water and glycerol. Deviations are positive for water at all concentrations, and positive for glycerol in very dilute solutions but turning negative in concentrated ones. The all-atom and coarse-grained models reveal an unexpected crossover in the dynamics of the 1% and 10 % w/w glycerol at the lowest simulated temperatures. This crossover manifests in the diffusion coefficients of water and glycerol, as well as in the viscosity and lifetime of hydrogen-bonds in water. We interpret that the crossover originates on the opposing dependence with glycerol concentration of the two factors controlling the solution's slow-down: the increase in tetrahedrally coordinated water and the dynamics and clustering of the glycerol molecules. We anticipate that this dynamic crossover will also occur for solution of water with other polyols.

cond-mat.soft↗

arXiv2024

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↗

arXiv2023

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

We report measurements of the shear viscosity $η$ in water up to $150\,\mathrm{MPa}$ and down to $229.5\,\mathrm{K}$. This corresponds to more than $30\,\mathrm{K}$ supercooling below the melting line. The temperature dependence is non-Arrhenius at all pressures, but its functional form at $0.1\,\mathrm{MPa}$ is qualitatively different from that at all pressures above $20\,\mathrm{MPa}$. 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 $D_\mathrm{s}$ of water, we check the Stokes-Einstein relation which, based on hydrodynamics, predicts constancy of $D_\mathrm{s} η/T$, where $T$ is the temperature. The observed temperature and pressure dependence of $D_\mathrm{s} η/T$ 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.

cond-mat.soft↗

arXiv2023

Interfacial Properties of Fluids Exhibiting Liquid Polyamorphism and Water-Like Anomalies

It has been hypothesized that liquid polyamorphism, the existence of multiple amorphous states in a single component substance, may be caused by molecular or supramolecular interconversion. A simple microscopic model [Caupin and Anisimov, Phys. Rev. Lett., 127, 185701, (2021)] introduces interconversion in a compressible binary lattice to generate various thermodynamic scenarios for fluids that exhibit liquid polyamorphism and/or water-like anomalies. Using this model, we demonstrate the dramatic effects of interconversion on the interfacial properties. In particular, we find that the liquid-vapor surface tension exhibits either an inflection point or two extrema in its temperature dependence. Correspondingly, we observe anomalous behavior of the interfacial thickness and a significant shift in the location of the concentration profile with respect to the location of the density profile.

cond-mat.soft↗

arXiv2022

Effects of compressibility and wetting on the liquid-vapor transition in a confined fluid

When a fluid is constrained to a fixed, finite volume, the conditions for liquid-vapor equilibrium are different from the infinite volume or constant pressure cases. There is even a range of densities for which no bubble can form, and the liquid at a pressure below the bulk saturated vapor pressure remains indefinitely stable. As fluid density in mineral inclusions is often derived from the temperature of bubble disappearance, a correction for the finite volume effect is required. Previous works explained these phenomena, and proposed a numerical procedure to compute the correction for pure water in a container completely wet by the liquid phase. Here we revisit these works, and provide an analytic formulation valid for any fluid and including the case of partial wetting. We introduce the Berthelot-Laplace length $λ=2γκ/3$, which combines the liquid isothermal compressibility $κ$ and its surface tension $γ$. The quantitative effects are fully captured by a single, non-dimensional parameter: the ratio of $λ$ to the container size.

physics.chem-ph↗

arXiv2022

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↗

arXiv2021

Interplay of vitrification and ice formation in a cryoprotectant aqueous solution at low temperature

The proneness of water to crystallize is a major obstacle to understanding its putative exotic behavior in the supercooled state. It also represents a strong practical limitation to cryopreservation of biological systems. Adding some concentration of glycerol, which has a cryoprotective effect preventing to some degree water crystallization, has been proposed as a possible way out, provided the concentration is small enough for water to retain some of its bulk character and/or for limiting the damage caused by glycerol on living organisms. Contrary to previous expectations, we show that in the ``marginal'' glycerol molar concentration $\approx18\%$, at which vitrification is possible with no crystallization on rapid cooling, water crystallizes upon isothermal annealing even below the calorimetric glass transition of the solution. Through a time-resolved polarized neutron scattering investigation, we extract key parameters, size and shape of the ice crystallites, fraction of water that crystallizes, crystallization time, which are important for cryoprotection, as a function of the annealing temperature. We also characterize the nature of the out-of-equilibrium liquid phases that are present at low temperature, providing more arguments against the presence of an iso-compositional liquid-liquid transition. Finally, we propose a rule-of-thumb to estimate the lower temperature limit below which water crystallization does not occur in aqueous solutions.

cond-mat.soft↗

arXiv2021

Minimal microscopic model for liquid polyamorphism and water-like anomalies

Liquid polyamorphism is the intriguing possibility for a single component substance to exist in multiple liquid phases. We propose a minimal model for this phenomenon. Starting with a binary lattice model with critical azeotropy and liquid-liquid demixing, we allow interconversion of the two species, turning the system into a single-component fluid with two states differing in energy and entropy. Unveiling the phase diagram of the non-interconverting binary mixture gives unprecedented insight on the phase behaviors accessible to the interconverting fluid, such as a liquid-liquid transition with a critical point, or a singularity-free scenario, exhibiting thermodynamic anomalies without polyamorphism. The model provides a unified theoretical framework to describe supercooled water and a variety of polyamorphic liquids with water-like anomalies.

cond-mat.stat-mech↗

arXiv2020

Effect of dissolved salt on the anomalies of water at negative pressure

Adding salt to water at ambient pressure affects its thermodynamic properties. At low salt concentration, anomalies such as the density maximum are shifted to lower temperature, while at large enough salt concentration they cannot be observed any more. Here we investigate the effect of salt on an anomaly recently observed in pure water at negative pressure: the existence of a sound velocity minimum along isochores. We compare experiments and simulations for an aqueous solution of sodium chloride with molality around $1.2\,\mathrm{mol\,kg^{-1}}$, reaching pressures beyond $-100\,\mathrm{MPa}$. We also discuss the origin of the minima in the sound velocity and emphasize the importance of the relative position of the temperatures of sound velocity and density anomalies.

physics.chem-ph↗

arXiv2018

Viscosity and self-diffusion of supercooled and stretched water from molecular dynamics simulations

Among the numerous anomalies of water, the acceleration of dynamics under pressure is particularly puzzling. Whereas the diffusivity anomaly observed in experiments has been reproduced in several computer studies, the parallel viscosity anomaly has received less attention. Here we simulate viscosity and self-diffusion coefficient of the TIP4P/2005 water model over a broad temperature and pressure range. We reproduce the experimental behavior, and find additional anomalies at negative pressure. The anomalous effect of pressure on dynamic properties becomes more pronounced upon cooling, reaching two orders of magnitude for viscosity at 220 K. We analyze our results with a dynamic extension of a thermodynamic two-state model, an approach which has proved successful in describing experimental data. Water is regarded as a mixture of interconverting species with contrasting dynamic behaviors, one being strong (Arrhenius), and the other fragile (non-Arrhenius). The dynamic parameters of the two-state models are remarkably close between experiment and simulations. The larger pressure range accessible to simulations suggests a modification of the dynamic two-state model, which in turn also improves the agreement with experimental data. Furthermore, our simulations demonstrate the decoupling between viscosity $η$ and self-diffusion coefficient $D$ as a function of temperature $T$. The Stokes-Einstein relation, which predicts a constant $D η/T$, is violated when $T$ is lowered, in connection with the Widom line defined by an equal fraction of the two interconverting species. These results provide a unifying picture of thermodynamics and dynamics in water, and call for experiments at negative pressure.

physics.chem-ph↗

arXiv2017

Two-structure thermodynamics for the TIP4P/2005 model of water covering supercooled and deeply stretched regions

One of the most promising frameworks for understanding the anomalies of cold and supercooled water postulates the existence of two competing, interconvertible local structures. If the non-ideality in the Gibbs energy of mixing overcomes the ideal entropy of mixing of these two structures, a liquid-liquid phase transition, terminated at a liquid-liquid critical point, is predicted. Various versions of the "two-structure equation of state" (TSEOS) based on this concept have shown remarkable agreement with both experimental data for metastable, deeply supercooled water and simulations of molecular water models. However, existing TSEOSs were not designed to describe the negative pressure region and do not account for the stability limit of the liquid state with respect to the vapor. While experimental data on supercooled water at negative pressures may shed additional light on the source of the anomalies of water, such data are very limited. To fill this gap, we have analyzed simulation results for TIP4P/2005, one of the most accurate classical water models available. We have used recently published simulation data, and performed additional simulations, over a broad range of positive and negative pressures, from ambient temperature to deeply supercooled conditions. We show that, by explicitly incorporating the liquid-vapor spinodal into a TSEOS, we are able to match the simulation data for TIP4P/2005 with remarkable accuracy. In particular, this equation of state quantitatively reproduces the lines of extrema in density, isothermal compressibility, and isobaric heat capacity. Contrary to an explanation of the thermodynamic anomalies of water based on a "retracing spinodal", the liquid-vapor spinodal in the present TSEOS continues monotonically to lower pressures upon cooling, influencing but not giving rise to density extrema and other thermodynamic anomalies.

cond-mat.stat-mech↗

arXiv2017

Shrinking of Rapidly Evaporating Water Microdroplets Reveals their Extreme Supercooling

The fast evaporative cooling of micrometer-sized water droplets in vacuum offers the appealing possibility to investigate supercooled water - below the melting point but still a liquid - at temperatures far beyond the state-of-the-art. However, it is challenging to obtain a reliable value of the droplet temperature under such extreme experimental conditions. Here, the observation of morphology-dependent resonances in the Raman scattering from a stream of perfectly uniform water droplets has allowed us to measure with an absolute precision of better than 0.2% the variation in droplet size resulting from evaporative mass losses. This finding proved crucial to an unambiguous determination of the droplet temperature. In particular, a fraction of water droplets with initial diameter of 6379$\pm$12 nm were found to remain liquid down to 230.6$\pm$0.6 K. Our results question temperature estimates reported recently for larger supercooled water droplets, and provide valuable information on the hydrogen-bond network in liquid water in the hard-to-access deeply supercooled regime.

cond-mat.other↗

arXiv2017

Thermodynamics of Fluid Polyamorphism

"Fluid polyamorphism" is the existence of different condensed amorphous states in a single-component fluid. It is either found or predicted, usually at extreme conditions, for a broad group of very different substances, including helium, carbon, silicon, phosphorous, sulfur,tellurium, cerium, hydrogen and tin tetraiodide. This phenomenon is also hypothesized for metastable and deeply supercooled water, presumably located a few degrees below the experimental limit of homogeneous ice formation. We present a generic phenomenological approach to describe polyamorphism in a single-component fluid, which is completely independent of the molecular origin of the phenomenon. We show that fluid polyamorphism may occur either in the presence or the absence of fluid phase separation depending on the symmetry of the order parameter. In the latter case, it is associated with a second-order transition, such as in liquid helium or liquid sulfur. To specify the phenomenology, we consider a fluid with thermodynamic equilibrium between two distinct interconvertible states or molecular structures. A fundamental signature of this concept is the identification of the equilibrium fraction of molecules involved in each of these alternative states. However, the existence of the alternative structures may result in polyamorphic fluid phase separation only if mixing of these structures is not ideal. The two-state thermodynamics unifies all the debated scenarios of fluid polyamorphism in different areas of condensed-matter physics, with or without phase separation, and even goes beyond the phenomenon of polyamorphism by generically describing the anomalous properties of fluids exhibiting interconversion of alternative molecular states.

cond-mat.stat-mech↗