Anomalies in bulk supercooled water at negative pressure.
ABSTRACT: Water anomalies still defy explanation. In the supercooled liquid, many quantities, for example heat capacity and isothermal compressibility ?T, show a large increase. The question arises if these quantities diverge, or if they go through a maximum. The answer is key to our understanding of water anomalies. However, it has remained elusive in experiments because crystallization always occurred before any extremum is reached. Here we report measurements of the sound velocity of water in a scarcely explored region of the phase diagram, where water is both supercooled and at negative pressure. We find several anomalies: maxima in the adiabatic compressibility and nonmonotonic density dependence of the sound velocity, in contrast with a standard extrapolation of the equation of state. This is reminiscent of the behavior of supercritical fluids. To support this interpretation, we have performed simulations with the 2005 revision of the transferable interaction potential with four points. Simulations and experiments are in near-quantitative agreement, suggesting the existence of a line of maxima in ?T (LM?T). This LM?T could either be the thermodynamic consequence of the line of density maxima of water [Sastry S, Debenedetti PG, Sciortino F, Stanley HE (1996) Phys Rev E 53:6144-6154], or emanate from a critical point terminating a liquid-liquid transition [Sciortino F, Poole PH, Essmann U, Stanley HE (1997) Phys Rev E 55:727-737]. At positive pressure, the LM?T has escaped observation because it lies in the "no man's land" beyond the homogeneous crystallization line. We propose that the LM?T emerges from the no man's land at negative pressure.
Project description:Using electron spin resonance spectroscopy (ESR), we measure the rotational mobility of probe molecules highly diluted in deeply supercooled bulk water and negligibly constrained by the possible ice fraction. The mobility increases above the putative glass transition temperature of water, T(g) = 136 K, and smoothly connects to the thermodynamically stable region by traversing the so called "no man's land" (the range 150-235 K), where it is believed that the homogeneous nucleation of ice suppresses the liquid water. Two coexisting fractions of the probe molecules are evidenced. The 2 fractions exhibit different mobility and fragility; the slower one is thermally activated (low fragility) and is larger at low temperatures below a fragile-to-strong dynamic cross-over at approximately 225 K. The reorientation of the probe molecules decouples from the viscosity below approximately 225 K. The translational diffusion of water exhibits a corresponding decoupling at the same temperature [Chen S-H, et al. (2006) The violation of the Stokes-Einstein relation in supercooled water. Proc Natl Acad Sci USA 103:12974-12978]. The present findings are consistent with key issues concerning both the statics and the dynamics of supercooled water, namely the large structural fluctuations [Poole PH, Sciortino F, Essmann U, Stanley HE (1992) Phase behavior of metastable water. Nature 360:324-328] and the fragile-to-strong dynamic cross-over at approximately 228 K [Ito K, Moynihan CT, Angell CA (1999) Thermodynamic determination of fragility in liquids and a fragile-to-strong liquid transition in water. Nature 398:492-494].
Project description:Possible transition between two phases of supercooled liquid water, namely the low- and high-density liquid water, has been only predicted to occur below 230 K from molecular dynamics (MD) simulation. However, such a phase transition cannot be detected in the laboratory because of the so-called "no-man's land" under deeply supercooled condition, where only crystalline ices have been observed. Here, we show MD simulation evidence that, inside an isolated carbon nanotube (CNT) with a diameter of 1.25 nm, both low- and high-density liquid water states can be detected near ambient temperature and above ambient pressure. In the temperature-pressure phase diagram, the low- and high-density liquid water phases are separated by the hexagonal ice nanotube (hINT) phase, and the melting line terminates at the isochore end point near 292 K because of the retracting melting line from 292 to 278 K. Beyond the isochore end point (292 K), low- and high-density liquid becomes indistinguishable. When the pressure is increased from 10 to 600 MPa along the 280-K isotherm, we observe that water inside the 1.25-nm-diameter CNT can undergo low-density liquid to hINT to high-density liquid reentrant first-order transitions.
Project description:Liquid water nanodroplets are important in earth's climate, and are valuable for studying supercooled water because they resist crystallisation well below the bulk freezing temperature. Bulk liquid water has well-known thermodynamic anomalies, such as a density maximum, and when supercooled is hypothesised to exhibit a liquid-liquid phase transition (LLPT) at elevated pressure. However, it is not known how these bulk anomalies might manifest themselves in nanodroplets. Here we show, using simulations of the TIP4P/2005 water model, that bulk anomalies occur in nanodroplets as small as 360 molecules. We also show that the Laplace pressure inside small droplets reaches 220?MPa at 180?K, conditions close to the LLPT of TIP4P/2005. While the density and pressure inside nanodroplets coincide with bulk values at moderate supercooling, we show that deviations emerge at lower temperature, as well as significant radial density gradients, which arise from and signal the approach to the LLPT.
Project description:Twenty years ago Poole et al. suggested that the anomalous properties of supercooled water may be caused by a critical point that terminates a line of liquid-liquid separation of lower-density and higher-density water. Here we present a thermodynamic model based on this hypothesis, which describes all available experimental data for supercooled water with better quality and fewer adjustable parameters than any other model. Liquid water at low temperatures is viewed as an 'athermal solution' of two molecular structures with different entropies and densities. Alternatively to popular models for water, in which liquid-liquid separation is driven by energy, the phase separation in the athermal two-state water is driven by entropy upon increasing the pressure, while the critical temperature is defined by the 'reaction' equilibrium constant. The model predicts the location of density maxima at the locus of a near-constant fraction of the lower-density structure.
Project description:Sr2RuO4 has long been the focus of intense research interest because of conjectures that it is a correlated topological superconductor. It is the momentum space (k-space) structure of the superconducting energy gap [Formula: see text] on each band i that encodes its unknown superconducting order parameter. However, because the energy scales are so low, it has never been possible to directly measure the [Formula: see text] of Sr2RuO4 Here, we implement Bogoliubov quasiparticle interference (BQPI) imaging, a technique capable of high-precision measurement of multiband [Formula: see text] At T = 90 mK, we visualize a set of Bogoliubov scattering interference wavevectors [Formula: see text] consistent with eight gap nodes/minima that are all closely aligned to the [Formula: see text] crystal lattice directions on both the ? and ? bands. Taking these observations in combination with other very recent advances in directional thermal conductivity [E. Hassinger et al., Phys. Rev. X 7, 011032 (2017)], temperature-dependent Knight shift [A. Pustogow et al., Nature 574, 72-75 (2019)], time-reversal symmetry conservation [S. Kashiwaya et al., Phys. Rev B, 100, 094530 (2019)], and theory [A. T. Rømer et al., Phys. Rev. Lett. 123, 247001 (2019); H. S. Roising, T. Scaffidi, F. Flicker, G. F. Lange, S. H. Simon, Phys. Rev. Res. 1, 033108 (2019); and O. Gingras, R. Nourafkan, A. S. Tremblay, M. Côté, Phys. Rev. Lett. 123, 217005 (2019)], the BQPI signature of Sr2RuO4 appears most consistent with [Formula: see text] having [Formula: see text] [Formula: see text] symmetry.
Project description:Understanding large-scale circulations (LSCs) in turbulent convective systems is important for the study of stars, planets, and in many industrial applications. The canonical model of the LSC is quasi-planar with additional horizontal sloshing and torsional modes [Brown E, Ahlers G (2009) J Fluid Mech 638:383-400; Funfschilling D, Ahlers G (2004) Phys Rev Lett 92:194502; Xi HD et al. (2009) Phys Rev Lett 102:044503; Zhou Q et al. (2009) J Fluid Mech 630:367-390]. Using liquid gallium as the working fluid, we show, via coupled laboratory-numerical experiments in tanks with aspect ratios greater than unity ([Formula: see text]), that the LSC takes instead the form of a "jump rope vortex," a strongly 3D mode that periodically orbits around the tank following a motion much like a jump rope on a playground. Further experiments show that this jump rope flow also exists in more viscous fluids such as water, albeit with a far smaller signal. Thus, this jump rope mode is an essential component of the turbulent convection that underlies our observations of natural systems.
Project description:An interaction model with core-softened potential in three dimensions was studied by Monte Carlo computer simulations and integral equation theory. We investigated the possibility that a fluid with a core-softened potential can reproduce anomalies found experimentally in liquid water, such as the density anomaly, the minimum in the isothermal compressibility as a function of temperature, and others. Critical points of the fluid were also determined. We provided additional arguments that the old notion, postulating that only angular-dependent interactions result in density anomaly, is incorrect. We showed that potential with two characteristic distances is sufficient for the system to exhibit water-like behavior and anomalies, including the famous density maximum. We also found that this model can properly describe the hydrophobic effect.
Project description:Monte Carlo simulations and integral equation theory were used to study the thermodynamics and structure of particles interacting through the smooth version of Stell-Hemmer interaction. We checked the possibility that a fluid with a core-softened potential reproduces anomalies of liquid water such as the density anomaly, the minimum in the isothermal compressibility as a function of temperature, and others. Critical points of the fluid were also determined. We showed that a potential with two characteristic distances is sufficient for the system to exhibit water-like behavior and anomalies, including the famous density maximum. We also showed that some versions of the integral equation theory completely fail to predict structure of such system, while others only predict it qualitatively.
Project description:Recent nanofluidic experiments revealed strongly different surface charge measurements for boron-nitride (BN) and graphitic nanotubes when in contact with saline and alkaline water (Nature 2013, 494, 455-458; Phys. Rev. Lett. 2016, 116, 154501). These observations contrast with the similar reactivity of a graphene layer and its BN counterpart, using density functional theory (DFT) framework, for intact and dissociative adsorption of gaseous water molecules. Here we investigate, by DFT in implicit water, single and multiple adsorption of anionic hydroxide on single layers. A differential adsorption strength is found in vacuum for the first ionic adsorption on the two materials-chemisorbed on BN while physisorbed on graphene. The effect of implicit solvation reduces all adsorption values, resulting in a favorable (nonfavorable) adsorption on BN (graphene). We also calculate a pKa ? 6 for BN in water, in good agreement with experiments. Comparatively, the unfavorable results for graphene in water echo the weaker surface charge measurements but point to an alternative scenario.
Project description:The nonlinear Poisson-Boltzmann equation (PBE) governing biomolecular electrostatics neglects ion size and ion correlation effects, and recent research activity has focused on accounting for these effects to achieve better physical modeling realism. Here, attention is focused on the comparatively simpler challenge of addressing ion size effects within a continuum-based solvent modeling framework. Prior works by Borukhov et al. (Phys. Rev. Lett. 1997, 79, 435; Electrochim. Acta 2000, 46, 221) have examined the case of uniform ion size in considerable detail. Generalizations to accommodate different species ion sizes have been performed by Li (Nonlinearity 2009, 22, 811; SIAM J. Math. Anal. 2009, 40, 2536) and Zhou et al. (Phys. Rev. E 2011, 84, 021901) using a variational principle, Chu et al. (Biophys. J. 2007, 93, 3202) using a lattice gas model, and Tresset (Phys. Rev. E 2008, 78, 061506) using a generalized Poisson-Fermi distribution. The current work provides an alternative derivation using simple statistical mechanics principles that place the ion size effects and energy distributions on a consistent statistical footing. The resulting expressions differ from the prior nonuniform ion-size developments. However, all treatments reduce to the same form in the cases of uniform ion-size and zero ion size (the PBE). Because of their importance to molecular modeling and salt-dependent behavior, expressions for the salt sensitivities and ionic forces are also derived using the nonuniform ion size description. Emphasis in this article is on formulation and numerically robust evaluation; results are presented for a simple sphere and a previously considered DNA structure for comparison and validation. More extensive application to biomolecular systems is deferred to a subsequent article.