The phase diagram of water at negative pressures: Virtual ices

Conde, M. M.; Vega, Carlos; Tribello, Gareth A.; Slater, Ben

doi:10.1063/1.3182727

Cited by 70 publications

(91 citation statements)

References 63 publications

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“…The parametrization of TIP4P/2005 has been based on a fit of the temperature of maximum density and a great variety of properties and wide range thereof for the liquid and its polymorphs. TIP4P/2005 has been used to calculate a broad variety of thermodynamic properties of the liquid and solid phases, such as the phase diagram involving condensed phases (45)(46)(47), properties at melting and vaporization (34,48), dielectric constants (49), pair distribution function, and self-diffusion coefficient. These properties cover a temperature range from 123 to 573 K and pressures up to 4,000 MPa (32).…”

Section: Methodsmentioning

confidence: 99%

Anomalies in bulk supercooled water at negative pressure

Pallares

Azouzi

González

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

116

129

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Water anomalies still defy explanation. In the supercooled liquid, many quantities, for example heat capacity and isothermal compressibility κ 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 κ T (LMκ T ). This LMκ 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 LMκ T has escaped observation because it lies in the "no man's land" beyond the homogeneous crystallization line. We propose that the LMκ T emerges from the no man's land at negative pressure.scenarios for water | Widom line | Berthelot tube W ater differs in many ways from standard liquids: ice floats on water, and, upon cooling below 48C, the liquid density decreases. In the supercooled liquid, many quantities, for example heat capacity and isothermal compressibility, show a large increase. Extrapolation of experimental data suggested a powerlaw divergence of these quantities at −458C (1). Thirty years ago, the stability-limit conjecture proposed that an instability of the liquid would cause the divergence (2) (Fig. 1A). This is supported by equations of state (EoSs), such as the International Association for the Properties of Water and Steam (IAPWS) EoS (3), fitted on the stable liquid and extrapolated to the metastable regions. Ten years later, the second critical point interpretation, based on simulations (4), proposed that, instead of diverging, the anomalous quantities would reach a peak, near a Widom line (5, 6) that emanates from a liquid-liquid critical point (LLCP) terminating a first-order liquid-liquid transition (LLT) between two distinct liquid phases at low temperature (Fig. 1B). The two scenarios differ in the shape of the line of density maxima (LDM) of water ( Fig. 1 A and B). A recent work (7) has added one point on this line at large negative pressure, but this was not enough to decide between the two scenarios.It has been argued (8) that ...

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Section: Methodsmentioning

confidence: 99%

Anomalies in bulk supercooled water at negative pressure

Pallares

Azouzi

González

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

116

129

View full text Add to dashboard Cite

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“…This is the case of the concept of negative pressure which was presented in different works [48][49][50] and variously commented [51,52]. In non-extensive thermodynamics, nothing opposes to a negative value of the nonextensive pressure for condensed phases, since we consider negative intensities, τ,…”

Section: Resultsmentioning

confidence: 99%

Solubility of gas in confined systems. Nonextensive thermodynamics approach

Letellier¹,

Turmine²

2013

Journal of Colloid and Interface Science

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The use of the concepts of the nonextensive thermodynamics allows reconsidering the equilibrium of bubble solubilization, and more commonly of gaseous aggregates in supersaturated solutions of gas. The introduced relations are general and include as particular cases the equations usually used to describe these phenomena. These equations are discussed.Especially, we specified the domain of application of Kelvin's relation which was illustrated by the solubility of gases in fogs and clouds. Various possibilities of thoughts on the behavior of the gaseous aggregates and nano-systems are proposed. Thus, the introduced relations permit to consider the presence of gaseous aggregates in equilibrium with the solution even for undersaturated solution. Non-extensive thermodynamics admits the notion of negative pressure at the inner of confined phases (solid or liquid).

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“…The remaining difference to the range in Table II can be attributed to variations between functionals, or the use of a larger ice i supercell in Ref. 36 which may have contained a particularly stable proton configuration not sampled in our smaller unit cells. In either case it is clear that ice 0 and ice i cannot easily be separated on DFT lattice energies alone.…”

Section: Comparison To Other Metastable Icesmentioning

confidence: 96%

“…Conde et al 36 previously computed the energy of a single proton realisation of ice i to be only 12 meV/molecule higher in energy than ice XI. This calculation used anti-ferroelectric ice XI 37 rather than the ferroelectric form used here, and the PW91 functional.…”

Section: Comparison To Other Metastable Icesmentioning

confidence: 99%

Communication: On the stability of ice 0, ice i, and Ih

Quigley

Slater

2014

The Journal of Chemical Physics

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Using ab initio methods, we examine the stability of ice 0, a recently proposed tetragonal form of ice implicated in the homogeneous freezing of water [J. Russo, F. Romano, and H. Tanaka, Nat. Mater. 13, 670 (2014)]. Vibrational frequencies are computed across the complete Brillouin Zone using Density Functional Theory (DFT), to confirm mechanical stability and quantify the free energy of ice 0 relative to ice I h . The robustness of this result is tested via dispersion corrected semi-local and hybrid DFT, and Quantum Monte-Carlo calculation of lattice energies. Results indicate that popular molecular models only slightly overestimate the stability of ice zero. In addition, we study all possible realisations of proton disorder within the ice zero unit cell, and identify the ground state as ferroelectric. Comparisons are made to other low density metastable forms of ice, suggesting that the ice i structure [C. J. Fennel and J. D. Gezelter, J. Chem. Theory Comput.

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The phase diagram of water at negative pressures: Virtual ices

Cited by 70 publications

References 63 publications

Anomalies in bulk supercooled water at negative pressure

Anomalies in bulk supercooled water at negative pressure

Solubility of gas in confined systems. Nonextensive thermodynamics approach

Communication: On the stability of ice 0, ice i, and Ih

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