Pressure-Induced Polyamorphism in Salty Water

Bove, L. E.; Klotz, Stefan; Philippe, J.; Saitta, A. Marco

doi:10.1103/physrevlett.106.125701

Cited by 34 publications

(53 citation statements)

References 25 publications

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“…1. Pressure-temperature phase diagram of salty ice as sketched from our previous neutron diffraction experiments and MD simulations on LiClwater solutions under pressure (37,38,49). In the present experiment, we probed the ice VII to ice X transition, both in compression and decompression, in the 10-to 150-GPa range and room temperature by Raman scattering.…”

Section: Resultsmentioning

confidence: 97%

“…In particular, the observation of a single O-O vibrational mode of T 2g symmetry in the low-frequency range (5, 6) is commonly used to identify the transition to the cuprite-type structure of ice X. A sketch of the high-pressure phase diagram of salty LiCl water so far known (37,38,41,49) is represented in Fig. 1, where the thermodynamic paths followed in the present experiment are also indicated.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, unexpected evidence has emerged that high-pressure water polymorphs can contain a substantial amount of small ions in salty ice structures (37)(38)(39)(40)(41)(42), and, similarly to what is observed in ice clathrates (43,44), they transform under pressure into bcc O lattices with ions either occupying interstices (37) or being substitutional to water molecules (37,39). These "filled" ice structures can be stable over several gigapascals and hundreds of Kelvins, conditions encountered in large ice bodies in the universe.…”

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confidence: 90%

“…These "filled" ice structures can be stable over several gigapascals and hundreds of Kelvins, conditions encountered in large ice bodies in the universe. Combined neutron scattering experiments and molecular dynamics simulations have allowed sketching of the pressure and Temperature (p-T) phase diagram of LiCl-water and NaCl-water mixtures up to a few gigapascals, and have shown that the presence of salt suppresses the ordered ice VIII phase and modifies the boundary of the proton-disordered ice VII phase (37)(38)(39)(40)(41)(42). Orientational disorder of water molecules is also enhanced by the presence of salt, as demonstrated by the Significance Ice-VII and ice-X phases are the most stable forms of ice at high temperature and extreme pressures, typical of the interiors of satellites and planets.…”

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confidence: 99%

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Effect of salt on the H-bond symmetrization in ice

Bove

Gáal

Raza

et al. 2015

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

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The richness of the phase diagram of water reduces drastically at very high pressures where only two molecular phases, protondisordered ice VII and proton-ordered ice VIII, are known. Both phases transform to the centered hydrogen bond atomic phase ice X above about 60 GPa, i.e., at pressures experienced in the interior of large ice bodies in the universe, such as Saturn and Neptune, where nonmolecular ice is thought to be the most abundant phase of water. In this work, we investigate, by Raman spectroscopy up to megabar pressures and ab initio simulations, how the transformation of ice VII in ice X is affected by the presence of salt inclusions in the ice lattice. Considerable amounts of salt can be included in ice VII structure under pressure via rock-ice interaction at depth and processes occurring during planetary accretion. Our study reveals that the presence of salt hinders proton order and hydrogen bond symmetrization, and pushes ice VII to ice X transformation to higher and higher pressures as the concentration of salt is increased.salty ices | extreme conditions | ice bodies | H-bond symmetrization | proton quantum effects A ll models of the interior of ice bodies in the universe rely on our knowledge of the behavior of a few simple molecules under high pressure and temperature (1-22), water being the most intriguing of them, due to its abundance and its connection to life existence.New data delivered by various space missions, such as the Voyager, Galileo, and Cassini-Huygens missions, have greatly improved our understanding of the icy bodies within the solar system (23-25), and recent discoveries of extrasolar planets with significant water ice content have highlighted the importance of high-pressure H 2 O-rich phases in planetary physics beyond the solar system (26).Water displays an unusually rich pressure-temperature phase diagram, which mainly derives from the open geometry of the water molecule, which favors tetrahedral arrangements, and from the possibility of configurational disorder of the protons in the lattice. However, at high pressure (above about 2 GPa), the system experiences a large densification as a result of the interpenetration of low-pressure structures, and only two molecular phases are known, ice VIII and VII (3, 4). Ice VII is composed of two interpenetrating but not interconnected tetrahedral hydrogen-bonded networks of water molecules of normal cubic ice, Ic, with a body-centered-cubic (bcc) oxygen structure. The orientation of the water molecules is disordered, resulting in a paraelectric phase. In the antiferroelectric ice VIII phase, the water molecules and the associated dipole moments on the two sublattices possess long-range order and point in opposite directions, promoting a slight tetragonal distortion of the cubic unit cell along the staggered polarization (3, 4). In these two phases, the hydrogen bonds are characterized by a pronounced double-well proton transfer potential. Upon reducing the distance between donor and acceptor oxygens, the proton potential degenerate...

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 90%

mentioning

confidence: 99%

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Effect of salt on the H-bond symmetrization in ice

Bove

Gáal

Raza

et al. 2015

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

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“…To facilitate vitrification of the bulk state of water, either NaK tartrate [sodium potassium tartrate, 0.9 M; mole fraction (moles salt/total moles) of 0.016 or hydration number R (moles H 2 O/moles salt) of 62] or NaCl (sodium chloride, 1.5 M; mole fraction of 0.027 or R of 37) were added. Although salt additives in water are known to perturb the structure (19)(20)(21)(22)(23) and glass-forming properties (24,25) of water, insight on the thermodynamic properties of pure water has been obtained from aqueous solutions (6,(26)(27)(28). Fig.…”

Section: Resultsmentioning

confidence: 99%

Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

Kim

Täte

Grüner

2015

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

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Observation of theorized glass-to-liquid transitions between lowdensity amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-toliquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-toliquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water.glass-to-liquid transition | high-density amorphous ice | low-density amorphous ice | quenched HDA | first-order phase transition W ater has glassy states, including low-density amorphous (LDA) and high-density amorphous (HDA) ice (1-3). The glass-to-liquid transition in these polyamorphic forms of ice is the focus of theories proposed to explain anomalous properties of supercooled water (4-8). Although supporting experimental evidence exists (9-15), it remains controversial as the direct observation of a glass-to-liquid transition has been stymied by rapid crystallization below the homogeneous nucleation temperature (∼235 K at 0.1 MPa).In general, glasses are nonergodic, noncrystalline solids, in which atoms are fixed to their initial positions for macroscopically long periods of time (16). As is well known, when stress is applied, glasses can be cracked. Above the glass transition temperature, T g , the ergodic liquid is restored, and the stress-induced cracks in glasses can be healed by the diffusive motions of liquids. Indeed, it has been shown that the crack-healing process is reproducible and correlated with the glass transition temperatures, independent of liquid fragility (17, 18). ResultsBulk Water. In this study, crack healing is used to probe the molecular mobility in cryogenic transitions between glassy states of water or between glassy and crystalline states. Cracks do not heal for a sample held within any particular cryogenic solid state, indicating a low mobility in each of these states. Crack healing observed during phase transformations requires a high molecular mobility and is suggestive of an intermediate glass-to-liquid transition in the pathway between solid states. Fig. 1 shows the paths in a schematic phase diagram of water that were used to form and probe LDA and HDA ice. To facilitate vitrification of the bulk state of water, either NaK tartrate [sodium potassium tartrate, 0.9 M; mole fraction (moles salt/total moles) of 0.016 or hydration number R (moles H 2 O/moles salt) of 62] or NaCl (sodium chloride, 1.5 M; m...

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Overview of the recent studies on high‐pressure impurity ices

Yoshimura

2022

J Raman Spectroscopy

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In the present short review, we briefly overview the history of ice polymorphism under high-pressure and the recent progress on impurity ices (clathrate ice, salty ice, doped ice, empty ice, etc.), including our contributions due form high-pressure Raman investigations to these research fields. In particular, the unique roles of impurities in ice, which are (1) acceleration of proton ordering at lower temperatures, (2) offering a clue to form new ice phases, and (3) phase transitions other than the original equilibrium stability region of pure H 2 O, ice are introduced. Then, as prospects, we address promising impacts on a new area of ice physics with the active use of impurities.

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Pressure-Induced Polyamorphism in Salty Water

Cited by 34 publications

References 25 publications

Effect of salt on the H-bond symmetrization in ice

Effect of salt on the H-bond symmetrization in ice

Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

Overview of the recent studies on high‐pressure impurity ices

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