Dielectric properties of high-density amorphous ice under pressure

Andersson, Ove; Inaba, Akira

doi:10.1103/physrevb.74.184201

Cited by 46 publications

(60 citation statements)

References 66 publications

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“…A dielectric spectroscopy study (20) has already shown the presence of reorientational motions with a relaxation time of approximately 0.3 s at 140 K (20,21), which is in good agreement with the C p results (see Fig. S3 and SI Text).…”

Section: Resultssupporting

confidence: 77%

Glass–liquid transition of water at high pressure

Andersson

2011

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

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The knowledge of the existence of liquid water under extreme conditions and its concomitant properties are important in many fields of science. Glassy water has previously been prepared by hyperquenching micron-sized droplets of liquid water and vapor deposition on a cold substrate (ASW), and its transformation to an ultraviscous liquid form has been reported on heating. A densified amorphous solid form of water, high-density amorphous ice (HDA), has also been made by collapsing the structure of ice at pressures above 1 GPa and temperatures below approximately 140 K, but a corresponding liquid phase has not been detected. Here we report results of heat capacity C p and thermal conductivity, in situ, measurements, which are consistent with a reversible transition from annealed HDA to ultraviscous high-density liquid water at 1 GPa and 140 K. On heating of HDA, the C p increases abruptly by ð3.4 AE 0.2Þ J mol −1 K −1 before crystallization starts at ð153 AE 1Þ K. This is larger than the C p rise at the glass to liquid transition of annealed ASW at 1 atm, which suggests the existence of liquid water under these extreme conditions. glass transition | pressure-induced amorphization | relaxation U nlike most liquids that vitrify by normal supercooling, water vitrifies only by hyperquenching of its micron-size droplets, and its porous amorphous state is made by vapor deposition (1-3). Pure bulk water densified by high pressure also does not vitrify on normal cooling; instead it freezes to proton-disordered high-density ices. However, in 1984 Mishima et al. (4) discovered a path to obtain a high-density amorphous ice (HDA) by pressurization of hexagonal ice, ice Ih, to approximately 1.5 GPa at 77 K. This amorphous form is characterized by the absence of Bragg peaks, but it is heterogeneous on a mesoscopic length scale (5). On heating at high pressures above approximately 0.5 GPa (6), it relaxes, homogenizes, and densifies before crystallization, and the ultimately densified form has been referred to as very highdensity amorphous ice (vHDA) (7). There are thus a multiplicity of amorphous states with densities in between HDA and vHDA, which are produced by isothermal pressurization of ice Ih at temperatures below approximately 140 K, and these are here generically referred to as HDA.States of water at extreme pressure and temperature conditions are important for, for example, understanding of tectonics in large bodies of the outer solar system where ice is one of the rock-forming minerals (8), and for water's phase diagram and properties (9), but it is not known whether HDA transforms to glassy and liquid states on heating. This work reports a unique high-pressure, in situ, heat capacity C p study of HDA just below its crystallization point where a glass to liquid transition may occur. It is here shown that HDA exhibits a glass transition with a heat capacity rise larger than that for amorphous solid water and hyperquenched water at 1 atm, which suggests a thermodynamic path between the annealed state of HDA and liquid wa...

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Section: Resultssupporting

confidence: 77%

Glass–liquid transition of water at high pressure

Andersson

2011

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

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“…What needs to be done here is to measure the in situ relaxation times directly and to determine whether a glass!liquid transition occurs during isobaric heating. The first results obtained by dielectric relaxation spectroscopy of VHDA at 1 GPa suggest that VHDA indeed shows liquid-like relaxation behavior at 140 K [205,206]. The question of whether the amorphous states of water behave like glasses (i.e., vitrified liquids), which turn into liquids during heating, or whether they behave like crystals, which do not liquify during heating, is highly disputed as outlined in the following section.…”

Section: Reversible In Situ Structural Transitionsmentioning

confidence: 99%

Multiple Amorphous–Amorphous Transitions

Loerting

Бражкин

Morishita

2009

Advances in Chemical Physics

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“…The molecular environment in LDA is more similar to that of crystalline ice (cubic or hexagonal) while that of HDA is more disordered and similar to liquid water at standard temperature and pressure (STP). Furthermore, there is some experimental evidence for the existence of two metastable liquid states above the corresponding two glass transition temperatures [18][19][20] , and these two liquid extensions of the amorphous ices are respectively called the low-density (LDL) and high-density liquids (HDL). In this regard, it has been suggested that the coexistence line separating LDA and HDA would extend into the liquid regime terminating at a critical point called the liquid-liquid (LL) critical point (LLCP) 21 , and this scenario would provide a possible explanation for the anomalous response properties of water.…”

Section: Introductionmentioning

confidence: 99%

Local structure analysis in ab initio liquid water

et al. 2015

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Within the framework of density functional theory, the inclusion of exact exchange and non-local van der Waals/dispersion (vdW) interactions is crucial for predicting a microscopic structure of ambient liquid water that quantitatively agrees with experiment. In this work, we have used the local structure index (LSI) order parameter to analyze the local structure in such highly accurate ab initio liquid water. At ambient conditions, the LSI probability distribution, P(I), was unimodal with most water molecules characterized by more disordered high-density-like local environments. With thermal excitations removed, the resultant bimodal P(I) in the inherent potential energy surface (IPES) exhibited a 3:1 ratio between high-and low-density-like molecules, with the latter forming small connected clusters amid the predominant population. By considering the spatial correlations and hydrogen bond network topologies among water molecules with the same LSI identities, we demonstrate that the signatures of the experimentally observed low-(LDA) and highdensity (HDA) amorphous phases of ice are present in the IPES of ambient liquid water. Analysis of the LSI autocorrelation function uncovered a persistence time of ∼ 4 ps-a finding consistent with the fact that natural thermal fluctuations are responsible for transitions between these distinct yet transient local aqueous environments in ambient liquid water.

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Dielectric properties of high-density amorphous ice under pressure

Cited by 46 publications

References 66 publications

Glass–liquid transition of water at high pressure

Glass–liquid transition of water at high pressure

Multiple Amorphous–Amorphous Transitions

Local structure analysis in ab initio liquid water

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