Annealed high-density amorphous ice under pressure

Nelmes, R. J.; Loveday, J. S.; Strässle, Thierry; Bull, Craig L.; Guthrie, Malcolm; Hamel, G.; Klotz, Stefan

doi:10.1038/nphys313

Cited by 176 publications

(225 citation statements)

References 28 publications

Supporting

Mentioning

211

Contrasting

Unclassified

Order By: Relevance

“…Using high-pressure cryocooling, HDA ice is induced by pressurizing samples at 283 K, which are then cooled to 77 K while still under pressure (23). As shown in this study, the HDA ice induced by high-pressure cryocooling leads to a first-order phase transition to LDA ice even without annealing at high pressure (13). More importantly, our observations provide evidence for a liquid state of water during the ice transition, suggesting a possible glass transition of HDA ice, which opens the possibility that the HDA ice induced by high-pressure cryocooling may be a true glassy form of HDL.…”

Section: Discussionmentioning

confidence: 71%

“…However, experimental study of the HDL-LDL phase transition is challenging as supercooled water spontaneously converts to crystalline forms below the homogeneous nucleation temperature (Ϸ235 K at 0.1 MPa). The transition between 2 glassy forms of water, high-density amorphous (HDA) and low-density amorphous (LDA) ice, has been extensively studied (9)(10)(11)(12)(13)(14)(15)(16)(17)(18), as an analogue of the HDL-LDL transition. Controversy still exists as to whether the HDA-LDA ice transition is truly a first-order phase transition (10)(11)(12)(13) or if it occurs because of a relaxation process of an unstable amorphous structure (15)(16)(17)(18).…”

mentioning

confidence: 99%

“…The transition between 2 glassy forms of water, high-density amorphous (HDA) and low-density amorphous (LDA) ice, has been extensively studied (9)(10)(11)(12)(13)(14)(15)(16)(17)(18), as an analogue of the HDL-LDL transition. Controversy still exists as to whether the HDA-LDA ice transition is truly a first-order phase transition (10)(11)(12)(13) or if it occurs because of a relaxation process of an unstable amorphous structure (15)(16)(17)(18). More importantly, the connection between the HDA-LDA ice transition and the HDL-LDL phase transition, implied by thermodynamic and structural studies on water (19)(20)(21)(22), remains challenging to prove experimentally (8).…”

mentioning

confidence: 99%

See 2 more Smart Citations

Evidence for liquid water during the high-density to low-density amorphous ice transition

Kim

Barstow²,

Täte

et al. 2009

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

View full text Add to dashboard Cite

Polymorphism of water has been extensively studied, but controversy still exists over the phase transition between high-density amorphous (HDA) and low-density amorphous (LDA) ice. We report the phase behavior of HDA ice inside high-pressure cryocooled protein crystals. Using X-ray diffraction, we demonstrate that the intermediate states in the temperature range from 80 to 170 K can be reconstructed as a linear combination of HDA and LDA ice, suggesting a first-order transition. We found evidence for a liquid state of water during the ice transition based on the protein crystallographic data. These observations open the possibility that the HDA ice induced by high-pressure cryocooling is a genuine glassy form of high-density liquid.liquid-liquid hypothesis ͉ supercooled water ͉ water phases ͉ high-density liquid S upercooled water shows anomalous thermodynamic behavior (1-3). Theories that account for these anomalous properties include the stability limit (4), the singularity-free (5, 6), and the liquid-liquid (LL) critical point (7) hypotheses. The latter 2 hypotheses propose the existence of 2 distinct forms of supercooled water: high-density liquid (HDL) and low-density liquid (LDL) water (8). In the singularity-free hypothesis, HDL transforms continuously to LDL. In the LL critical point theory, HDL undergoes a first-order phase transition to LDL (8). However, experimental study of the HDL-LDL phase transition is challenging as supercooled water spontaneously converts to crystalline forms below the homogeneous nucleation temperature (Ϸ235 K at 0.1 MPa). The transition between 2 glassy forms of water, high-density amorphous (HDA) and low-density amorphous (LDA) ice, has been extensively studied (9-18), as an analogue of the HDL-LDL transition. Controversy still exists as to whether the HDA-LDA ice transition is truly a first-order phase transition (10-13) or if it occurs because of a relaxation process of an unstable amorphous structure (15-18). More importantly, the connection between the HDA-LDA ice transition and the HDL-LDL phase transition, implied by thermodynamic and structural studies on water (19-22), remains challenging to prove experimentally (8).We used X-ray diffraction to study the transition of HDA to LDA ice in protein crystals. HDA ice was induced inside protein crystals by a high-pressure cryocooling method (23) originally developed for macromolecular crystallography (23-26). The Bragg diffraction from protein crystals mainly provides information on protein structure. The simultaneously recorded water diffuse diffraction (WDD) profile reports on the phase of the water in the protein crystal, which accounts for typically 40-60% of its volume. Fig. 1 shows diffraction images and the WDD profiles from a high-pressure cryocooled crystal of the globular protein thaumatin. As the crystal temperature is increased from 80 to 170 K, the primary WDD peak, corresponding to the mean distance between neighboring water molecule oxygen atoms, shifts to lower momentum transfer (Q) region [Q ϭ 4 sin( )/ , wh...

show abstract

Section: Discussionmentioning

confidence: 71%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Evidence for liquid water during the high-density to low-density amorphous ice transition

Kim

Barstow²,

Täte

et al. 2009

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

View full text Add to dashboard Cite

show abstract

“…In the case of HDA, two different forms are commonly discussed, unrelaxed HDA (uHDA) and expanded HDA (eHDA). 54,59 Similarly, a few sub-families of LDA have been introduced, such as LDA I and LDA II . 58 Other well-known low-density amorphous ices, such as hyperquenched glassy water (HGW) 61 and amorphous solid water (ASW), 62 are usually considered to belong to the LDA family.…”

Section: Introductionmentioning

confidence: 99%

Pressure-induced transformations in computer simulations of glassy water

Chiu

Starr

Giovambattista

2013

The Journal of Chemical Physics

View full text Add to dashboard Cite

Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and highdensity amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a lowdensity and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water. © 2013 AIP Publishing LLC.

show abstract

“…As pointed out by Nelmes et al this difference in thermal stability reflects the degree of relaxation (23), with pressure annealing at ∼0.1 GPa significantly enhancing thermal stability at ambient pressure (24). Work on HDA, including calorimetry studies (20), was traditionally carried out using unannealed (uHDA) samples prepared by pressure-induced amorphization of hexagonal ice at 77 K (25), whereas the study of annealed, expanded forms of HDA (eHDA) has only begun in recent years (14,21,23,24). Here we present differential scanning calorimetry (DSC) experiments ( Fig.…”

mentioning

confidence: 99%

Water’s second glass transition

Amann‐Winkel

Gainaru

Handle

et al. 2013

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

269

301

View full text Add to dashboard Cite

The glassy states of water are of common interest as the majority of H 2 O in space is in the glassy state and especially because a proper description of this phenomenon is considered to be the key to our understanding why liquid water shows exceptional properties, different from all other liquids. The occurrence of water's calorimetric glass transition of low-density amorphous ice at 136 K has been discussed controversially for many years because its calorimetric signature is very feeble. Here, we report that high-density amorphous ice at ambient pressure shows a distinct calorimetric glass transitions at 116 K and present evidence that this second glass transition involves liquid-like translational mobility of water molecules. This "double T g scenario" is related to the coexistence of two liquid phases. The calorimetric signature of the second glass transition is much less feeble, with a heat capacity increase at T g,2 about five times as large as at T g,1 . By using broadband-dielectric spectroscopy we resolve loss peaks yielding relaxation times near 100 s at 126 K for low-density amorphous ice and at 110 K for high-density amorphous ice as signatures of these two distinct glass transitions. Temperature-dependent dielectric data and heating-rate-dependent calorimetric data allow us to construct the relaxation map for the two distinct phases of water and to extract fragility indices m = 14 for the low-density and m = 20-25 for the high-density liquid. Thus, low-density liquid is classified as the strongest of all liquids known ("superstrong"), and also high-density liquid is classified as a strong liquid.

show abstract

Annealed high-density amorphous ice under pressure

Cited by 176 publications

References 28 publications

Evidence for liquid water during the high-density to low-density amorphous ice transition

Evidence for liquid water during the high-density to low-density amorphous ice transition

Pressure-induced transformations in computer simulations of glassy water

Water’s second glass transition

Contact Info

Product

Resources

About