Structure of a new dense amorphous ice

The detailed structure of a new dense amorphous ice, VHDA, is determined by isotope substitution neutron diffraction. Its structure is characterized by a doubled occupancy of the stabilizing interstitial location that was found in high density amorphous ice, HDA. As would be expected for a thermally activated unlocking of the stabilizing "interstitial," the transition from VHDA to LDA (low-density amorphous ice) is very sharp. Although its higher density makes VHDA a better candidate than HDA for a physical manifestation of the second putative liquid phase of water, as for the HDA case, the VHDA to LDA transition also appears to be kinetically controlled

The Glass Transition Temperature of Water: A Simulation Study

We report a computer simulation study of the glass transition for water. To mimic the difference between standard and hyperquenched glass, we generate glassy configurations with different cooling rates and calculate the $T$ dependence of the specific heat on heating. The absence of crystallization phenomena allows us, for properly annealed samples, to detect in the specific heat the simultaneous presence of a weak pre-peak (``shadow transition''), and an intense glass transition peak at higher temperature. We discuss the implications for the currently debated value of the glass transition temperature of water. We also compare our simulation results with the Tool-Narayanaswamy-Moynihan phenomenological model.Comment: submitted to Phys. Re

Interplay Between Time-Temperature-Transformation and the Liquid-Liquid Phase Transition in Water

We study the TIP5P water model proposed by Mahoney and Jorgensen, which is closer to real water than previously-proposed classical pairwise additive potentials. We simulate the model in a wide range of deeply supercooled states and find (i) the existence of a non-monotonic ``nose-shaped'' temperature of maximum density line and a non-reentrant spinodal, (ii) the presence of a low temperature phase transition, (iii) the free evolution of bulk water to ice, and (iv) the time-temperature-transformation curves at different densities.Comment: RevTeX4, 4 pages, 4 eps figure

Partitioning of crystalline and amorphous phases during freezing of simulated Enceladus ocean fluids

This work was supported by The Leverhulme Trust (grant number RPG‐2016‐153).Saturn's ice‐covered moon Enceladus may contain the requisite conditions for life. Its potentially habitable subsurface ocean is vented into space as large cryovolcanic plumes that can be sampled by spacecraft, acting as a window to the ocean below. However, little is known about how Enceladus’ ocean fluids evolve as they freeze. Using cryo‐imaging techniques, we investigated solid phases produced by freezing simulated Enceladean ocean fluids at endmember cooling rates. Our results show that under flash‐freezing conditions (>10 K s−1), Enceladus‐relevant fluids undergo segregation, whereby the precipitation of ice templates the formation of brine vein networks. The high solute concentrations and confined nature of these brine veins means that salt crystallization is kinetically inhibited and glass formation (vitrification) can occur at lower cooling rates than typically required for vitrification of a bulk solution. Crystalline salts also form if flash‐frozen fluids are re‐warmed. The 10 µm‐scale distribution of salt phases produced by this mechanism differs markedly from that of gradually cooled (∼1 K min−1) fluids, showing that they inherit a textural signature of their formation conditions. The mineralogy of cryogenic carbonates can be used as a probe for cooling rate and parent fluid pH. Our findings reveal possible endmember routes for solid phase production from Enceladus’ ocean fluids and mechanisms for generating compositional heterogeneity within ice particles on a sub‐10 µm scale. This has implications for understanding how Enceladus' ocean constituents are incorporated into icy particles and delivered to space.Publisher PDFPeer reviewe

Characterizing the secondary hydration shell on hydrated myoglobin, hemoglobin, and lysozyme powders by its vitrification behavior on cooling and its calorimetric glass-->liquid transition and crystallization behavior on reheating.

For hydrated metmyoglobin, methemoglobin, and lysozyme powders, the freezable water fraction of between approximately 0.3-0.4 g water/g protein up to approximately 0.7-0.8 g water/g protein has been fully vitrified by cooling at rates up to approximately 1500 K min-1 and the influence of cooling rate characterized by x-ray diffractograms. This vitreous but freezable water fraction started to crystallize at approximately 210 K to cubic ice and at approximately 240 K to hexagonal ice. Measurements by differential scanning calorimetry have shown that this vitreous but freezable water fraction undergoes, on reheating at a rate of 30 K min-1, a glass-->liquid transition with an onset temperature of between approximately 164 and approximately 174 K, with a width of between approximately 9 and approximately 16 degrees and an increase in heat capacity of between approximately 20 and approximately 40 J K-1 (mol of freezable water)-1 but that the glass transition disappears upon crystallization of the freezable water. These calorimetric features are similar to those of water imbibed in the pores of a synthetic hydrogel but very different from those of glassy bulk water. The difference to glassy bulk water's properties is attributed to hydrophilic interaction and H-bonding of the macromolecules' segments with the freezable water fraction, which thereby becomes dynamically modified. Abrupt increase in minimal or critical cooling rate necessary for complete vitrification is observed at approximately 0.7-0.8 g water/g protein, which is attributed to an abrupt increase of water's mobility, and it is remarkably close to the threshold value of water's mobility on a hydrated protein reported by Kimmich et al. (1990, Biophys. J. 58:1183). The hydration level of approximately 0.7-0.8 g water/g protein is approximately that necessary for completing the secondary hydration shell

Structural characterization of hyperquenched glassy water and vapor-deposited amorphous ice

Neutron diffraction experiments have been made on hyperquenched glassy water (D2O). After subtraction of a small crystalline component (I(c)) it is found that the structure is based on a continuous random network (CRB) of hydrogen-bonded molecules similar to that describing the low-density form of amorphous ice

Structures of high and low density amorphous ice by neutron diffraction

Neutron diffraction with isotope substitution is used to determine the structures of high (HDA) and low (LDA) density amorphous ice. Both "phases" are fully hydrogen bonded, tetrahedral networks, with local order similarities between LDA and ice Ih , and HDA and liquid water. Moving from HDA, through liquid water and LDA to ice Ih , the second shell radial order increases at the expense of spatial order. This is linked to a fifth first neighbor "interstitial" that restricts the orientations of first shell waters. This "lynch pin" molecule which keeps the HDA structure intact has implications for the nature of the HDA-LDA transition that bear on the current metastable water debate