Amorphous water ice comes in at least three distinct structural forms, all lacking long-range crystalline order. High-density amorphous ice (HDA) was first produced by compressing ice I to 11 kilobar at temperatures below 130 kelvin, and the process was described as thermodynamic melting1, implying that HDA is a glassy state of water. This concept, and the ability to transform HDA reversibly into low-density amorphous ice, inspired the two-liquid water model, which relates the amorphous phases to two liquid waters in the deeply supercooled regime (below 228 kelvin) to explain many of the anomalies of water2 (such as density and heat capacity anomalies). However, HDA formation has also been ascribed3 to a mechanical instability causing structural collapse and associated with kinetics too sluggish for recrystallization to occur. This interpretation is supported by simulations3, analogy with a structurally similar system4, and the observation of lattice-vibration softening as ice is compressed5,6. It also agrees with recent observations of ice compression at higher temperatures—in the ‘no man’s land’ regime, between 145 and 200 kelvin, where kinetics are faster—resulting in crystalline phases7,8. Here we further probe the role of kinetics and show that, if carried out slowly, compression of ice I even at 100 kelvin (a region in which HDA typically forms) gives proton-ordered, but non-interpenetrating, ice IX′, then proton-ordered and interpenetrating ice XV′, and finally ice VIII′. By contrast, fast compression yields HDA but no ice IX, and direct transformation of ice I to ice XV′ is structurally inhibited. These observations suggest that HDA formation is a consequence of a kinetically arrested transformation between low-density ice I and high-density ice XV′ and challenge theories that connect amorphous ice to supercooled liquid water.
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The data that support the findings shown in the figures are available from the corresponding author upon reasonable request.
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This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. We thank the Sloan Foundation’s Deep Carbon Observatory for supporting this work.
The authors declare no competing interests.
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Extended data figures and tables
It should be noted that this curve is not from the dataset presented in Fig. 2, as that sample contained no lead. Thus, no direct one-to-one comparison can be made.
Extended Data Fig. 2 Data from separate experimental run, showing the crystallographic transformation sequence.
Initial compression of ice Ih, showing the crystalline sequence of transitions at 100 K. In the initial runs, the cooled sample was predominantly composed of ice Ih with a small amount of ice IX; hence the ‘sealing’ load that was applied to the gasket was slightly too high, and upon cooling the pressure was such that high-pressure crystalline phases were present. To remove ice IX, the sample was melted at 275 K and the pressure was reduced to atmospheric. Upon re-cooling the sample was determined to be pure ice Ih, as shown in the figure. The data shown in Fig. 2b were obtained from a subsequent loading, with a fresh sample in an unused gasket cooled to 100 K under a small sealing load; no ice IX was found to be present until initial compression at 100 K.
Transformation of pure ice Ih to HDA and recrystallization to ice VII′ with some remnant HDA. In this case the sample was pressurized directly to 15 kbar in 1,740 s at 100 K. These datasets have been normalized to vanadium.
Comparison of initial ice Ih with ice XV and ice VIII′. The sample was pressurized slowly with 1-h isobaric breaks to collect diffraction data. The data were collected using a detector at a greater diffraction angle, thus providing increased resolution at the expense of the momentum-transfer range. These datasets have been normalized to vanadium.
Comparison of the crystal phases resulting from the transformation of ice XV to ice VIII′ and from re-crystallization of HDA ice. All datasets were collected at 100 K.
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Tulk, C.A., Molaison, J.J., Makhluf, A.R. et al. Absence of amorphous forms when ice is compressed at low temperature. Nature 569, 542–545 (2019). https://doi.org/10.1038/s41586-019-1204-5
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