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Link to original content: https://pubmed.ncbi.nlm.nih.gov/33602936
Experimental evidence for the existence of a second partially-ordered phase of ice VI - PubMed Skip to main page content
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. 2021 Feb 18;12(1):1129.
doi: 10.1038/s41467-021-21351-9.

Experimental evidence for the existence of a second partially-ordered phase of ice VI

Ryo Yamane  1   2 , Kazuki Komatsu  3 , Jun Gouchi  4 , Yoshiya Uwatoko  4 , Shinichi Machida  5 , Takanori Hattori  6 , Hayate Ito  3 , Hiroyuki Kagi  3
Affiliations

Experimental evidence for the existence of a second partially-ordered phase of ice VI

Ryo Yamane et al. Nat Commun. .

Erratum in

Abstract

Ice exhibits extraordinary structural variety in its polymorphic structures. The existence of a new form of diversity in ice polymorphism has recently been debated in both experimental and theoretical studies, questioning whether hydrogen-disordered ice can transform into multiple hydrogen-ordered phases, contrary to the known one-to-one correspondence between disordered ice and its ordered phase. Here, we report a high-pressure phase, ice XIX, which is a second hydrogen-partially-ordered phase of ice VI. We demonstrate that disordered ice undergoes different manners of hydrogen ordering, which are thermodynamically controlled by pressure in the case of ice VI. Such multiplicity can appear in all disordered ice, and it widely provides a research approach to deepen our knowledge, for example of the crucial issues of ice: the centrosymmetry of hydrogen-ordered configurations and potentially induced (anti-)ferroelectricity. Ultimately, this research opens up the possibility of completing the phase diagram of ice.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Fig. 1
Fig. 1. Representative experimental paths of dielectric and neutron diffraction experiments described in the phase diagram of ice obtained herein.
Dielectric experiments of ice VI and its hydrogen-ordered phases were conducted at 0.88–2.2 GPa. HCl (99.9%, Wako) was introduced as a dopant (concentration: 10−2 M) to accelerate the hydrogen ordering of ice VI. The measured temperature was in the range 100–150 K and changed at a rate of 2 K/h for all dielectric measurements. Neutron diffraction experiments of DCl-doped D2O (concentration: 10−2 M) were conducted using a more complicated path to ensure that the sample was a fine powder through solid–solid phase transitions, i.e., ice III → ice V → ice VI. Sample diffraction was collected at 1.6 and 2.2 GPa, and the temperature range was 80–150 K. Temperature was changed at a rate of 6 K/h. Diffraction patterns were collected using new samples in each run at different pressures to confirm reproducibility. Phase boundaries among ice VI, ice XV, and ice XIX are described by black solid lines, based on dielectric experiments (red and blue squares correspond to phase transition temperatures from ice VI to ice XV and XIX, respectively). The dotted line shows the provisional phase boundary between ice XV and ice XIX (see main text).
Fig. 2
Fig. 2. Temperature dependence of dielectric properties of HCl-doped ice VI and its hydrogen-ordered phases.
a Dielectric constant and dielectric loss of HCl-doped ice VI and its hydrogen-ordered phase (ice XIX) obtained at 1.9 GPa upon cooling using an LCR meter (NF corp., ZM2371). The measured frequency was from 3 mHz to 2 MHz. b Temperature dependence of dielectric loss peak intensity of HCl-doped ice VI and its hydrogen-ordered phases obtained in the pressure range 0.88–2.2 GPa upon cooling (black diamonds). Each peak intensity of dielectric loss was estimated using a model fitting for the corresponding dielectric loss spectrum based on the Debye dielectric-relaxation equation (polydispersion type). Under each pressure, peak intensities were normalised by that obtained at the highest temperature. Each plot was shifted by 0.7 with increasing pressure for clarity. In each pressure, the transition temperature whose determination is described in Supplementary Method 2.2 is indicated by black arrows.
Fig. 3
Fig. 3. Temperature dependence of neutron diffraction patterns and lattice parameters of DCl-doped D2O ice VI and ice XIX.
a Neutron diffraction patterns of ice VI and XIX obtained at 1.6 GPa in the cooling run. Only an expanded area showing new peaks of ice XIX is displayed. The blue and black ticks represent all the peak positions expected from the unit cells of ice XIX and ice XV, respectively. Blue triangles indicate new peaks at 2.20 Å and 2.26 Å, which do not appear from the unit cell of ice XV. b Temperature dependence of lattice parameters, a and c, of ice VI or ice XIX obtained at 1.6 GPa. The values were calculated based on the ice VI structure model even for ice XIX because of a common oxygen framework between ice VI and XIX. c Temperature dependence of c/a at two different pressures, 1.6 and 2.2 GPa, indicated by black and grey. Phase transition from ice VI to ice XIX started at around 117 K and 124 K in the respective cooling runs. The c/a values are normalised by that at 102 K. Diffraction patterns were collected using new samples in each run under different pressures to confirm reproducibility.
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