Pressure-driven symmetry transitions in dense ${\mathrm{H}}_{2}\mathrm{O}$ ice

Pressure-driven symmetry transitions in dense $H_{2} O$ ice

Zachary M. Grande, C. Huy Pham, Dean Smith, John H. Boisvert, Chenliang Huang, Jesse S. Smith, Nir Goldman, Jonathan L. Belof, Oliver Tschauner, Jason H. Steffen, and Ashkan Salamat

Phys. Rev. B 105, 104109 – Published 17 March 2022

Abstract

X-ray diffraction and Raman spectroscopy of $H_{2} O$ (ice) structures are measured under static compression in combination with grain normalizing heat treatment via direct laser heating. We report the transition from cubic ice-VII to a structure of tetragonal symmetry, ice- ${VII}_{t}$ at $5.1 \pm 0.5 GPa$ . This is succeeded by the H-bond symmetrization transition occurring at a pressure of $30.9 \pm 3 GPa$ . Both experimental observations are supported by simulated Raman spectra from density-functional theory quantum calculations. The transition to H-bond symmetrization is evidenced by the reversible emergence of its characteristic Raman mode and a 2.5-fold increase in bulk modulus, implying a significant increase in bonding strength.

Received 9 December 2021
Revised 18 February 2022
Accepted 24 February 2022

DOI:https://doi.org/10.1103/PhysRevB.105.104109

Physics Subject Headings (PhySH)

Earth's interior Phase transitions Structural properties

Crystal structures Ice Molecular solids

Laser techniques Pressure techniques X-ray diffraction

Condensed Matter, Materials & Applied Physics

Authors & Affiliations

Zachary M. Grande¹, C. Huy Pham², Dean Smith ^1,3, John H. Boisvert¹, Chenliang Huang^1,4, Jesse S. Smith³, Nir Goldman², Jonathan L. Belof², Oliver Tschauner⁵, Jason H. Steffen ¹, and Ashkan Salamat ^1,*

¹Department of Physics and Astronomy, University of Nevada Las Vegas, Las Vegas, Nevada 89154, USA
²Lawrence Livermore National Laboratory, 7000 East Ave., Livermore, California 94550, USA
³HPCAT, X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA
⁴Lunar and Planetary Laboratory, University of Arizona, Tucson, Arizona 85721, USA
⁵Department of Geoscience, University of Nevada Las Vegas, Las Vegas, Nevada 89154, USA

^*salamat@physics.unlv.edu

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Vol. 105, Iss. 10 — 1 March 2022

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Figure 1
2-D x-ray diffraction images. (a) 2D diffraction image of ice at 23 GPa with no heat treatment displaying high degree of texturing and broadening of multigrain peaks. (b) 2D diffraction image of ice at 19 GPa post melt (PM) showing full Debye-Scherrer rings for an extensive $q$ range with minimal broadening.
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Figure 2
Evidence for ice- ${VII}_{t}$ . (a) Rietveld refinement of ice- ${VII}_{t} P \bar{4} 2 m$ at $6.5 \pm 0.5 GPa$ Inset, left: Rietveld refinement of the (2 0 0) Bragg peak using a cubic cell ( $P n \bar{3} m$ ); right: improvement when using a tetragonal cell ( $P \bar{4} 2 m$ ). (b) Progression of Raman features on increasing pressure. The dominant mode near 280 ${cm}^{- 1}$ exhibits asymmetry above 5 GPa, and tends back to a single mode above 21 GPa. Red asterisks (*) denote the emergence of the ice-X $T_{2g}$ Raman mode. (c) Simulated Raman spectra at 0 K for two DFT computed ice- ${VII}_{t}$ structures compared to the experimental spectra, both at approximately 10 GPa. (d) Dominant Raman feature of ice-VII at 3.3 GPa fit to a single peak whereas the feature in ice- ${VII}_{t}$ at 11.3 GPa requires a triplet to fit in agreement with the simulated spectra.
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Figure 3
Raman spectrum of heat-treated $H_{2} O$ ices under compression. (a) Frequency shift of measured Raman modes of $H_{2} O$ ice with pressure. Splitting of the dominant lattice mode near 280 ${cm}^{- 1}$ due to tetragonal distortion above 5 GPa is highlighted in blue and green. Red points show the emergence of the ice-X $T_{2g}$ mode above 33 GPa. Dashed lines represent transition pressures based on analysis of XRD data. (b) Bottom to top: Development of ice-X $T_{2g}$ mode on compression above 33 GPa and its reversible disappearance on decompression. (c) Frequency shift of ice-X $T_{2g}$ Raman mode with pressure as determined by this study (experimentally and theoretically) and an interpolating line, as a guide, connecting to those reported by Goncharov et al. [12] at higher pressures.
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Figure 4
Equation of state fitting. (a) Pressure-volume plot of our data and Vinet EOS fit from MCMC for the three phases. The calculated uncertainties in transition pressures are indicated by the blue shaded regions at $5.1 \pm 0.5 GPa$ and $30.9 \pm 3 GPa$ , respectively, and the grey lines are results from previous experiments. Curves are color coded by phase (blue: cubic ice-VII; black: noncubic ice- ${VII}_{t}$ ; and red: ice-X. Orange error bars indicate our systematic uncertainty from deviatoric stresses in non-heat-treated data. (b) Linearized Vinet EOS. Left: When assuming a single phase model. Right: When assuming a three-phase model.
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Figure 5
Phase diagram of ice. Dark blue-, green-, and red-shaded regions denote ice-VII, ${VII}_{t}$ and X, respectively, and projected phase boundaries separating high-pressure ice phases from our work are shown as solid black lines. Ice-X phase boundaries connect our measured transition at $30.9 \pm 3 GPa$ and 300 K to the inflection point in the melt curve observed by Schwager and Boehler [53] and Goncharov et al. [54], which have been associated with the transition from molecular to ionic fluid. The same procedure has been used to project phase boundaries from Loubeyre et al. [13] and Meier et al. [18] In doing so, we deduce a steep, positive Clapeyron slope defining the transition from hydrogen bonding to ionic bonding in dense $H_{2} O$ , consistent with a pressure-driven change in bonding nature. Dashed lines show measured melting curves [53, 54, 55, 56]. Superionic boundary from Sugimura et al. [57] is highlighted.
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Physical Review B

covering condensed matter and materials physics

Pressure-driven symmetry transitions in dense $H_{2} O$ ice

Zachary M. Grande, C. Huy Pham, Dean Smith, John H. Boisvert, Chenliang Huang, Jesse S. Smith, Nir Goldman, Jonathan L. Belof, Oliver Tschauner, Jason H. Steffen, and Ashkan Salamat

Phys. Rev. B 105, 104109 – Published 17 March 2022

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Physical Review B

covering condensed matter and materials physics

Pressure-driven symmetry transitions in dense H2O ice

Zachary M. Grande, C. Huy Pham, Dean Smith, John H. Boisvert, Chenliang Huang, Jesse S. Smith, Nir Goldman, Jonathan L. Belof, Oliver Tschauner, Jason H. Steffen, and Ashkan Salamat

Phys. Rev. B 105, 104109 – Published 17 March 2022

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Pressure-driven symmetry transitions in dense $H_{2} O$ ice