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H2O transforms to two forms of superionic (SI) ice at high pressures and temperatures, which contain highly mobile protons within a solid oxygen sublattice. Yet the stability field of both phases remains debated. Here, we present the results of an ultrafast X-ray heating study utilizing MHz pulse trains produced by the European X-ray Free Electron Laser to create high temperature states of H2O, which were probed using X-ray diffraction during dynamic cooling. We confirm an isostructural transition during heating in the 26-69 GPa range, consistent with the formation of SI-bcc. In contrast to prior work, SI-fcc was observed exclusively above ~50 GPa, despite evidence of melting at lower pressures. The absence of SI-fcc in lower pressure runs is attributed to short heating timescales and the pressure-temperature path induced by the pump-probe heating scheme in which H2O was heated above its melting temperature before the observation of quenched crystalline states, based on the earlier theoretical prediction that SI-bcc nucleates more readily from the fluid than SI-fcc. Our results may have implications for the stability of SI phases in ice-rich planets, for example during dynamic freezing, where the preferential crystallization of SI-bcc may result in distinct physical properties across mantle ice layers. The authors perform heating experiments using femtosecond X-ray free electron laser pulses to explore the phase stability of superionic H2O. The absence of a face-centered cubic phase below 50 GPa, where superionic ice forms from the melt, is attributed to the short heating time and may help understanding the stability of superionic phases in ice-rich planets. [ABSTRACT FROM AUTHOR]

The phase diagram and melting behavior of the equimolar water–ammonia mixture have been investigated by Raman spectroscopy, x-ray diffraction, and visual observations from 295 K to 675 K and up to 9 GPa. Our results show non-congruent melting behavior of ammonia monohydrate (AMH) solid below 324 K and congruent melting at higher temperatures. The congruent melting is associated with the stability of a previously unobserved solid phase of AMH, which we named AMH-VII. Another, presumably water-rich, hydrate has also been detected in the range 4 GPa–7 GPa at 295 K on decompression of the high pressure disordered ionico-molecular alloy (DIMA) phase. Comparing our melting data to the literature suggests that non-congruent melting extends from 220 K to 324 K and that the solid phase that borders the fluid between 220 K and 270 K, called AMH-III, is not a proper phase of AMH but a solid solution of ammonia hemihydrate and ice. These results allow us to propose a revised and extended experimental phase diagram of AMH. [ABSTRACT FROM AUTHOR]

H 2 O transforms to two forms of superionic (SI) ice at high pressures and temperatures, which contain highly mobile protons within a solid oxygen sublattice. Yet the stability field of both phases remains debated. Here, we present the results of an ultrafast X-ray heating study utilizing MHz pulse trains produced by the European X-ray Free Electron Laser to create high temperature states of H 2 O, which were probed using X-ray diffraction during dynamic cooling. We confirm an isostructural transition during heating in the 26-69 GPa range, consistent with the formation of SI-bcc. In contrast to prior work, SI-fcc was observed exclusively above ~50 GPa, despite evidence of melting at lower pressures. The absence of SI-fcc in lower pressure runs is attributed to short heating timescales and the pressure-temperature path induced by the pump-probe heating scheme in which H 2 O was heated above its melting temperature before the observation of quenched crystalline states, based on the earlier theoretical prediction that SI-bcc nucleates more readily from the fluid than SI-fcc. Our results may have implications for the stability of SI phases in ice-rich planets, for example during dynamic freezing, where the preferential crystallization of SI-bcc may result in distinct physical properties across mantle ice layers., (© 2024. The Author(s).)

In the 2-10 GPa pressure range, ammonia hemihydrate H_{2}O:(NH_{3})_{2} (AHH) is a molecular solid in which intermolecular interactions are ruled by distinct types of hydrogen bonds. Upon heating, the low-temperature ordered P2_{1}/c crystal (AHH-II) transits to a bcc phase (AHH-pbcc) where each site is randomly occupied by water or ammonia. In addition to the site disorder, experiments suggest that AHH-pbcc is a plastic solid, but the physical origin and mechanisms at play for the rotational and site disordering remain unknown. Using large-scale (∼10^{5}  atoms) and long-time (>10  ns) simulations, we show that, as temperature rises above the transition line, orientational disorder sets in, breaking the strongest hydrogen bonds that provide the largest contribution to the cohesion of the ordered AHH-II phase and enabling the molecules to migrate from a crystal site to a neighboring one. This generates a plastic molecular alloy with site disorder while the solid state is overall maintained until melting at a higher temperature. The case of high (P,T) plastic ammonia hemihydrate can be extended to other water-ammonia alloys where a similar interplay between distinct hydrogen bonds occurs.

Hydrogen hydrates are among the basic constituents of our solar system's outer planets, some of their moons, as well Neptune-like exo-planets. The details of their high-pressure phases and their thermodynamic conditions of formation and stability are fundamental information for establishing the presence of hydrogen hydrates in the interior of those celestial bodies, for example, against the presence of the pure components (water ice and molecular hydrogen). Here, we report a synthesis path and experimental observation, by X-ray diffraction and Raman spectroscopy measurements, of the most H[Formula: see text]-dense phase of hydrogen hydrate so far reported, namely the compound 3 (or C[Formula: see text]). The detailed characterisation of this hydrogen-filled ice, based on the crystal structure of cubic ice I (ice I[Formula: see text]), is performed by comparing the experimental observations with first-principles calculations based on density functional theory and the stochastic self-consistent harmonic approximation. We observe that the extreme (up to 90 GPa and likely beyond) pressure stability of this hydrate phase is due to the close-packed geometry of the hydrogen molecules caged in the ice I[Formula: see text] skeleton.