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Abstract 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.

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.

Solid mixtures of ammonia and water, the so-called ammonia hydrates, are thought to be major components of solar and extra-solar icy planets. We present here a thorough characterization of the recently reported high pressure ( P )-temperature ( T ) phase VII of ammonia monohydrate (AMH) using Raman spectroscopy, X-ray diffraction, and quasi-elastic neutron scattering (QENS) experiments in the ranges 4-10 GPa, 450-600 K. Our results show that AMH-VII exhibits common structural features with the disordered ionico-molecular alloy (DIMA) phase, stable above 7.5 GPa at 300 K: both present a substitutional disorder of water and ammonia over the sites of a body-centered cubic lattice and are partially ionic. The two phases however markedly differ in their hydrogen dynamics, and QENS measurements show that AMH-VII is characterized by free molecular rotations around the lattice positions which are quenched in the DIMA phase. AMH-VII is thus a peculiar crystalline solid in that it combines three types of disorder: substitutional, compositional, and rotational.