Hydrogen is widely regarded as a cornerstone of future low-carbon energy technologies, yet the lack of safe, efficient, and reversible solid-state storage materials remains a major barrier to its large-scale deployment. Although porous frameworks and metal hydrides have been extensively explored, far less is known about the ability of dense molecular solids to stabilize hydrogen at near-ambient pressure. Here we show that fully crystalline cubic ice, despite its non-porous nature, can retain molecular hydrogen as an interstitial guest following controlled decompression from a high-pressure hydrogen hydrate precursor. Using synchrotron X-ray diffraction, neutron diffraction, and Raman spectroscopy, we demonstrate that hydrogen is retained within the ice structure up to about 130 K, producing reproducible lattice expansion and distinct spectroscopic signatures. We further show that pure cubic ice can be partially refilled with hydrogen at 0.18 GPa and 130 K, while fully hydrogen-filled cubic structure can be preserved at the same pressure up to 90 K. The retained hydrogen content reaches several percent of the parent hydrate composition, corresponding to gravimetric and volumetric storage densities comparable to those of interstitial hydrogen in metals. These results reveal an unexpected ability of a dense hydrogen-bonded crystal structure to host molecular hydrogen without permanent porosity or chemical bonding, establishing cubic ice as a minimal model for hydrogen-lattice interactions. More broadly, our findings identify dense hydrogen-bonded solids as an unexplored class of materials for hydrogen storage physics, with implications extending from energy materials to planetary and astrophysical ice environments.

Water is the third most abundant molecule in the universe and a key component in the interiors of icy moons, giant planets and Uranus- and Neptune-like exoplanets1, 2-3. Owing to its distinct molecular structure and flexible hydrogen bonds that readily adapt to a wide range of pressures and temperatures, water forms numerous crystalline and amorphous phases4, 5-6. Most relevant for the high pressures and temperatures of planetary interiors is ice VII (ref. 4), and simulations have identified along its melting curve the existence of a so-called plastic phase7, 8, 9, 10, 11-12 in which individual molecules occupy fixed positions as in a solid yet are able to rotate as in a liquid. Such plastic ice has not yet been directly observed in experiments. Here we present quasi-elastic neutron scattering measurements, conducted at temperatures between 450 and 600 K and pressures up to 6 GPa, that reveal the existence of a body-centred cubic structure, as found in ice VII, with water molecules showing picosecond rotational dynamics typical for liquid water. Comparison with molecular dynamics simulations indicates that this plastic ice VII does not conform to a free rotor phase but rather shows rapid orientational jumps, as observed in jump-rotor plastic crystals13,14. We anticipate that our observation of plastic ice VII will affect our understanding of the geodynamics of icy planets and the differentiation processes of large icy moons.

Computational studies using effective potentials that treat water as a rigid molecule were the first to predict the existence of a plastic phase of ice VII. Fifteen years later, this prediction was confirmed experimentally: in the plastic phase, water molecules retain the translational order of the body-centered cubic lattice while undergoing jump-like rotational motion typical of the liquid. Here, we show that this plastic phase also emerges in simulations employing the data-driven many-body MB-pol potential. The phase appears at high pressure, sandwiched between the liquid and ice VII phases. Our results confirm the first-order nature of both the ice VII-plastic and plastic-liquid transitions. Moreover, we find that ice VII exhibits rotational motion of hydrogen atoms on the nanosecond timescale near the melting line, although this motion is qualitatively distinct from that observed in the plastic phase. These results support the existence of the plastic phase beyond rigid-molecule models and provide new insight into the rotational dynamics of ice under extreme conditions.

The experimental results on molecular diffusion in supercritical methane in a wide pressure range reported by [U. Ranieri et al., Nat. Commun. 15, 4142 (2024)2041-172310.1038/s41467-024-47961-7] are compared with the theoretical expectations based on the Lennard-Jones model. In the low-pressure low-density limit, the kinetic approach within the Chapman-Enskog approximation is shown to be adequate. At higher pressures and densities, the freezing density scaling approach becomes appropriate. In this approach, the properly reduced transport coefficients along isotherms appear as quasi-universal functions of the density divided by the density at the freezing point. We analyze the transition from gaslike to liquidlike dynamical behavior from the perspective of the Stokes-Einstein-Sutherland relation linking self-diffusion and shear viscosity coefficients. This analysis locates the dynamical crossover close to the transition from gas- to liquidlike molecular diffusion in methane, which is observed experimentally. We emphasize the importance of distinguishing between two separate transitions: the intersection of gaslike and liquidlike asymptotes of transport-related properties and the onset of the rigid-fluid regime. These transitions occur at significantly different locations on the phase diagram, which explains the conflicting criteria often used to define the gas-to-liquid-like dynamical crossover and the Frenkel line. In addition, our results offer a practical and predictive framework for estimating the transport properties of supercritical methane in pressure and temperature regimes where experimental data are currently unavailable.

According to textbooks, no physical observable can be discerned allowing to distinguish a liquid from a gas beyond the critical point. Yet, several proposals have been put forward challenging this view and various transition boundaries between a gas-like and a liquid-like behaviour, including the so-called Widom and Frenkel lines, and percolation line, have been suggested to delineate the supercritical state space. Here we report observation of a crossover from gas-like (Gaussian) to liquid-like (Lorentzian) self-dynamic structure factor by incoherent quasi-elastic neutron scattering measurements on supercritical fluid methane as a function of pressure, along the 200 K isotherm. The molecular self-diffusion coefficient was derived from the best Gaussian (at low pressures) or Lorentzian (at high pressures) fits to the neutron spectra. The Gaussian-to-Lorentzian crossover is progressive and takes place at about the Widom line intercept (59 bar). At considerably higher pressures, a liquid-like jump diffusion mechanism properly describes the supercritical fluid on both sides of the Frenkel line. The present observation of a gas-like to liquid-like crossover in the self dynamics of a simple supercritical fluid confirms emerging views on the unexpectedly complex physics of the supercritical state, and could have planet-wide implications and possible industrial applications in green chemistry.

Abstract Ammonium fluoride (NH₄F) exhibits a variety of crystalline phases depending on temperature and pressure. By employing Raman spectroscopy and synchrotron X-ray diffraction beyond megabar pressures (up to 140 GPa), we have here observed a novel dense solid phase of NH₄F, characterised by the tetragonal P4/nmm structure also observed in other ammonium halides under less extreme pressure conditions, typically a few GPa. Using detailed ab-initio calculations and reevaluating earlier theoretical models pertaining to other ammonium halides, we examine the microscopic mechanisms underlying the transition from the low-pressure cubic phase (P-43m) to the newly identified high-pressure tetragonal phase (P4/nmm). Notably, NH₄F exhibits distinctive properties compared to its counterparts, resulting in a significantly broader pressure range over which this transition unfolds, facilitating the identification of its various stages. Our analysis points to a synergistic interplay driving the transition to the P4/nmm phase, which we name phase VIII. At intermediate pressures (around 40 GPa), a displacive transition of fluorine ions initiates a tetragonal distortion of the cubic phase. Subsequently, at higher pressures (around 115 GPa), every second ammonium ion undergoes a rotational shift, adopting an anti-tetrahedral arrangement. This coupled effect orchestrates the transition process, leading to the formation of the tetragonal phase.

Hydrogen hydrates exhibit a rich phase diagram influenced by both pressure and temperature, with the so-called C_{2} phase emerging prominently above 2.5 GPa. In this phase, hydrogen molecules are densely packed within a cubic icelike lattice and the interaction with the surrounding water molecules profoundly affects their quantum rotational dynamics. Herein, we delve into this intricate interplay by directly solving the Schrödinger's equation for a quantum H_{2} rotor in the C_{2} crystal field at finite temperature, generated through density functional theory. Our calculations reveal a giant energy splitting relative to the magnetic quantum number of ±3.2  meV for l=1. Employing inelastic neutron scattering, we experimentally measure the energy levels of H_{2} within the C_{2} phase at 6.0 and 3.4 GPa and low temperatures, finding good agreement with our theoretical predictions. These findings underscore the pivotal role of hydrogen-water interactions in dictating the rotational behavior of the hydrogen molecules within the C_{2} phase and indicate heightened van der Waals interactions compared to other hydrogen hydrates.

Hydrogen clathrate hydrates are ice-like crystalline substances in which hydrogen molecules are trapped inside polyhedral cages formed by the water molecules. Small cages can host only a single H2 molecule, while each large cage can be occupied by up to four H2 molecules. Here, we present a neutron scattering study on the structure of the sII hydrogen clathrate hydrate and on the low-temperature dynamics of the hydrogen molecules trapped in its large cages, as a function of the gas content in the samples. We observe spectral features at low energy transfer (between 1 and 3 meV), and we show that they can be successfully assigned to the rattling motion of a single hydrogen molecule occupying a large water cage. These inelastic bands remarkably lose their intensity with increasing the hydrogen filling, consistently with the fact that the probability of single occupation (as opposed to multiple occupation) increases as the hydrogen content in the sample gets lower. The spectral intensity of the H2 rattling bands is studied as a function of the momentum transfer for partially emptied samples and compared with three distinct quantum models for a single H2 molecule in a large cage: (i) the exact solution of the Schrödinger equation for a well-assessed semiempirical force field, (ii) a particle trapped in a rigid sphere, and (iii) an isotropic three-dimensional harmonic oscillator. The first model provides good agreement between calculations and experimental data, while the last two only reproduce their qualitative trend. Finally, the radial wavefunctions of the three aforementioned models, as well as their potential surfaces, are presented and discussed.

The dynamical properties of water molecules confined in the unidirectional hydrophilic nanopores of AlPO4-54 are investigated with quasi-elastic neutron scattering as a function of temperature down to 118 K. AlPO4-54 has among the largest pores known for aluminophosphates and zeolites (about 1.3 nm), though they are small enough to prevent water crystallization due to the high degree of confinement. Water molecular diffusion into the pore is here measured down to 258 K. Diffusion is slower than in bulk water and has an activation energy of Ea = (20.8 ± 2.8) kJ/mol, in agreement with previous studies on similar confining media. Surprisingly, local hydrogen dynamics associated with water reorientation is measured down to temperatures (118 K), i.e., well below the expected glass transition temperature of bulk water. The reorientational time scale shows the well-known non-Arrhenius behavior down to the freezing of water mass diffusion, while it shows a feeble temperature dependence below. This fast local dynamics, of the order of fractions of nanoseconds, is believed to take place in the dense, highly disordered amorphous water occupying the pore center, indicating its possible plastic nature.

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 H2-dense phase of hydrogen hydrate so far reported, namely the compound 3 (or C3). The detailed characterisation of this hydrogen-filled ice, based on the crystal structure of cubic ice I (ice Ic), 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 Ic 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.

We model, via classical molecular dynamics simulations, the plastic phase of ice VII across a wide range of the phase diagram of interest for planetary investigations. Although structural and dynamical properties of plastic ice VII are mostly independent on the thermodynamic conditions, the hydrogen bond network (HBN) acquires a diverse spectrum of topologies distinctly different from that of liquid water and of ice VII simulated at the same pressure. We observe that the HBN topology of plastic ice carries some degree of similarity with the crystal phase, stronger at thermodynamic conditions proximal to ice VII, and gradually lessening when approaching the liquid state. Our results enrich our understanding of the properties of water at high pressure and high temperature and may help in rationalizing the geology of water-rich planets.

Methane, the principal component of natural gas, is an important energy source and raw material for chemical reactions. It also plays a significant role in planetary physics, being one of the major constituents of giant planets. Here, we report measurements of the molecular self-diffusion coefficient of dense supercritical CH 4 reaching the freezing pressure. We find that the high-pressure behaviour of the self-diffusion coefficient measured by quasi-elastic neutron scattering at 300 K departs from that expected for a dense fluid of hard spheres and suggests a density-dependent molecular diameter. Breakdown of the Stokes–Einstein–Sutherland relation is observed and the experimental results suggest the existence of another scaling between self-diffusion coefficient D and shear viscosity η , in such a way that D η / ρ =constant at constant temperature, with ρ the density. These findings underpin the lack of a simple model for dense fluids including the pressure dependence of their transport properties.

The structure and vibrational properties of water molecules confined in unidirectional hydrophilic nanopores of AlPO4-54•xH2O were investigated from room temperature down to 10 K by single crystal synchrotron X-ray diffraction, neutron pair distribution function analysis, incoherent inelastic neutron scattering, farand mid-infrared spectroscopy, ab-initio Molecular Dynamics and Grand Canonical Monte Carlo Simulations. The ensemble of results indicates that water confined in AlPO4-54•xH2O nanopores does not crystallize down to 10 K and points at the existence of two different types of water networks, whose local arrangement and dynamical behavior become more and more distinguished when lowering the temperature below 150 K. The dependence of temperature of the infrared spectroscopy points at two transitions at 250 and 150 K. Upon cooling, water close to the zeolite pore wall shows a highly ordered local arrangement induced by the pore wall, with more defined site occupancy and lower density with respect to bulk water. Conversely, water in the pore core shows a denser, more disordered and orientationally distorted arrangement, and a glassy-like behavior down to the lowest investigated temperature.

In recent years, evidence has emerged that solid water can contain substantial amounts of guest species, such as small gas molecules—in gas hydrate structures—or ions—in salty ice structures—and that these ‘filled’ ice structures can be stable under pressures of tens of Gigapascals and temperatures of hundreds of Kelvins. The inclusion of guest species can strongly modify the density, vibrational, diffusive and conductivity properties of ice under high pressure, and promote novel exotic properties. In this review, we discuss our experimental findings and molecular dynamics simulation results on the structures formed by salt- and gas-filled ices, their unusual properties, and the unexpected dynamical phenomena observed under pressure and temperature conditions relevant for planetary interiors modelling. This article is part of the theme issue ‘The physics and chemistry of ice: scaffolding across scales, from the viability of life to the formation of planets’.

We investigate the state of water confined in the cylindrical pores of MCM-41 type mesoporous silica, with pore diameters of 2.8 nm and 4.5 nm, over the temperature range 160–290 K by combining small angle neutron scattering and wide angle diffraction.

The quest for a possible liquid-liquid coexistence line in supercooled water below its homogeneous nucleation temperature is faced by confining water within a porous silica substrate (MCM-41). This system is investigated by synchrotron radiation infrared spectroscopy, exploring both the intramolecular and the intermolecular vibrational dynamics, in the temperature range from ambient down to ∼120 K, along several isobaric paths between 0.7 kbar and 3.0 kbar. Upon lowering the temperature, the OH-stretching band shows that the intramolecular vibrational dynamics continuously evolves from predominantly liquidlike to predominantly icelike. An abrupt change in the line shape of the intermolecular vibrational band between 220 K and 240 K, depending on the pressure, is the signature of nucleation of ice within the MCM-41 pores. These findings do not support the presence of two liquid phases and provide evidence for the coexistence of liquid water and ice in water confined in MCM-41.

Methane hydrates naturally form on Earth and in the interiors of some icy bodies of the Universe, and are also expected to play a paramount role in future energy and environmental technologies. Here we report experimental observation of an extremely fast methane diffusion at the interface of the two most common clathrate hydrate structures, namely clathrate structures I and II. Methane translational diffusion—measured by quasielastic neutron scattering at 0.8 GPa—is faster than that expected in pure supercritical methane at comparable pressure and temperature. This phenomenon could be an effect of strong confinement or of methane aggregation in the form of micro-nanobubbles at the interface of the two structures. Our results could have implications for understanding the replacement kinetics during sI–sII conversion in gas exchange experiments and for establishing the methane mobility in methane hydrates embedded in the cryosphere of large icy bodies in the Universe.