Ross T. Howie

Evidence for a new phase of dense hydrogen above 325 gigapascals

Almost 80 years ago it was predicted that, under sufficient compression, the H–H bond in molecular hydrogen (H2) would break, forming a new, atomic, metallic, solid state of hydrogen. Reaching this predicted state experimentally has been one of the principal goals in high-pressure research for the past 30 years. Here, using in situ high-pressure Raman spectroscopy, we present evidence that at pressures greater than 325 gigapascals at 300 kelvin, H2 and hydrogen deuteride (HD) transform to a new phase—phase V. This new phase of hydrogen is characterized by substantial weakening of the vibrational Raman activity, a change in pressure dependence of the fundamental vibrational frequency and partial loss of the low-frequency excitations. We map out the domain in pressure–temperature space of the suggested phase V in H2 and HD up to 388 gigapascals at 300 kelvin, and up to 465 kelvin at 350 gigapascals; we do not observe phase V in deuterium (D2). However, we show that the transformation to phase IV′ in D2 occurs above 310 gigapascals and 300 kelvin. These values represent the largest known isotropic shift in pressure, and hence the largest possible pressure difference between the H2 and D2 phases, which implies that the appearance of phase V of D2 must occur at a pressure of above 380 gigapascals. These experimental data provide a glimpse of the physical properties of dense hydrogen above 325 gigapascals and constrain the pressure and temperature conditions at which the new phase exists. We speculate that phase V may be the precursor to the non-molecular (atomic and metallic) state of hydrogen that was predicted 80 years ago.

Raman spectroscopy of hot hydrogen above 200 GPa

It has been theorized that at high pressure the increased energy of the zero-point oscillations in hydrogen would destabilize the lattice and form a ground fluid state at 0 K (ref. 1). Theory has also suggested that this fluid state, representing a new state of matter, might have unusual properties governed by quantum effects, such as superfluidity or superconductivity. Here, by combining Raman spectroscopy and in situ high-temperature, high-pressure techniques, we demonstrate that above 200 GPa a new phase transition occurs as temperature is increased, for example 480 K at 255 GPa. If the transformation is interpreted as melting, it would be the lowest melting temperature of any material at these high pressures. We also find a new triple point between phases I and IV and the new phase, and demonstrate that hydrogen retains its molecular character around this point. These data may require a significant revision of the phase diagram of hydrogen above 200 GPa.

Hydrogenation of Graphene by Reaction at High Pressure and High Temperature

The chemical reaction between hydrogen and purely sp(2)-bonded graphene to form graphenes purely sp(3)-bonded analogue, graphane, potentially allows the synthesis of a much wider variety of novel two-dimensional materials by opening a pathway to the application of conventional chemistry methods in graphene. Graphene is currently hydrogenated by exposure to atomic hydrogen in a vacuum, but these methods have not yielded a complete conversion of graphene to graphane, even with graphene exposed to hydrogen on both sides of the lattice. By heating graphene in molecular hydrogen under compression to modest high pressure in a diamond anvil cell (2.6-5.0 GPa), we are able to react graphene with hydrogen and propose a method whereby fully hydrogenated graphane may be synthesized for the first time.

Comment on “Observation of the Wigner-Huntington transition to metallic hydrogen”

Dias and Silvera (Research Article, 17 February 2017, p. 715) claim the observation of the Wigner-Huntington transition to metallic hydrogen at 495 gigapascals. We show that neither the claims of the record pressure nor the phase transition to a metallic state are supported by data and that the data contradict the authors’ own unconfirmed previous results.

Hydrogen at extreme pressures (Review Article)

Here we review recent experimental and theoretical studies of hydrogen approaching metallization regime. Experimental techniques have made great advances over the last several years making it possible to reach previously unachievable conditions of pressure and temperature and to probe hydrogen at these conditions. Theoretical methods have also greatly improved; exemplified through the prediction of new structural and ordered quantum states. Recently, a new solid phase of hydrogen, phase IV, has been discovered in a high-pressure high-temperature domain. This phase is quite unusual structurally and chemically as it represents an intermediate state between common molecular and monatomic configurations. Moreover, it shows remarkable fluxional characteristics related to its quantum nature, which makes it unique among the solid phases, even of light elements. However, phase IV shows the presence of a band gap and exhibits distinct phonon and libron characteristic of classical solids. The quantum behavior of hydrogen in the limit of very high pressure remains an open question. Prospects of studying hydrogen at more extreme conditions by static and combined static-dynamic methods are also presented.

Formation of xenon-nitrogen compounds at high pressure

Molecular nitrogen exhibits one of the strongest known interatomic bonds, while xenon possesses a closed-shell electronic structure: a direct consequence of which renders both chemically unreactive. Through a series of optical spectroscopy and x-ray diffraction experiments, we demonstrate the formation of a novel van der Waals compound formed from binary Xe-N2 mixtures at pressures as low as 5 GPa. At 300 K and 5 GPa Xe(N2)2-I is synthesised, and if further compressed, undergoes a transition to a tetragonal Xe(N2)2-II phase at 14 GPa; this phase appears to be unexpectedly stable at least up to 180 GPa even after heating to above 2000 K. Raman spectroscopy measurements indicate a distinct weakening of the intramolecular bond of the nitrogen molecule above 60 GPa, while transmission measurements in the visible and mid-infrared regime suggest the metallisation of the compound at ~100 GPa.

Locating Gases in Porous Materials: Cryogenic Loading of Fuel‐Related Gases Into a Sc‐based Metal–Organic Framework under Extreme Pressures

An alternative approach to loading metal organic frameworks with gas molecules at high (kbar) pressures is reported. The technique, which uses liquefied gases as pressure transmitting media within a diamond anvil cell along with a single-crystal of a porous metal-organic framework, is demonstrated to have considerable advantages over other gas-loading methods when investigating host-guest interactions. Specifically, loading the metal-organic framework Sc2BDC3 with liquefied CO2 at 2 kbar reveals the presence of three adsorption sites, one previously unreported, and resolves previous inconsistencies between structural data and adsorption isotherms. A further study with supercritical CH4 at 3-25 kbar demonstrates hyperfilling of the Sc2 BDC3 and two high-pressure displacive and reversible phase transitions are induced as the filled MOF adapts to reduce the volume of the system.

Hydrogen (deuterium) vibron frequency as a pressure comparison gauge at multi-Mbar pressures

The Raman spectra of compressed hydrogen (deuterium) have been measured in the multi-Mbar pressure range in the diamond anvil cell using the position of the stressed first-order Raman diamond edge (DE) to estimate pressure. We find that the Raman spectra are very consistent in repeated experiments for the critical frequencies of the hydrogen (deuterium) bands at the phase transition pressure-temperature (P-T) points. However, measurements of pressure determined from the DE in different experiments vary substantially with virtually identical Raman spectra of H2 (D2), giving in some cases a pressure variation as high as 20 GPa. These variations do not only depend on sample and sample chamber geometry but also on the P-T path taken, thus making the DE pressure determination uncertain. Therefore, we propose in experiments on hydrogen (deuterium) to use the Raman frequency of the intramolecular vibration (vibron) of H2(D2) as a pressure sensor. By comparing the vibron frequencies and considering the geometrical changes of the sample chamber caused by very high pressures, we propose an alternative explanation to the recent claims of a transformation to a metallic liquid state of hydrogen (deuterium).

High pressure synthesis and stability of cobalt hydrides

In situ high-pressure high-temperature X-ray powder diffraction studies of the cobalt-hydrogen system reveal the direct synthesis of both the binary cobalt hydride (CoH) and a novel cobalt dihydride (CoH2). We observe the formation of fcc CoH at pressures of 4 GPa, which persists to pressures of 45 GPa. At this pressure, we see the emergence with time of a further expanded fcc lattice, which we identify as CoH2, where the hydrogen atoms occupy the tetrahedral vacancies. We have explored alternative synthesis routes of CoH2 and can lower the synthesis pressure to 35 GPa by the application of high temperature. CoH2 is stable to at least 55 GPa and decomposes into CoH below 10 GPa, releasing molecular hydrogen before further decomposing completely into its constituent elements below 3 GPa. As a first-row transition metal, cobalt has a relatively lower mass than other hydride-forming transition metals, and as a result, CoH2 has a high hydrogen content of 3.3 wt. % and a volumetric hydrogen density of 214 g/l.

High-pressure behavior of superconducting boron-doped diamond

This work investigates the high-pressure structure of freestanding superconducting