Synthesis of LaCN3, TbCN3, CeCN5, and TbCN5 Polycarbonitrides at Megabar Pressures.

Inorganic ternary metal-C-N compounds with covalently bonded C-N anions encompass important classes of solids such as cyanides and carbodiimides, well known at ambient conditions and composed of [CN]- and [CN2]2- anions, as well as the high-pressure formed guanidinates featuring [CN3]5- anion. At still higher pressures, carbon is expected to be 4-fold coordinated by nitrogen atoms, but hitherto, such CN4-built anions are missing. In this study, four polycarbonitride compounds (LaCN3, TbCN3, CeCN5, and TbCN5) are synthesized in laser-heated diamond anvil cells at pressures between 90 and 111 GPa. Synchrotron single-crystal X-ray diffraction (SCXRD) reveals that their crystal structures are built of a previously unobserved anionic single-bonded carbon-nitrogen three-dimensional (3D) framework consisting of CN4 tetrahedra connected via di- or oligo-nitrogen linkers. A crystal-chemical analysis demonstrates that these polycarbonitride compounds have similarities to lanthanide silicon phosphides. Decompression experiments reveal the existence of LaCN3 and CeCN5 compounds over a very large pressure range. Density functional theory (DFT) supports these discoveries and provides further insight into the stability and physical properties of the synthesized compounds.

Synthesis and characterization of XeAr2 under high pressure.

The binary Xe-Ar system has been studied in a series of high pressure diamond anvil cell experiments up to 60 GPa at 300 K. In-situ x-ray powder diffraction and Raman spectroscopy indicate the formation of a van der Waals compound, XeAr2, at above 3.5 GPa. Powder x-ray diffraction analysis demonstrates that XeAr2 adopts a Laves MgZn2-type structure with space group P63/mmc and cell parameters a = 6.595 Å and c = 10.716 Å at 4 GPa. Density functional theory calculations support the structure determination, with agreement between experimental and calculated Raman spectra. Our DFT calculations suggest that XeAr2 would remain stable without a structural transformation or decomposition into elemental Xe and Ar up to at least 80 GPa.

Counterintuitive effects of isotopic doping on the phase diagram of H2-HD-D2 molecular alloy.

Molecular hydrogen forms the archetypical quantum solid. Its quantum nature is revealed by behavior which is classically impossible and by very strong isotope effects. Isotope effects between [Formula: see text], [Formula: see text], and HD molecules come from mass difference and the different quantum exchange effects: fermionic [Formula: see text] molecules have antisymmetric wavefunctions, while bosonic [Formula: see text] molecules have symmetric wavefunctions, and HD molecules have no exchange symmetry. To investigate how the phase diagram depends on quantum-nuclear effects, we use high-pressure and low-temperature in situ Raman spectroscopy to map out the phase diagrams of [Formula: see text]-HD-[Formula: see text] with various isotope concentrations over a wide pressure-temperature (P-T) range. We find that mixtures of [Formula: see text], HD, and [Formula: see text] behave as an isotopic molecular alloy (ideal solution) and exhibit symmetry-breaking phase transitions between phases I and II and phase III. Surprisingly, all transitions occur at higher pressures for the alloys than either pure [Formula: see text] or [Formula: see text] This runs counter to any quantum effects based on isotope mass but can be explained by quantum trapping of high-kinetic energy states by the exchange interaction.

Formation and Stability of Dense Methane-Hydrogen Compounds.

Through a series of x-ray diffraction, optical spectroscopy diamond anvil cell experiments, combined with density functional theory calculations, we explore the dense CH_{4}-H_{2} system. We find that pressures as low as 4.8 GPa can stabilize CH_{4}(H_{2})_{2} and (CH_{4})_{2}H_{2}, with the latter exhibiting extreme hardening of the intramolecular vibrational mode of H_{2} units within the structure. On further compression, a unique structural composition, (CH_{4})_{3}(H_{2})_{25}, emerges. This novel structure holds a vast amount of molecular hydrogen and represents the first compound to surpass 50 wt % H_{2}. These compounds, stabilized by nuclear quantum effects, persist over a broad pressure regime, exceeding 160 GPa.

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.

High-temperature phase transitions in dense germanium.

Through a series of high-pressure x-ray diffraction experiments combined with in situ laser heating, we explore the pressure-temperature phase diagram of germanium (Ge) at pressures up to 110 GPa and temperatures exceeding 3000 K. In the pressure range of 64-90 GPa, we observe orthorhombic Ge-IV transforming above 1500 K to a previously unobserved high-temperature phase, which we denote as Ge-VIII. This high-temperature phase is characterized by a tetragonal crystal structure, space group I4/mmm. Density functional theory simulations confirm that Ge-IV becomes unstable at high temperatures and that Ge-VIII is highly competitive and dynamically stable at these conditions. The existence of Ge-VIII has profound implications for the pressure-temperature phase diagram, with melting conditions increasing to much higher temperatures than previous extrapolations would imply.

Structure and Metallicity of Phase V of Hydrogen.

A new phase V of hydrogen was recently claimed in experiments above 325 GPa and 300 K. Because of the extremely small sample size at such record pressures the measurements were limited to Raman spectroscopy. The experimental data on increase of pressure show decreasing Raman activity and darkening of the sample, which suggests band gap closure and impending molecular dissociation, but no definite conclusions could be reached. Furthermore, the available data are insufficient to determine the structure of phase V, which remains unknown. Introducing saddle-point ab initio random structure searching, we find several new structural candidates of hydrogen which could describe the observed properties of phase V. We investigate hydrogen metallization in the proposed candidate structures, and demonstrate that smaller band gaps are associated with longer bond lengths. We conclude that phase V is a stepping stone towards metallization.

Reactivity of Hydrogen-Helium and Hydrogen-Nitrogen Mixtures at High Pressures.

Through a series of Raman spectroscopy studies, we investigate the behavior of hydrogen-helium and hydrogen-nitrogen mixtures at high pressure across a wide range of concentrations. We find that there is no evidence of chemical association or increased miscibility of hydrogen and helium in the solid state up to pressures of 250 GPa at 300 K. In contrast, we observe the formation of concentration-dependent N_{2}-H_{2} van der Waals solids, which react to form N-H bonded compounds above 50 GPa. Through this combined study, we can demonstrate that the recently reported chemical association of H_{2}-He can be attributed to significant N_{2} contamination and subsequent formation of N_{2}-H_{2} compounds.

Structures of lithium-zinc compounds at high pressures.

Intermetallic lithium compounds have found a wide range of applications owing to their light mass and desirable electronic and mechanical properties. Here, by compressing pure lithium and zinc mixtures in a diamond-anvil cell, we observe a direct reaction forming the stoichiometric compound LiZn, at pressures below 1 GPa. On further compression above 10 GPa, we observe the formation of Li2Zn, which is the highest lithium content compound to be discovered in the Li-Zn system. Our results constrain the structures of these compounds and their evolution with pressure, furthering our understanding of potentially useful light volume-efficient energy storage materials.

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 Hydrogen and Deuterium at Low Temperatures.

In situ high-pressure low-temperature high-quality Raman data for hydrogen and deuterium demonstrate the presence of a novel phase, phase II^{'}, unique to deuterium and distinct from the known phase II. Phase II^{'} of D_{2} is not observed in hydrogen, making it the only phase that does not exist in both isotopes and occupies a significant part of P-T space from ∼25 to 110 GPa and below 125 K. For H_{2}, the data show that below 30 K the transition to phase II happens at as low as 73 GPa. The transformation from phase II to III commences at around ∼155 GPa and is completed by 170 GPa with the average pressure of ∼160 GPa being slightly higher than previously thought. The updated phase diagrams of H_{2} and D_{2} demonstrate the difference between the isotopes at low temperatures and moderate pressures, providing new information on the phase diagrams of both elements.

Synthesis and stability of hydrogen selenide compounds at high pressure.

The observation of high-temperature superconductivity in hydride sulfide (H2S) at high pressures has generated considerable interest in compressed hydrogen-rich compounds. High-pressure hydrogen selenide (H2Se) has also been predicted to be superconducting at high temperatures; however, its behaviour and stability upon compression remains unknown. In this study, we synthesize H2Se in situ from elemental Se and molecular H2 at pressures of 0.4 GPa and temperatures of 473 K. On compression at 300 K, we observe the high-pressure solid phase sequence (I-I'-IV) of H2Se through Raman spectroscopy and x-ray diffraction measurements, before dissociation into its constituent elements. Through the compression of H2Se in H2 media, we also observe the formation of a host-guest structure, (H2Se)2H2, which is stable at the same conditions as H2Se, with respect to decomposition. These measurements show that the behaviour of H2Se is remarkably similar to that of H2S and provides further understanding of the hydrogen chalcogenides under pressure.

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.

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.

Phonon localization by mass disorder in dense hydrogen-deuterium binary alloy.

Using a combination of the Raman spectroscopy and density functional theory calculations on dense hydrogen-deuterium mixtures of various concentrations, we demonstrate that, at 300 K and above 200 GPa, they transform into phase IV, forming a disordered binary alloy with six highly localized intramolecular vibrational (vibrons) and four delocalized low-frequency (<1200 cm(-1)) modes. Hydrogen-deuterium mixtures are unique in showing a purely mass-induced localization effect in the quantum solid: chemical bonding is isotope-independent while the mass varies by a factor of 2.

High-pressure synthesis and characterization of iridium trihydride.

We have performed in situ synchrotron x-ray diffraction studies of the iridium-hydrogen system up to 125 GPa. At 55 GPa, a phase transition in the metal lattice from the fcc to a distorted simple cubic phase is observed. The new phase is characterized by a drastically increased volume per metal atom, indicating the formation of a metal hydride, and substantially decreased bulk modulus of 190 GPa (383 GPa for pure Ir). Ab initio calculations show that the hydrogen atoms occupy the face-centered positions in the metal matrix, making this the first known noninterstitial noble metal hydride and, with a stoichiometry of IrH(3), the one with the highest volumetric hydrogen content. Computations also reveal that several energetically competing phases exist, which can all be seen as having distorted simple cubic lattices. Slow kinetics during decomposition at pressures as low as 6 GPa suggest that this material is metastable at ambient pressure and low temperatures.

Pressure-Induced Metallization of BaH2 and the Effect of Hydrogenation.

Using optical spectroscopy, X-ray diffraction, and electrical transport measurements, we have studied the pressure-induced metallization in BaH2 and Ba8H46. Our combined measurements suggest a structural phase transition from BaH2-II to BaH2-III accompanied by band gap closure and transformation to a metallic state at 57 GPa. The metallization is confirmed by resistance measurements as a function of the pressure and temperature. We also confirm that, with further hydrogenation, BaH2 forms the previously observed Weaire-Phelan Ba8H46, synthesized at 45 GPa and 1200 K. In this compound, metallization pressure is shifted to 85 GPa. Through a comparison of the properties of these two compounds, a question is raised about the importance of the hydrogen content in the electronic properties of hydride systems.

High pressure study of sodium trihydride.

The reactivity between NaH and H2 has been investigated through a series of high-temperature experiments up to pressures of 78 GPa in diamond anvil cells combined with first principles calculations. Powder X-ray diffraction measurements show that heating NaH in an excess of H2 to temperatures around 2000 K above 27 GPa yields sodium trihydride (NaH3), which adopts an orthorhombic structure (space group Cmcm). Raman spectroscopy measurements indicate that NaH3 hosts quasi-molecular hydrogen (H2δ-) within a NaH lattice, with the H2δ- stretching mode downshifted compared to pure H2 (Δν ∼-120 cm-1 at 50 GPa). NaH3 is stable under room temperature compression to at least 78 GPa, and exhibits remarkable P-T stability, decomposing at pressures below 18 GPa. Contrary to previous experimental and theoretical studies, heating NaH (or NaH3) in excess H2 between 27 and 75 GPa does not promote further hydrogenation to form sodium polyhydrides other than NaH3.

Mixed molecular and atomic phase of dense hydrogen.

We used Raman and visible transmission spectroscopy to investigate dense hydrogen (deuterium) up to 315 (275) GPa at 300 K. At around 200 GPa, we observe the phase transformation, which we attribute to phase III, previously observed only at low temperatures. This is succeeded at 220 GPa by a reversible transformation to a new phase, IV, characterized by the simultaneous appearance of the second vibrational fundamental and new low-frequency phonon excitations and a dramatic softening and broadening of the first vibrational fundamental mode. The optical transmission spectra of phase IV show an overall increase of absorption and a closing band gap which reaches 1.8 eV at 315 GPa. Analysis of the Raman spectra suggests that phase IV is a mixture of graphenelike layers, consisting of elongated H2 dimers experiencing large pairing fluctuations, and unbound H2 molecules.