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.

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.

Chemically Assisted Precompression of Hydrogen Molecules in Alkaline-Earth Tetrahydrides.

Through a series of high pressure diamond anvil experiments, we report the synthesis of alkaline earth (Ca, Sr, Ba) tetrahydrides, and investigate their properties through Raman spectroscopy, X-ray diffraction, and density functional theory calculations. The tetrahydrides incorporate both atomic and quasi-molecular hydrogen, and we find that the frequency of the intramolecular stretching mode of the H2δ- units downshifts from Ca to Sr and to Ba upon compression. The experimental results indicate that the larger the host cation, the longer the H2δ- bond. Analysis of the electron localization function (ELF) demonstrates that the lengthening of the H-H bond is caused by the charge transfer from the metal to H2δ- and by the steric effect of the metal host on the H-H bond. This effect is most prominent for BaH4, where the precompression of H2δ- units at 50 GPa results in bond lengths comparable to that of pure H2 above 275 GPa.

Superconductivity up to 243 K in the yttrium-hydrogen system under high pressure.

The discovery of superconducting H3S with a critical temperature Tc∼200 K opened a door to room temperature superconductivity and stimulated further extensive studies of hydrogen-rich compounds stabilized by high pressure. Here, we report a comprehensive study of the yttrium-hydrogen system with the highest predicted Tcs among binary compounds and discuss the contradictions between different theoretical calculations and experimental data. We synthesized yttrium hydrides with the compositions of YH3, YH4, YH6 and YH9 in a diamond anvil cell and studied their crystal structures, electrical and magnetic transport properties, and isotopic effects. We found superconductivity in the Im-3m YH6 and P63/mmc YH9 phases with maximal Tcs of ∼220 K at 183 GPa and ∼243 K at 201 GPa, respectively. Fm-3m YH10 with the highest predicted Tc > 300 K was not observed in our experiments, and instead, YH9 was found to be the hydrogen-richest yttrium hydride in the studied pressure and temperature range up to record 410 GPa and 2250 K.

High-pressure phase transition of AB3-type compounds: case of tellurium trioxide.

Tellurium trioxide, TeO3, is the only example of a trioxide adopting at ambient conditions the VF3-type structure (a distorted variant of the cubic ReO3 structure). Here we present a combined experimental (Raman scattering) and theoretical (DFT modelling) study on the influence of high pressure (exceeding 100 GPa) on the phase stability of this compound. In experiments the ambient-pressure VF3-type structure (R3̄c symmetry) is preserved up to 110 GPa. In contrast, calculations indicate that above 66 GPa the R3̄c structure should transform to a YF3-type polymorph (Pnma symmetry) with the coordination number of Te6+ increasing from 6 to 8 upon the transition. The lack of this transition in the room-temperature experiment is most probably connected with energetic barriers, in analogy to what is found for compressed WO3. The YF3-type phase is predicted to be stable up to 220 GPa when it should transform to a novel structure of R3̄ symmetry and Z = 18. We analyse the influence of pressure on the band gap of TeO3, and discuss the present findings in the context of structural transformations of trioxides and trifluorides adopting an extended structure in the solid state.

Hydrogen solubility in cristobalite at high pressure.

Powder samples of cristobalite-I are loaded with hydrogen at pressures up to 90 kbar and T = 250 °C and quenched under pressure to the liquid N2 temperature. The quenched samples are examined at ambient pressure by X-ray diffraction, Raman spectroscopy, and thermal desorption analysis. The hydrogen content of the samples is found to increase with pressure and reach a molecular ratio of H2/SiO2 ∼ 0.10 at P = 90 kbar. At ambient pressure, the samples consist of a mixture of approximately 80% cristobalite-I phase and 20% cristobalite-II-like phase, the crystal lattices of both phases being slightly expanded due to the hydrogen uptake. According to Raman spectroscopy, the hydrogen is dissolved in these phases in the form of H2 molecules.

Hydrogen solubility in amorphous silica at pressures up to 75 kbar.

The solubility of hydrogen in amorphous silica at a temperature of 250 °C and pressures up to 75 kbar is studied using a quenching technique. The molar ratio H(2)/SiO(2) is found to linearly increase with pressure from X = 0.16 at P = 6 kbar to X = 0.53 at P = 75 kbar. An investigation of a sample with X = 0.47 by Raman spectroscopy demonstrated that hydrogen dissolves in silica in the form of H(2) molecules, and these molecules occupy voids of, at least, two different types in the silica network. An X-ray diffraction study showed that the hydrogen molecules penetrating in the silica glass network prevented its irreversible densification occurring if the silica glass is compressed to the same pressure without hydrogen.