High-Pressure Synthesis of a Pentazolate Salt

The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N5-, which is achieved by compressing and laser heating cesium azide (CsN3) mixed with N2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN5). Electron transfer from Cs atoms to N5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN5 crystal. This work provides a critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species

A study of tantalum pentoxide Ta2O5 structures up to 28 GPa

Tantalum pentoxide Ta2O5 with the orthorhombic L-Ta2O5 structure has been experimentally studied up to 28.3 GPa (at ambient temperature) using synchrotron angle-dispersive powder X-ray diffraction (XRD). The ambient pressure phase remains stable up to 25 GPa where with increased pressure a crystalline to amorphous phase transition occurs. A detailed equation of state (EOS), including pressure dependent lattice parameters, is reported. The results of this study were compared with a previous high-pressure XRD study by Li et al. A clear discrepancy between the ambient-pressure crystal structures and, consequently, the reported EOSs between the two studies was revealed. The origin of this discrepancy is attributed to two different crystal structures used to index the XRD patterns

Anharmonicity-induced isostructural phase transition of Zirconium under pressure

We have performed a detailed x-ray diffraction structural study of Zr under pressure and unambiguously identify the existence of a first-order isostructural bcc-to-bcc phase transition near 58 GPa. First-principles quantum molecular dynamics lattice dynamics calculations support the existence of this phase transition, in excellent agreement with experimental results, triggered by anharmonic effects. Our results highlight the potential ubiquity of anharmonically driven isostructural transitions within the periodic table under pressure and calls for follow-up experimental and theoretical studies

Synthesis of sodium polyhydrides at high pressures.

The only known compound of sodium and hydrogen is archetypal ionic NaH. Application of high pressure is known to promote states with higher atomic coordination, but extensive searches for polyhydrides with unusual stoichiometry have had only limited success in spite of several theoretical predictions. Here we report the first observation of the formation of polyhydrides of Na (NaH3 and NaH7) above 40 GPa and 2,000 K. We combine synchrotron X-ray diffraction and Raman spectroscopy in a laser-heated diamond anvil cell and theoretical random structure searching, which both agree on the stable structures and compositions. Our results support the formation of multicenter bonding in a material with unusual stoichiometry. These results are applicable to the design of new energetic solids and high-temperature superconductors based on hydrogen-rich materials.High pressure experiments were supported by DOE/BES under contracts No. DE-FG02- 02ER45955 and DE-FG02-99ER45775. DuckYoung Kim and T. Muramatsu acknowledge salary support by Energy Frontier Research in Extreme Environments Center (EFree), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science under Award Number DE-SC0001057. C. J. Pickard and R. J. Needs were supported by the Engineering and Physical Sciences Research Council (EPSRC) of the UK. E. Stavrou and A. F. Goncharov acknowledge support of DARPA under contracts No. W31P4Q1310005 and No. W31P4Q1210008. A. F. Goncharov acknowledges support of NSFC (No. 21473211). Portions of this work were performed at GeoSoilEnviroCARS (Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation - Earth Sciences (EAR-1128799) and Department of Energy - Geosciences (DE-FG02- 94ER14466). Use of the Advanced Photon Source was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.This is the author accepted manuscript. It is currently under an indefinite embargo pending publication by Nature Publishing Group

Equation of State for Natural Almandine, Spessartine, Pyrope Garnet: Implications for Quartz-In-Garnet Elastic Geobarometry

The equation of state (EoS) of a natural almandine74spessartine13pyrope10grossular3 garnet of a typical composition found in metamorphic rocks in Earth’s crust was obtained using single crystal synchrotron X-ray diffraction under isothermal room temperature compression. A third-order Birch-Murnaghan EoS was fitted to P-V data and the results are compared with published EoS for iron, manganese, magnesium, and calcium garnet compositional end-members. This comparison reveals that ideal solid solution mixing can reproduce the EoS for this intermediate composition of garnet. Additionally, this new EoS was used to calculate geobarometry on a garnet sample from the same rock, which was collected from the Albion Mountains of southern Idaho. Quartz-ingarnet elastic geobarometry was used to calculate pressures of quartz inclusion entrapment using alternative methods of garnet mixing and both the hydrostatic and Grunëisen tensor approaches. QuiG barometry pressures overlap within uncertainty when calculated using EoS for pure endmember almandine, the weighted averages of end-member EoS, and the EoS presented in this study. Grunëisen tensors produce apparent higher pressures relative to the hydrostatic method, but with large uncertainties