High-pressure reactions between the pnictogens: the rediscovery of BiN.

We explore chemical reactions within pnictogens with an example of bismuth and nitrogen under extreme conditions. Understanding chemical reactions between Bi and N, elements representing the first and the last stable elements of the nitrogen group, and the physical properties of their compounds under ambient and high pressure is far from being complete. Here, we report the high-pressure high-temperature synthesis of orthorhombic Pbcn BiN (S.G. #60) from Bi and N2 precursors at pressures above 40 GPa. Using synchrotron single-crystal X-ray diffraction on the polycrystalline sample, we solved and refined the compound's structure and studied its behavior and compressibility on decompression to ambient pressure. We confirm the stability of Pbcn BiN to pressures as low as 12.5(4) GPa. Below that pressure value, a group-subgroup phase transformation occurs, resulting in the formation of a non-centrosymmetric BiN solid with a space group Pca21 (S.G. #29). We use ab initio calculations to characterize the polymorphs of BiN. They also provide support and explanation for our experimental observations, in particular those corresponding to peculiar Bi-N bond evolution under pressure, resulting in a change in the coordination numbers of Bi and N as a function of pressure within the explored stability field of Pbcn BiN.

Sub-micrometer focusing setup for high-pressure crystallography at the Extreme Conditions beamline at PETRA†III.

Scientific tasks aimed at decoding and characterizing complex systems and processes at high pressures set new challenges for modern X-ray diffraction instrumentation in terms of X-ray flux, focal spot size and sample positioning. Presented here are new developments at the Extreme Conditions beamline (P02.2, PETRA III, DESY, Germany) that enable considerable improvements in data collection at very high pressures and small scattering volumes. In particular, the focusing of the X-ray beam to the sub-micrometer level is described, and control of the aberrations of the focusing compound refractive lenses is made possible with the implementation of a correcting phase plate. This device provides a significant enhancement of the signal-to-noise ratio by conditioning the beam shape profile at the focal spot. A new sample alignment system with a small sphere of confusion enables single-crystal data collection from grains of micrometer to sub-micrometer dimensions subjected to pressures as high as 200 GPa. The combination of the technical development of the optical path and the sample alignment system contributes to research and gives benefits on various levels, including rapid and accurate diffraction mapping of samples with sub-micrometer resolution at multimegabar pressures.

Hexagonal Layered Polymeric Nitrogen Phase Synthesized near 250 GPa.

The nitrogen triple bond dissociates in the 100 GPa pressure range and a rich variety of single-bonded polymeric nitrogen structures unique to this element have been predicted up to the terapascal pressure range. The nonmolecular cubic-gauche (cg-N) structure was first observed above 110 GPa, coupled to high temperature (>2000 K) to overcome the kinetic barrier. A mixture of cg-N with a layered phase was afterwards reported between 120 and 180 GPa. Here, by laser heating pure nitrogen from 180 GPa, a sole crystalline phase is characterized above 240 GPa while an amorphous transparent phase is obtained at pressures below. X-ray diffraction and Raman vibrational data reveal a tetragonal lattice (P4_{2}bc) that matches the predicted hexagonal layered polymeric nitrogen (HLP-N) structure. Density-functional theory calculations which include the thermal and dispersive interaction contributions are performed to discuss the stability of the HLP-N structure.

High-Pressure Synthesized Lithium Pentazolate Compound Metastable under Ambient Conditions.

Polynitrogen compounds have been actively pursued driven by their potential as ultra-high-performing propellants or explosives. Despite remarkable breakthroughs over the past two decades, the two figures of merit for a compelling material, namely a large fraction of nitrogen by weight and a bulk stability under ambient conditions, have not yet been achieved. We report the synthesis of a lithium pentazolate solid by compressing and laser-heating lithium embedded in molecular N2 around 45 GPa along with its recovery under ambient conditions. The observation by Raman spectroscopy of vibrational modes unique to the cyclo-N5- anion is the signature of the formation of LiN5. Mass spectroscopy experiments confirm the presence of the pentazolate anion in the recovered compound. A monoclinic lattice is obtained from X-ray diffraction measurements and the volume of the LiN5 compound under pressure is in good agreement with the theoretical calculations.

Pressure-induced chemical reactions in the N2(H2)2 compound: from the N2 and H2 species to ammonia and back down into hydrazine.

Theory predicts a very rich high pressure chemistry of hydronitrogens with the existence of many NxHy compounds. The stability of these phases under pressure is being investigated by the compression of N2-H2 mixtures of various compositions. A previous study had disclosed a eutectic-type N2-H2 phase diagram with two stoichiometric van der Waals compounds: (N2)6(H2)7 and N2(H2)2. The structure and pressure induced chemistry of the (N2)6(H2)7 compound have already been investigated. Here, we determine the structure of the N2(H2)2 compound and characterize using Raman spectroscopy measurements the chemical changes under a pressure cycle up to 60 GPa and back to ambient conditions. A N2(H2)2 single crystal was grown from a 1 : 2 N2-H2 mixture and its crystalline structure was solved using synchrotron X-ray diffraction. Similar to the (N2)6(H2)7 solid, N2(H2)2 has a remarkable host-guest structure containing N2 molecules orientationally disordered with spherical, ellipsoidal and planar shapes. Above 50 GPa, N2(H2)2 was found to undergo a chemical reaction. The reaction products were determined to be of the azane family, with NH3 as the main constituent, along with molecular nitrogen. Upon pressure decrease, the reaction products are found to react in such a way that below 10 GPa, hydrazine is the sole azane detected. Observed down to the opening of the diamond anvil cell, the formation of metastable hydrazine instead of the energetically favorable ammonia is puzzling and remains to be elucidated. That could change the current view of Jovian planets' atmospheres in which ammonia is assumed the only stable hydronitrogen molecule.

[Difficulties in the radiologic diagnosis of mono-cortical mandibular fractures. Apropos of 2 cases]. / Difficultés de diagnostic radiologique des fractures mandibulaires mono-corticales. A propos de deux cas.

The authors report two cases of mono-cortical fractures of the mandible. The initial radio-clinical discordance required tomographies for the diagnosis. With regard to these fractures, few described in the literature and whose treatment is simple, the authors insist upon the medico-legal value of radiological pictures.