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At high pressures, autoionization – along with polymerization and metallization – is one of the responses of simple molecular systems to a rise in electron density. Nitrosonium nitrate (NO+NO3−), known for this property, has attracted a large interest in recent decades and was reported to be synthesized at high pressure and high temperature from a variety of nitrogen–oxygen precursors, such as N2O4, N2O and N2–O2 mixtures. However, its structure has not been determined unambiguously. Here, we present the first structure solution and refinement for nitrosonium nitrate on the basis of single-crystal X-ray diffraction at 7.0 and 37.0 GPa. The structure model (P21/m space group) contains the triple-bonded NO+ cation and the NO3− sp2-trigonal planar anion. Remarkably, crystal-chemical considerations and accompanying density-functional-theory calculations show that the oxygen atom of the NO+ unit is positively charged – a rare occurrence when in the presence of a less-electronegative element.
The complete elastic stiffness tensor of thiourea has been determined from thermal diffuse scattering (TDS) using high-energy photons (100 keV). Comparison with earlier data confirms a very good agreement of the tensor coefficients. In contrast with established methods to obtain elastic stiffness coefficients (e.g. Brillouin spectroscopy, inelastic X-ray or neutron scattering, ultrasound spectroscopy), their determination from TDS is faster, does not require large samples or intricate sample preparation, and is applicable to opaque crystals. Using high-energy photons extends the applicability of the TDS-based approach to organic compounds which would suffer from radiation damage at lower photon energies.
Tetra-auricupride, ideally AuCu, represents the only species showing the coexistence of Au with an elevated level of Pt, as in the case of a detrital grain studied structurally for the first time, from an ophiolite-associated placer at Bolshoy Khailyk, western Sayans, Russia. We infer that tetra-auricupride can incorporate as much as ~30 mol. % of a “PtCu” component, apparently without significant modification of the unit cell. The unit-cell parameters of platiniferous tetra-auricupride are: a 2.790(1) Å, c 3.641(4) Å, with c/a = 1.305, which are close to those reported for ordered AuCu(I) in the system Au–Cu, and close also to the cell parameters of tetraferroplatinum (PtFe), which both appear to crystallize in the same space group, P4/mmm. These intermetallic compounds and natural alloys are thus isostructural. The closeness of their structures presumably allows Pt to replace Au atoms so readily. The high extent of Cu + Au enrichment is considered to be a reflection of geochemical evolution and buildup in levels of the incompatible Cu and Au with subordinate Pt in a remaining volume of melt at low levels of fO2 and fS2 in the system.
The synthesis of polynitrogen compounds is of fundamental importance due to their potential as environmentally-friendly high energy density materials. Attesting to the intrinsic difficulties related to their formation, only three polynitrogen ions, bulk stabilized as salts, are known. Here, magnesium and molecular nitrogen are compressed to about 50 GPa and laser-heated, producing two chemically simple salts of polynitrogen anions, MgN4 and Mg2N4. Single-crystal X-ray diffraction reveals infinite anionic polythiazyl-like 1D N-N chains in the crystal structure of MgN4 and cis-tetranitrogen N44− units in the two isosymmetric polymorphs of Mg2N4. The cis-tetranitrogen units are found to be recoverable at atmospheric pressure. Our results respond to the quest for polynitrogen entities stable at ambient conditions, reveal the potential of employing high pressures in their synthesis and enrich the nitrogen chemistry through the discovery of other nitrogen species, which provides further possibilities to design improved polynitrogen arrangements.
This article reviews the most recent results concerning second harmonic generation (SHG) experiments of non-phase matchable and phase matchable powder samples at high pressures and explains the pressure dependence of the intensity of the SHG signal by correlating it to the ratio between the average coherence length and the average particle size. The examples discussed here include pressure-induced structural changes in quartz, ZnO, ice VII and KIO3. It is shown that the second harmonic generation technique is a unique tool for the detection of pressure-induced structural phase transitions. It is laboratory based and allows fast measurements. It is complementary to X-ray diffraction and provides additional information about the presence of an inversion center for unknown or controversially discussed structures at high pressure.