Stishovite's Relative: A Post‐Coesite Form of Phosphorus Oxonitride

Phosphorus oxonitride (PON) is isoelectronic with SiO₂ and may exhibit a similar broad spectrum of intriguing properties as silica. However, PON has only been sparsely investigated under high‐pressure conditions and there has been no evidence on a PON polymorph with a coordination number of P greater than 4. Herein, we report a post‐coesite (pc) PON polymorph exhibiting a stishovite‐related structure with P in a (5+1) coordination. The pc‐PON was synthesized using the multianvil technique and characterized by powder X‐ray diffraction, solid‐state NMR spectroscopy, TEM measurements and in situ synchrotron X‐ray diffraction in diamond anvil cells. The structure model was verified by single‐crystal X‐ray diffraction at 1.8 GPa and the isothermal bulk modulus of pc‐PON was determined to K₀=163(2) GPa. Moreover, an orthorhombic PON polymorph (o‐PON) was observed under high‐pressure conditions and corroborated as the stable modification at pressures above 17 GPa by DFT calculations.     

Equation of State and Crystal Structure of NaAlSiO 4 with Calcium-Ferrite Type Structure in the Conditions of the Lower Mantle

The full profile refinement of the structure of the calcium-ferrite type NaAlSiO 4 was carried out at pressures up to 40 GPa. This high-pressure modification of NaAlSiO 4 is known to be stable at least to 75 GPa and 2450 K that corresponds to a middle part of the Earth's lower mantle. A zero-pressure unit cell volume V 0 =36.58(2) cm 3 /mol was obtained from a sample synthesized from natural albite. In situ pressure-volume data (with found V 0 ) was fitted to the Birch-Murnaghan equation of state, and it yielded the bulk modulus equal to 220(1) GPa and its pressure derivative equal to 4.1(1).     

High-pressure and high-temperature polymorphism in silica

We synthesised a number of new silica modifications in the electrically heated diamond anvil cells at pressures over 100 GPa and temperatures over 1200 K. The structure of these polymorphs is based on hexagonal close packing of oxygen atoms with different degree of ordering of silicon atoms in octahedral and tetrahedral sites.     

Beating the miscibility barrier between iron group elements and magnesium by high-pressure alloying

Iron and magnesium are almost immiscible at ambient pressure. The low solubility of Mg in Fe is due to a very large size mismatch between the alloy components. However, the compressibility of Mg is much higher than that of Fe, and therefore the difference in atomic sizes between elements decreases dramatically with pressure. Based on the predictions of ab initio calculations, we demonstrate in a series of experiments in a multianvil apparatus and in electrically and laser-heated diamond anvil cells that high pressure promotes solubility of magnesium in iron. At the megabar pressure range, more than 10 at. % of Mg can dissolve in Fe and then the alloy can be quenched to ambient conditions. A generality of the concept of high-pressure alloying between immiscible elements is demonstrated by its application to two other Fe group elements, Co and Ni.     

Pressure-induced Invar effect in Fe-Ni alloys

We have measured the pressure-volume (P-V) relations for cubic iron-nickel alloys for three different compositions: Fe 0.64Ni (0.36), Fe 0.55Ni (0.45), and Fe 0.20Ni (0.80). It is observed that for a certain pressure range the bulk modulus does not change or can even decrease to some minimum value, after which it begins to increase under still higher pressure. In our experiment, we observe for the first time a new effect, namely, that the Fe-Ni alloys with high Ni concentrations, which show positive thermal expansion at ambient pressure, become Invar system upon compression over a certain pressure range.     

Noblest of all metals is structurally unstable at high pressure

In a series of experiments in externally electrically heated diamond anvil cells we demonstrate that at pressures above approximately 240 GPa gold adopts a hexagonal-close-packed structure. Ab initio calculations predict that at pressures about 250 GPa different stacking sequences of close-packed atomic layers in gold become virtually degenerate in energy, strongly supporting the experimental observations.     

Stabilization Of The CN35− Anion In Recoverable High-pressure Ln3O2(CN3) (Ln=La,Eu, Gd,Tb, Ho,Yb) Oxoguanidinates

A series of isostructural Ln₃O₂(CN₃) (Ln=La, Eu, Gd, Tb, Ho, Yb) oxoguanidinates was synthesized under high-pressure (25–54 GPa) high-temperature (2000–3000 K) conditions in laser-heated diamond anvil cells. The crystal structure of this novel class of compounds was determined via synchrotron single-crystal X-ray diffraction (SCXRD) as well as corroborated by X-ray absorption near edge structure (XANES) measurements and density functional theory (DFT) calculations. The Ln₃O₂(CN₃) solids are composed of the hitherto unknown CN₃⁵⁻ guanidinate anion—deprotonated guanidine. Changes in unit cell volumes and compressibility of Ln₃O₂(CN₃) (Ln=La, Eu, Gd, Tb, Ho, Yb) compounds are found to be dictated by the lanthanide contraction phenomenon. Decompression experiments show that Ln₃O₂(CN₃) compounds are recoverable to ambient conditions. The stabilization of the CN₃⁵⁻ guanidinate anion at ambient conditions provides new opportunities in inorganic and organic synthetic chemistry.