| 1. |
- Aslandukov, Andrey, et al.
(author)
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Anionic N18 Macrocycles and a Polynitrogen Double Helix in Novel Yttrium Polynitrides YN6 and Y2N11 at 100 GPa
- 2022
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In: Angewandte Chemie International Edition. - Weinheim, Germany : Wiley-VCH Verlagsgesellschaft. - 1433-7851 .- 1521-3773. ; 61:34
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Journal article (peer-reviewed)abstract
- Two novel yttrium nitrides, YN6 and Y2N11, were synthesized by direct reaction between yttrium and nitrogen at 100 GPa and 3000 K in a laser-heated diamond anvil cell. High-pressure synchrotron single-crystal X-ray diffraction revealed that the crystal structures of YN6 and Y2N11 feature a unique organization of nitrogen atoms-a previously unknown anionic N-18 macrocycle and a polynitrogen double helix, respectively. Density functional theory calculations, confirming the dynamical stability of the YN6 and Y2N11 compounds, show an anion-driven metallicity, explaining the unusual bond orders in the polynitrogen units. As the charge state of the polynitrogen double helix in Y2N11 is different from that previously found in Hf2N11 and because N-18 macrocycles have never been predicted or observed, their discovery significantly extends the chemistry of polynitrides.
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| 2. |
- Aslandukov, Andrey, et al.
(author)
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Domain Auto Finder (DAFi) program : the analysis of single-crystal X-ray diffraction data from polycrystalline samples
- 2022
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In: Journal of applied crystallography. - : Wiley-Blackwell Publishing Ltd.. - 0021-8898 .- 1600-5767. ; 55, s. 1383-1391
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Journal article (peer-reviewed)abstract
- This paper presents the Domain Auto Finder (DAFi) program and its application to the analysis of single-crystal X-ray diffraction (SC-XRD) data from multiphase mixtures of microcrystalline solids and powders. Superposition of numerous reflections originating from a large number of single-crystal domains of the same and/or different (especially unknown) phases usually precludes the sorting of reflections coming from individual domains, making their automatic indexing impossible. The DAFi algorithm is designed to quickly find subsets of reflections from individual domains in a whole set of SC-XRD data. Further indexing of all found subsets can be easily performed using widely accessible crystallographic packages. As the algorithm neither requires a priori crystallographic information nor is limited by the number of phases or individual domains, DAFi is powerful software to be used for studies of multiphase polycrystalline and microcrystalline (powder) materials. The algorithm is validated by testing on X-ray diffraction data sets obtained from real samples: a multi-mineral basalt rock at ambient conditions and products of the chemical reaction of yttrium and nitrogen in a laser-heated diamond anvil cell at 50 GPa. The high performance of the DAFi algorithm means it can be used for processing SC-XRD data online during experiments at synchrotron facilities.
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| 3. |
- Bykova, Elena, et al.
(author)
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Novel Class of Rhenium Borides Based on Hexagonal Boron Networks Interconnected by Short B-2 Dumbbells
- 2022
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In: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 34:18, s. 8138-8152
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Journal article (peer-reviewed)abstract
- Transition metal borides are known due to their attractive mechanical, electronic, refractive, and other properties. A new class of rhenium borides was identified by synchrotron single-crystal X-ray diffraction experiments in laser-heated diamond anvil cells between 26 and 75 GPa. Recoverable to ambient conditions, compounds rhenium triboride (ReB3) and rhenium tetraboride (ReB4) consist of close-packed single layers of rhenium atoms alternating with boron networks built from puckered hexagonal layers, which link short bonded (similar to 1.7 angstrom) axially oriented B-2 dumbbells. The short and incompressible Re-B and B-B bonds oriented along the hexagonal c-axis contribute to low axial compressibility comparable with the linear compressibility of diamond. Sub-millimeter samples of ReB3 and ReB4 were synthesized in a large-volume press at pressures as low as 33 GPa and used for material characterization. Crystals of both compounds are metallic and hard (Vickers hardness, H-V = 34(3) GPa). Geometrical, crystal-chemical, and theoretical analysis considerations suggest that potential ReBx compounds with x > 4 can be based on the same principle of structural organization as in ReB3 and ReB4 and possess similar mechanical and electronic properties.
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| 4. |
- Bykova, Elena, et al.
(author)
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Synthesis, crystal structure, and properties of stoichiometric hard tungsten tetraboride, WB4
- 2022
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In: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 10:37, s. 20111-20120
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Journal article (peer-reviewed)abstract
- Tungsten tetraboride has been known so far as a non-stoichiometric compound with a variable composition (e.g. WB4-x, WB4+x). Its mechanical properties could exceed those of hard tungsten carbide, which is widely used nowadays in science and technology. The existence of stoichiometric WB4 has not been proven yet, and its structure and crystal chemistry remain debatable to date. Here we report the synthesis of single crystals of the stoichiometric WB4 phase under high-pressure high-temperature conditions. The crystal structure of WB4 was determined using synchrotron single-crystal X-ray diffraction. In situ high-pressure compressibility measurements show that the bulk modulus of WB4 is 238.6(2) GPa for B = 5.6(0). Measurements of mechanical properties of bulk polycrystalline sub-millimeter size samples under ambient conditions reveal a hardness of similar to 36 GPa, confirming that the material falls in the category of superhard materials.
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| 5. |
- Dong, Weiwei, et al.
(author)
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Fe0.79Si0.07B0.14 metallic glass gaskets for high-pressure research beyond 1 Mbar
- 2022
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In: Journal of Synchrotron Radiation. - : Wiley-Blackwell Publishing Ltd. - 0909-0495 .- 1600-5775. ; 29, s. 1167-1179
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Journal article (peer-reviewed)abstract
- A gasket is an important constituent of a diamond anvil cell (DAC) assembly, responsible for the sample chamber stability at extreme conditions for X-ray diffraction studies. In this work, we studied the performance of gaskets made of metallic glass Fe0.79Si0.07B0.14 in a number of high-pressure X-ray diffraction (XRD) experiments in DACs equipped with conventional and toroidal-shape diamond anvils. The experiments were conducted in either axial or radial geometry with X-ray beams of micrometre to sub-micrometre size. We report that Fe0.79Si0.07B0.14 metallic glass gaskets offer a stable sample environment under compression exceeding 1 Mbar in all XRD experiments described here, even in those involving small-molecule gases (e.g. Ne, H-2) used as pressure-transmitting media or in those with laser heating in a DAC. Our results emphasize the materials importance for a great number of delicate experiments conducted under extreme conditions. They indicate that the application of Fe0.79Si0.07B0.14 metallic glass gaskets in XRD experiments for both axial and radial geometries substantially improves various aspects of megabar experiments and, in particular, the signal-to-noise ratio in comparison to that with conventional gaskets made of Re, W, steel or other crystalline metals.
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| 6. |
- Dubrovinsky, Leonid, et al.
(author)
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Materials synthesis at terapascal static pressures
- 2022
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In: Nature. - London, United Kingdom : Nature Publishing Group. - 0028-0836 .- 1476-4687. ; 605:7909, s. 274-278
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Journal article (peer-reviewed)abstract
- Theoretical modelling predicts very unusual structures and properties of materials at extreme pressure and temperature conditions(1,2). Hitherto, their synthesis and investigation above 200 gigapascals have been hindered both by the technical complexity of ultrahigh-pressure experiments and by the absence of relevant in situ methods of materials analysis. Here we report on a methodology developed to enable experiments at static compression in the terapascal regime with laser heating. We apply this method to realize pressures of about 600 and 900 gigapascals in a laser-heated double-stage diamond anvil cell(3), producing a rhenium-nitrogen alloy and achieving the synthesis of rhenium nitride Re7N3-which, as our theoretical analysis shows, is only stable under extreme compression. Full chemical and structural characterization of the materials, realized using synchrotron single-crystal X-ray diffraction on microcrystals in situ, demonstrates the capabilities of the methodology to extend high-pressure crystallography to the terapascal regime.
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| 7. |
- Gorelova, Liudmila, et al.
(author)
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Edge-sharing BO4 tetrahedra and penta-coordinated silicon in the high-pressure modification of NaBSi3O8
- 2022
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In: Inorganic Chemistry Frontiers. - : ROYAL SOC CHEMISTRY. - 2052-1545 .- 2052-1553. ; 9:8, s. 1735-1742
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Journal article (peer-reviewed)abstract
- The high-pressure behavior of the borosilicate reedmergnerite NaBSi3O8 has been studied using in situ single-crystal X-ray diffraction and Raman spectroscopy up to 35 GPa. The crystal structure of NaBSi3O8 contracts homogeneously upon compression up to 12 GPa, while at higher pressures it undergoes two phase transitions. Above 16 GPa the unit-cell volume is doubled, whereas the coordination numbers of all cations and the structural topology are preserved. Above 25 GPa the crystal structure of NaBSi3O8 contains extremely rare dimers of edge-sharing BO4 tetrahedra and earlier unknown Si2O5 groups consisting of edge-sharing SiO5 square pyramids. The structural model was corroborated by DFT calculations. This HP modification results in the first example of a borosilicate compound with edge-sharing BO4 tetrahedra.
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| 8. |
- Khandarkhaeva, Saiana, et al.
(author)
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Structural Diversity of Magnetite and Products of Its Decomposition at Extreme Conditions
- 2022
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In: Inorganic Chemistry. - : AMER CHEMICAL SOC. - 0020-1669 .- 1520-510X. ; 61:2, s. 1091-1101
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Journal article (peer-reviewed)abstract
- Magnetite, Fe3O4, is the oldest known magnetic mineral and archetypal mixed-valence oxide. Despite its recognized role in deep Earth processes, the behavior of magnetite at extreme high-pressure high-temperature (HPHT) conditions remains insufficiently studied. Here, we report on single-crystal synchrotron X-ray diffraction experiments up to similar to 80 GPa and 5000 K in diamond anvil cells, which reveal two previously unknown Fe3O4 polymorphs, gamma-Fe3O4 with the orthorhombic Yb3S4-type structure and delta-Fe3O4 with the modified Th3P4-type structure. The latter has never been predicted for iron compounds. The decomposition of Fe3O4 at HPHT conditions was found to result in the formation of exotic phases, Fe5O7 and Fe25O32, with complex structures. Crystal-chemical analysis of iron complex Crystal-chemical analysis oxides suggests the high-spin to low-spin crossover in octahedrally coordinated Fe3+ in the pressure interval between 43 and 51 GPa. Our experiments demonstrate that HPHT conditions promote the formation of ferric-rich Fe-O compounds, thus arguing for the possible involvement of magnetite in the deep oxygen cycle.
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| 9. |
- Khandarkhaeva, Saiana, et al.
(author)
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Testing the performance of secondary anvils shaped with focused ion beam from the single-crystal diamond for use in double-stage diamond anvil cells
- 2022
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In: Review of Scientific Instruments. - : AIP Publishing. - 0034-6748 .- 1089-7623. ; 93:3
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Journal article (peer-reviewed)abstract
- The success of high-pressure research relies on the inventive design of pressure-generating instruments and materials used for their construction. In this study, the anvils of conical frustum or disk shapes with flat or modified culet profiles (toroidal or beveled) were prepared by milling an Ia-type diamond plate made of a (100)-oriented single crystal using the focused ion beam. Raman spectroscopy and synchrotron x-ray diffraction were applied to evaluate the efficiency of the anvils for pressure multiplication in different modes of operation: as single indenters forced against the primary anvil in diamond anvil cells (DACs) or as pairs of anvils forced together in double-stage DACs (dsDACs). All types of secondary anvils performed well up to about 250 GPa. The pressure multiplication factor of single indenters appeared to be insignificantly dependent on the shape of the anvils and their culets profiles. The enhanced pressure multiplication factor found for pairs of toroidally shaped secondary anvils makes this design very promising for ultrahigh-pressure experiments in dsDACs.
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| 10. |
- Laniel, Dominique, et al.
(author)
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A reentrant phase transition and a novel polymorph revealed in high-pressure investigations of CF4 up to 46.5 GPa
- 2022
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In: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 156:4
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Journal article (peer-reviewed)abstract
- The high-pressure behavior of simple molecular systems, devoid of strong intermolecular interactions, provides a unique avenue toward a fundamental understanding of matter. Tetrahalides of the carbon group elements (group 14), lacking all intermolecular interactions but van der Waals, are among the most elementary of molecular compounds. Here, we report the investigation of CF4 up to 46.5 GPa-the highest pressure up to which any tetrahalides of group 14 elements have been studied so far-by a combination of single-crystal x-ray diffraction (SC-XRDp), Raman spectroscopy, and ab initio calculations. These measurements reveal a pressure-induced reentrant phase transition (phase II phase III phase IIR) Room temperature and the formation of a previously unknown CF4 cubic polymorph, named phase IV, after the laser heating of CF4 at 46.5 GPa. In this work, the structures of phases II(R), III, and IV were solved and the atomic coordinates were refined on the basis of SC-XRDp. A comparison of tetrahalides of group 14 elements underlines that reducing the intermolecular halogen-halogen distances leads to a structural rearrangement from close packing of the tetrahedral molecules to close packing of the halogen atoms.
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