Single-crystal Synchrotron X-ray Diffraction Research Articles

Direct observation of one-dimensional disordered diffusion channel in a chain-like thermoelectric with ultralow thermal conductivity

Structural disorder, highly effective in reducing thermal conductivity, is important in technological applications such as thermal barrier coatings and thermoelectrics. In particular, interstitial, disordered, diffusive atoms are common in complex crystal structures with ultralow thermal conductivity, but are rarely found in simple crystalline solids. Combining single-crystal synchrotron X-ray diffraction, the maximum entropy method, diffuse scattering, and theoretical calculations, here we report the direct observation of one-dimensional disordered In1+ chains in a simple chain-like thermoelectric InTe, which contains a significant In1+ vacancy along with interstitial indium sites. Intriguingly, the disordered In1+ chains undergo a static-dynamic transition with increasing temperature to form a one-dimensional diffusion channel, which is attributed to a low In1+-ion migration energy barrier along the c direction, a general feature in many other TlSe-type compounds. Our work provides a basis towards understanding ultralow thermal conductivity with weak temperature dependence in TlSe-type chain-like materials.

Structural and vibrational properties of methane up to 71 GPa

Single-crystal synchrotron X-ray diffraction, Raman spectroscopy, and first principles calculations have been used to identify the structure of the high-pressure (HP) phase of molecular methane above 20 GPa up to 71 GPa. The structure of HP phase is trigonal R3, which can be represented as a distortion of the cubic phase B, previously documented at 7-15 GPa and confirmed here. The positions of hydrogen atoms in HP phase have been 19 obtained from first principles calculations. The molecules occupy four different crystallographic sites in phases B and eleven sites in the HP phase, which result in splitting of molecular stretching modes detected in Raman spectroscopy and assigned here based on 22 a good agreement with the Raman spectra calculated from the first principles.

Crystal structure of the high-P polymorph of Ca2B6O6(OH)10·2(H2O) (meyerhofferite)

The crystal structure of the high-pressure polymorph of meyerhofferite, ideally Ca2B6O6(OH)10·2(H2O), has been determined by means of single-crystal synchrotron X-ray diffraction data. Meyerhofferite undergoes a first-order isosymmetric phase transition to meyerhofferite-II, bracketed between 3.15 and 3.75 GPa, with a large volume discontinuity. The phase transition is marked by an increase in the coordination number of the boron B1 site, from III to IV, leading to a more interconnected and less compressible structure. The main structural differences between the two polymorphs and the P-induced deformation mechanisms at the atomic scale are discussed.

High-pressure single-crystal synchrotron X-ray diffraction study of lillianite

Abstract In this paper, high-pressure data from a synchrotron X-ray diffraction study on a lillianite (Pb3Bi2S6) single crystal up to ~21 GPa are presented. A phase transition from lillianite (space group Bbmm, LP lillianite) to the high-pressure form β-Pb3Bi2S6 (space group Pbnm, HP lillianite) was confirmed and bracketed between 4.90 and 4.92 GPa. The transition is reversible but of first-order with a hysteresis of ~2.8 GPa. It showed weak effects of pseudo-merohedral twinning that disappeared upon decompression, testifying to a full recovery of the single crystal of lillianite. This makes lillianite an interesting shape-memory material. With a bulk modulus K4.9 = 78(3) GPa and K′ = 5.1(4), β-Pb3Bi2S6 is markedly less compressible than lillianite [K0 = 44(2) GPa, K′ = 7(1)]. Compressional anisotropy increases markedly in β-Pb3Bi2S6 with compressibility along the b axis [M0b = 130(6) GPa and Mb′ = 19(3) in lillianite, M4.9b = 145(4) GPa and Mb′ = 16.0(7) in β-Pb3Bi2S6] significantly larger than that along the other two axes [M0a = 118(5) GPa, Ma′ = 21(3), M0c = 139(12) GPa, and Mc′ = 31(10) in lillianite, M4.9a = 242(12) GPa, Ma′ = 8(1), M4.9c = 242(5) GPa, and Mc′ = 29(1) in β-Pb3Bi2S6]. The behavior of lillianite at high pressure is an interesting case study in relation to non-quenchable ultrahigh-pressure phases likely occurring in the inner Earth, like post-perovskite MgSiO3, the oxide homologue N = 1 of the lillianite series. The β-Pb3Bi2S6 structure, on the other hand, is the N = 3 homologue of the meneghinite series to which the higher-pressure modification of the post-perovskite structure also belongs (homologue N = 1). This makes the two forms of Pb3Bi2S6 potential equivalents of high- and ultrahigh-pressure Mg silicates that could occur both in the deep earth and in other rocky extrasolar planetary bodies.

Charge Transfer Complexes of 1,3,6-Trinitro-9,10-phenanthrenequinone with Polycyclic Aromatic Compounds.

Understanding the interactions of organic donor and acceptor molecules in binary associates is crucial for design and control of their functions. Herein, we carried out a theoretical study on the properties of charge transfer complexes of 1,3,6-trinitro-9,10-phenanthrenequinone (PQ) with 23 aromatic π-electron donors. Density functional theory (DFT) was employed to obtain geometries, frontier orbital energy levels and amounts of charge transfer in the ground and first excited states. For the most effective donors, namely, dibenzotetrathiafulvalene, pentacene, tetrathiafulvalene, 5,10-dimethylphenazine, and tetramethyl-p-phenylenediamine, the amount of charge transfer in the ground state was shown to be 0.134−0.240 e−. Further, a novel charge transfer complex of PQ with anthracene was isolated in crystalline form and its molecular and crystal structure elucidated by single-crystal synchrotron X-ray diffraction.

Novel High-Pressure Yttrium Carbide γ-Y_{4}C_{5} Containing [C_{2}] and Nonlinear [C_{3}] Units with Unusually Large Formal Charges.

Changes in the bonding of carbon under high pressure leads to unusual crystal chemistry and can dramatically alter the properties of transition metal carbides. In this work, the new orthorhombic polymorph of yttrium carbide, γ-Y_{4}C_{5}, was synthesized from yttrium and paraffin oil in a laser-heated diamond anvil cell at ∼50 GPa. The structure of γ-Y_{4}C_{5} was solved and refined using insitu synchrotron single-crystal x-ray diffraction. It includes two carbon groups: [C_{2}] dimers and nonlinear [C_{3}] trimers. Crystal chemical analysis and density functional theory calculations revealed unusually high noninteger charges ([C_{2}]^{5.2-} and [C_{3}]^{6.8-}) and unique bond orders (<1.5). Our results extend the list of possible carbon states at extreme conditions.

High-Pressure Synthesis of the β-Zn3N2 Nitride and the α-ZnN4 and β-ZnN4 Polynitrogen Compounds.

High-pressure nitrogen chemistry has expanded at a formidable rate over the past decade, unveiling the chemical richness of nitrogen. Here, the Zn-N system is investigated in laser-heated diamond anvil cells by synchrotron powder and single-crystal X-ray diffraction, revealing three hitherto unobserved nitrogen compounds: β-Zn3N2, α-ZnN4, and β-ZnN4, formed at 35.0, 63.5, and 81.7 GPa, respectively. Whereas β-Zn3N2 contains the N3- nitride, both ZnN4 solids are found to be composed of polyacetylene-like [N4]∞2- chains. Upon the decompression of β-ZnN4 below 72.7 GPa, a first-order displacive phase transition is observed from β-ZnN4 to α-ZnN4. The α-ZnN4 phase is detected down to 11.0 GPa, at lower pressures decomposing into the known α-Zn3N2 (space group Ia3̅) and N2. The equations of states of β-ZnN4 and α-ZnN4 are also determined, and their bulk moduli are found to be K0 = 126(9) GPa and K0 = 76(12) GPa, respectively. Density functional theory calculations were also performed and provide further insight into the Zn-N system. Moreover, comparing the Mg-N and Zn-N systems underlines the importance of minute chemical differences between metal cations in the resulting synthesized phases.

An electric field cell for performing in situ single-crystal synchrotron X-ray diffraction.

With the recent increase in research into ferroelectric, anti-ferroelectric and piezoelectric materials, studying the solid-state properties in situ under applied electric fields is vital in understanding the underlying processes. Where this behaviour is the result of atomic displacements, crystallographic insight has an important role. This work presents a sample environment designed to apply an electric field to single-crystal samples in situ on the small-molecule single-crystal diffraction beamline I19, Diamond Light Source (UK). The configuration and operation of the cell is described as well as its application to studies of a proton-transfer colour-change material.

Hydrothermal Syntheses of Uranium Oxide Hydrate Materials with Sm(III) Ions: pH-Driven Diversities in Structures and Morphologies and Sm-Doped Porous Uranium Oxides Derived from Their Thermal Decompositions.

We report the hydrothermal syntheses of three uranyl oxide hydroxy-hydrate (UOH) materials containing Sm(III) ions (UOH-Sm) by controlling the solution pH and a new way to make Sm-doped porous uranium oxides with different U-to-Sm atomic ratios via their thermal decompositions. While layer-structured UOH-Sm phases with U-to-Sm atomic ratios of 1 (UOH-Sm1) and 4 (UOH-Sm2) were obtained from the reaction of schoepite and samarium nitrate with final solution pH values of over 4, similar reactions without pH adjustment with final solution pH values of less than 4 led to the formation of a uranyl oxide framework (UOF-Sm) with a U-to-Sm atomic ratio of 5.5. The crystal structure of compound UOF-Sm was revealed with synchrotron single-crystal X-ray diffraction and confirmed with transmission electron microscopy. The two-dimensional uranyl oxide hydroxide layers, similar to that for β-U3O8, are linked by double pentagonal uranyl polyhedra to form a three-dimensional framework with Sm(III) ions in the channels. Scanning electron microscopy characterization revealed nanoplate crystal morphologies for the two UOH-Sm phases, in contrast to the needle morphology for UOF-Sm. Subsequent thermal treatments led to the formation of Sm-doped uranium oxides, maintaining the original crystal shapes and U-to-Sm ratios but with nanopores. This work demonstrated that the hydrothermal synthesis conditions, especially fine-tuning of the solution pH, have a significant impact on the uranium hydrolysis, thus leading to well-defined products. This will facilitate the targeted syntheses of UOH phases with lanthanide (Ln) ions and explore the subsequent applications of these materials and Ln-doped porous uranium oxides as potential nuclear or functional materials.

High Pressure Behavior of Mascagnite from Single Crystal Synchrotron X-ray Diffraction Data

High-pressure synchrotron X-ray diffraction was carried out on a single crystal of mascagnite, compressed in a diamond anvil cell. The sample maintained its crystal structure up to ~18 GPa. The volume–pressure data were fitted by a third-order Birch–Murnaghan equation of state (BM3-EOS) yielding K0 = 20.4(7) GPa, K’0 = 6.1(2), and V0 = 499(1) Å3, as suggested by the F-f plot. The axial compressibilities, calculated with BM3-EOS, were K0a = 35(3), K’0a = 7.7(7), K0b = 10(3), K’0b = 7(1), K0c = 25(1), and K’0c = 4.3(2) The axial moduli measured using a BM2-EOS and fixing K’0 equal to 4, were K0a = 52(2), K0b = 20 (1), and K0c = 29.6(4) GPa, and the anisotropic ratio of K0a:K0b:K0c = 1:0.4:0.5. The evolution of crystal lattice and geometrical parameters indicated no phase transition until 17.6 GPa. Sulphate polyhedra were incompressible and the density increase of 30% compared to investigated pressure should be attributed to the reduction of weaker hydrogen bonds. In contrast, some of them, directed along [100], were very short at room temperature, below 2 Å, and showed a very low compressibility. This configuration explains the anisotropic compressional behavior and the lowest compressibility of the a axis.

Comparison of the temperature- and pressure-dependent behavior of the crystal structure of CrAs

The crystal structure of CrAs was investigated using synchrotron X-ray single-crystal diffraction for separate dependences on temperature (30–400 K) and on pressure (0–9.46 GPa). The isosymmetrical magnetostructural phase transition at T N = 267 K can induce a change in the microstructure by twinning due to a crossing of the orthohexagonal setting of the unit-cell parameter ratio c/b. Within the crystal structure, one particular Cr–Cr distance exhibits anomalous behavior in that it is nearly unaffected by temperature and pressure in the paramagnetic phase, which is stable above 267 K and at high pressures. The distinction of this shortest Cr–Cr distance might be of importance for the superconducting properties of CrAs.

Hot isostatic pressed pyrochlore glass‐ceramics: Revealing structure insides at the reaction interface

AbstractAs potential waste forms for immobilizing actinide‐rich radioactive wastes, Eu2Ti2O7 (Eu as a surrogate for minor actinides) pyrochlore glass‐ceramics were fabricated via hot isostatic pressing (HIPing) at 1200°C. The structure and microstructure at the reaction interface between the glass‐ceramic waste form and the stainless steel (SS) canister under HIPing conditions were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and synchrotron single crystal X‐ray diffraction (SC‐XRD). The interactions at the reaction interface led to the formations of a ~10‐µm‐thick Cr2O3 layer as the oxidation front of the SS and a layer of a mixed oxide phase (Eu1.25SiCr0.8Ti1.2O7.5) on the glass‐ceramic side of the reaction interface. The crystal structure of such a unique mixed oxide phase was revealed indubitably with a combination of synchrotron SC‐XRD and TEM assisted with a focused ion beam (FIB) SEM system. The improved structural understanding of the reaction interface will help to support the utilization of HIPing as a versatile hot consolidation process for the treatment of radioactive wastes.

Synthesis and Structure of the Bis- and Tris-Polyhedral Hybrid Carboranoclathrochelates with Functionalizing Biorelevant Substituents-The Derivatives of Propargylamine Iron(II) Clathrochelates with Terminal Triple C≡C Bond(s).

A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate precursor with amine N-nucleophiles of different natures in various solvents was performed. One of its two chlorine atoms with morpholine or diethylamine in dichloromethane gave reactive monohalogenoclathrochelate complexes functionalized with abiorelevant substituents. Further nucleophilic substitution of their remaining chlorine atoms with propargylamine in DMF led to morpholine- and diethylamine-functionalized monopropargylamine cage complexes, the molecules of which contain the single terminal C≡C bond. Their “click” 1,3-cycloaddition reactions in toluene with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate gave spacer-containing di- and tritopic iron(II) carboranoclatrochelates formed by a covalent linking between their different polyhedral(cage) fragments. The obtained complexes were characterized using elemental analysis, MALDI-TOF mass, UV-Vis, 1H, 1H{11B}, 11B, 11B{1H}, 19F{1H} and 13C{1H}-NMR spectra, and by a single crystal synchrotron X-ray diffraction experiment for the diethylamine-functionalized iron(II) carboranoclathrochelate. Its encapsulated iron(II) ion is situated almost in the center of the FeN6-coordination polyhedron possessing a geometry intermediate between a trigonal prism and a trigonal antiprism with a distortion angle φ of approximately 28°. Conformation of this hybrid molecule is strongly affected by its intramolecular dihydrogen bonding: a flexibility of the carborane-terminated ribbed substituent allowed the formation of numerous C–H…H–B intramolecular interactions. The H(C) atom of this carborane core also forms the intermolecular C–H…F–B interaction with an adjacent carboranoclathrochelate molecule. The N–H…N intermolecular interaction between the diethylamine group of one hybrid molecule and the heterocyclic five-membered 1H-[1,2,3]-triazolyl fragment of the second molecule of this type caused formation of H-bonded carboranoclathrochelate dimers in the X-rayed crystal.

Potential Skyrmion Host Fe(IO3)3: Connecting Stereoactive Lone-Pair Electron Effects to the Dzyaloshinskii-Moriya Interaction

Magnetic skyrmions, which are topologically distinct magnetic spin textures, are gaining increased attention for their unique physical properties and potential applications in spintronic devices. Here we present a design strategy for skyrmion host candidates based on combinations of magnetic spin, asymmetric building units having stereoactive lone-pair electrons, and polar lattice symmetry. To demonstrate the viability of the proposed rational design principles, we successfully synthesized a Fe(IO3)3 polycrystalline sample and single crystals by using a new simplified low-temperature pathway, which is experimentally feasible for extending materials growth of transition metal iodates. Single crystal X-ray and powder synchrotron X-ray diffraction measurements demonstrated that Fe(IO3)3 crystallizes in the polar chiral hexagonal lattice with space group P63. The combined structural features of the macroscopic electric polarization along the c-axis stemming from the coalignment of the stereoactive lone-pairs of the IO3– trigonal pyramid and the magnetic Fe3+ cation residing on the 3-fold rotation axis were selected to promote asymmetric exchange coupling. We find evidence of a predicted skyrmion phase at 14 K ≤ T ≤ 16 K and 2.5 T ≤ μ0H ≤ 3.2 T driven by a Dzyaloshinskii–Moriya (DM) interaction, a conclusion supported by the appreciable DM exchange and the zero-field spiral antiferromagnetic ground state of Fe(IO3)3 deduced from neutron diffraction experiments. The associated magnetic modulation wavelength of the putative skyrmions is expected to be short ∼18 nm, comparable to the period of the DM-driven incommensurate order. This work links stereoactive lone-pair electron effects to enhanced DM interaction, demonstrating a new approach for chemical guidelines in the search for skyrmionic states of matter.

The crystal structure of a new calcium aluminate phase containing formate

A new calcium aluminate phase containing formate ions was synthesized and its crystal structure determined. This new phase is indicated as M-phase and was firstly observed in Portland cement pastes hydrated in presence of Ca-formate and in excess of water. The crystal structure of the M-phase was successfully solved in the R-3 space group of the trigonal system on the basis of synchrotron X-ray single crystal diffraction data. The structural model was confirmed by Rietveld refinement of the powder diffraction data acquired on the synthesized pure sample. The crystal structure of the M-phase is similar to that of ettringite, being characterized by columns of AlO6 octahedra alternating with groups of three edge-sharing CaO7 polyhedra. The formate ions (HCOO)− share two oxygens with Ca polyhedra and are located in the interspace between the columns. The crystal structure of the M-phase testifies the strong interaction occurring between small organic molecules as formate and the calcium aluminate components of Portland cement.

Synthesis and Compressibility of Novel Nickel Carbide at Pressures of Earth’s Outer Core

We report the high-pressure synthesis and the equation of state (EOS) of a novel nickel carbide (Ni3C). It was synthesized in a diamond anvil cell at 184(5) GPa through a direct reaction of a nickel powder with carbon from the diamond anvils upon heating at 3500 (200) K. Ni3C has the cementite-type structure (Pnma space group, a = 4.519(2) Å, b = 5.801(2) Å, c = 4.009(3) Å), which was solved and refined based on in-situ synchrotron single-crystal X-ray diffraction. The pressure-volume data of Ni3C was obtained on decompression at room temperature and fitted to the 3rd order Burch-Murnaghan equation of state with the following parameters: V0 = 147.7(8) Å3, K0 = 157(10) GPa, and K0′ = 7.8(6). Our results contribute to the understanding of the phase composition and properties of Earth’s outer core.

Phase transition and high-pressure behavior of ulexite, a potential aggregate in radiation-shielding concretes

The high-pressure behavior of ulexite [ideally NaCaB5O6(OH)6·5(H2O)], a B-bearing raw material (with B2O3 ≈ 43 wt%) and a potential B-rich aggregate, has been studied by in-situ single-crystal synchrotron X-ray diffraction up to 9.5 GPa, in order to explore its stability field at high pressure, the anisotropy of its compressional behavior and the deformation mechanisms at the atomic scale. Ulexite undergoes a first-order iso-symmetric phase transition, reconstructive in character, between 6.44 and 7.13 GPa (to the ulexite-II polymorph); the crystal structure of ulexite-II was successfully solved and refined. For the low-P polymorph of ulexite (stable in all the working conditions as aggregate in concretes), the isothermal bulk modulus here obtained is KV0 = 36.9(5) GPa, with a strongly anisotropic compressional pattern (finite-Eulerian principal components of the unit-strain ellipsoid: ε1:ε2:ε3 ∼7:3:1). Ulexite-II also shows a marked anisotropic compressional pattern and with a resulting bulk softening (KV0 = 26(4) GPa).

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-in-garnet elastic geobarometry was used to calculate pressures of quartz inclusion entrapment using alternative methods of garnet mixing and both the hydrostatic and Grüneisen tensor approaches. QuiG barometry pressures overlap within uncertainty when calculated using EoS for pure end-member almandine, the weighted averages of end-member EoS, and the EoS presented in this study. Grüneisen tensors produce apparent higher pressures relative to the hydrostatic method, but with large uncertainties.

Structure Insides at the Reaction Interface Between Pyrochlore Glass-Ceramics and Stainless Steel Canister Under Hot Isostatic Pressing Conditions

As potential waste forms for immobilizing actinide-rich radioactive wastes, Eu2Ti2O7 pyrochlore glass-ceramics were fabricated via hot isostatic pressing (HIPing) at 1200 oC. The structure at the reaction interface between the glass-ceramic waste form and the stainless steel (SS) canister under HIPing conditions were carefully investigated with SEM, TEM and synchrotron single crystal X-ray diffraction (SC-XRD). The interactions at the reaction interface led to the formations of a ∼10 µm thick Cr2O3 layer as the oxidation front of the SS and a layer of a mixed oxide phase (Eu1.25SiCr0.8Ti1.2O7.5) on the glass-ceramic side of the reaction interface. The crystal structure of such a unique mixed oxide phase was revealed indubitably with a combination of synchrotron SC-XRD and TEM assisted with a FIB-SEM system. The improved structural understanding of the reaction interface will help to support the utilization of HIPing as a versatile hot consolidation process for the treatment of radioactive wastes.

Synthesis, crystal structure and structure–property relations of strontium orthocarbonate, Sr2CO4

Carbonates containing CO4 groups as building blocks have recently been discovered. A new orthocarbonate, Sr2CO4 is synthesized at 92 GPa and at a temperature of 2500 K. Its crystal structure was determined by in situ synchrotron single-crystal X-ray diffraction, selecting a grain from a polycrystalline sample. Strontium orthocarbonate crystallizes in the orthorhombic crystal system (space group Pnma) with CO4, SrO9 and SrO11 polyhedra as the main building blocks. It is isostructural to Ca2CO4. DFT calculations reproduce the experimental findings very well and have, therefore, been used to predict the equation of state, Raman and IR spectra, and to assist in the discussion of bonding in this compound.