Atomic and electronic structure transformations in SnS2 at high pressures: a joint single crystal X-ray diffraction and DFT study.

The layered semiconductor SnS2 spurs much interest for both intercalation and optoelectronic applications. Despite the wealth of research in the field of metal dichalcogenides, the structure-property relationship of this compound remains unclear. Here we present a thorough study combining single-crystal X-ray diffraction and DFT calculations on SnS2 in the pressure range 0 < p < 20 GPa.

Ternary rare earth silicides RE2M3Si4 (RE = Sc, Y, Lu; M = Mo, W): crystal structure, coloring and electronic properties.

The ternary compounds Sc2Mo3Si4, Y2Mo3Si4, Lu2Mo3Si4 and Sc2W3Si4 have been synthesized using arc melting and structurally characterized using single crystal X-ray diffraction. The compounds are isostructural with Gd5Si4 but with coloring (order of the rare earth and transition metals) on the Gd site. In contrast to group 4 and 5 ternaries of the same type, we observe no site mixing between the rare earth and transition metals.

Synthesis and decomposition of Li3Na(NH2)4 and investigations of Li-Na-N-H based systems for hydrogen storage.

Previous studies have shown modified thermodynamics of amide-hydride composites by cation substitution, while this work systematically investigates lithium-sodium-amide, Li-Na-N-H, based systems. Li3Na(NH2)4 has been synthesized by combined ball milling and annealing of 3LiNH2-NaNH2 with LiNa2(NH2)3 as a minor by-product. Li3+xNa1-x(NH2)4 releases NaNH2 and forms non-stoichiometric Li3+xNa1-x(NH2)4 before it melts at 234 °C, as observed by in situ powder X-ray diffraction.

Magnetic properties of ball-milled SrFe12O19 particles consolidated by Spark-Plasma Sintering.

The room-temperature magnetic properties of ball-milled strontium hexaferrite particles consolidated by spark-plasma sintering are strongly influenced by the milling time. Scanning electron microscopy revealed the ball-milled SrFe12O19 particles to have sizes varying over several hundred nanometers. X-Ray powder-diffraction studies performed on the ball-milled particles before sintering clearly demonstrate the occurrence of a pronounced amorphization process.

Ammine Calcium and Strontium Borohydrides: Syntheses, Structures, and Properties.

A new series of solvent- and halide-free ammine strontium metal borohydrides Sr(NH3 )n (BH4 )2 (n=1, 2, and 4) and further investigations of Ca(NH3 )n (BH4 )2 (n=1, 2, 4, and 6) are presented. Crystal structures have been determined by powder XRD and optimized by DFT calculations to evaluate the strength of the dihydrogen bonds. Sr(NH3 )(BH4 )2 (Pbcn) and Sr(NH3 )2 (BH4 )2 (Pnc2) are layered structures, whereas M(NH3 )4 (BH4 )2 (M=Ca and Sr; P21 /c) are molecular structures connected by dihydrogen bonds.

A composite of complex and chemical hydrides yields the first Al-based amidoborane with improved hydrogen storage properties.

The first Al-based amidoborane Na[Al(NH2 BH3 )4 ] was obtained through a mechanochemical treatment of the NaAlH4 -4 AB (AB=NH3 BH3 ) composite releasing 4.5 wt % of pure hydrogen. The same amidoborane was also produced upon heating the composite at 70 °C.

Quantitative analysis of intermolecular interactions in orthorhombic rubrene.

Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconducting properties of rubrene to the presence of a large overlap of the extended π-conjugated core between molecules. We present here the electron density distribution in rubrene at 20 K and at 100 K obtained using a combination of high-resolution X-ray and neutron diffraction data.

Demonstration of thin film pair distribution function analysis (tfPDF) for the study of local structure in amorphous and crystalline thin films.

By means of normal-incidence, high-flux and high-energy X-rays, total scattering data for pair distribution function (PDF) analysis have been obtained from thin films (tf), suitable for local structure analysis. By using amorphous substrates as support for the films, the standard Rapid Acquisition PDF setup can be applied and the scattering signal from the film can be isolated from the total scattering data through subtraction of an independently measured background signal. No angular corrections to the data are needed, as would be the case for grazing incidence measurements.

Does the thermal evolution of molecular structures critically affect the magnetic anisotropy?

A dysprosium based single-ion magnet is synthesized and characterized by the angular dependence of the single-crystal magnetic susceptibility. and effective electrostatic analyses are performed using the molecular structures determined from single crystal X-ray diffraction at 20 K, 100 K and 300 K. Contrary to the common assumption, the results reveal that the structural thermal effects that may affect the energy level scheme and magnetic anisotropy below 100 K are negligible.

Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy).

Fourteen solvent- and halide-free ammine rare-earth metal borohydrides M(BH4)3·nNH3, M = Y, Gd, Dy, n = 7, 6, 5, 4, 2, and 1, have been synthesized by a new approach, and their structures as well as chemical and physical properties are characterized. Extensive series of coordination complexes with systematic variation in the number of ligands are presented, as prepared by combined mechanochemistry, solvent-based methods, solid-gas reactions, and thermal treatment. This new synthesis approach may have a significant impact within inorganic coordination chemistry.

High-pressure phase transitions in ordered and disordered Bi2Te2Se.

We report studies of pressure-induced phase transitions of ordered and disordered ternary tetradymite-like Bi2Te2Se by synchrotron powder X-ray diffraction (PXRD) in diamond anvil cells (DACs) for pressures up to 59 and 49 GPa, respectively. The first sample (SB) was prepared from a single crystal with ordered Se/Te sites while the second sample (Q) was prepared from a quenched melt resulting in disordered Se/Te. This allows for an investigation of the effect of disorder on the phase transitions and the equation of states (EoS) of the tetradymite-like α phase.

Structural Evolution of Iron Antimonides from Amorphous Precursors to Crystalline Products Studied by Total Scattering Techniques.

Homogeneous reaction precursors may be used to form several solid-state compounds inaccessible by traditional synthetic routes, but there has been little development of techniques that allow for a priori prediction of what may crystallize in a given material system. Here, the local structures of FeSbx designed precursors are determined and compared with the structural motifs of their crystalline products. X-ray total scattering and atomic pair distribution function (PDF) analysis are used to show that precursors that first nucleate a metastable FeSb3 compound share similar local structure to the product.

Insights on spin polarization through the spin density source function.

Understanding how spin information is transmitted from paramagnetic to non-magnetic centers is crucial in advanced materials research and calls for novel interpretive tools. Herein, we show that the spin density at a point may be seen as determined by a local source function for such density, operating at all other points of space. Integration of the local source over Bader's quantum atoms measures their contribution in determining the spin polarization at any system's location.

Nanoscale Atomic Displacements Ordering for Enhanced Piezoelectric Properties in Lead-Free ABO3 Ferroelectrics.

In situ synchrotron X-ray diffuse scattering and inelastic neutron scattering measurements from a prototype ABO3 ferroelectric single-crystal are used to elucidate how electric fields along a nonpolar direction can enhance its piezoelectric properties. The central mechanism is found to be a nanoscale ordering of B atom displacements, which induces increased lattice instability and therefore a greater susceptibility to electric-field-induced mechanical deformation.

High pressure induced charge transfer in 3d-4f bimetallic photomagnetic materials.

Pressure-induced crystal color change of photo-magnetic materials [Ln(DMF)4(H2O)3(μ-CN)M(CN)5]·H2O, Ln = Y, M = Fe (1), Ln = Y, M = Co (2), Ln = Nd, M = Fe (3) (DMF = N,N-dimethyl formamide) are investigated using variable pressure X-ray Absorption Near-Edge Structure (XANES) spectroscopy and X-ray diffraction. For 1 the effect is caused by ligand-to-metal charge transfer (LMCT) on the iron site.

Enhancement of the chemical stability in confined δ-Bi2O3.

Bismuth-oxide-based materials are the building blocks for modern ferroelectrics, multiferroics, gas sensors, light photocatalysts and fuel cells. Although the cubic fluorite δ-phase of bismuth oxide (δ-Bi2O3) exhibits the highest conductivity of known solid-state oxygen ion conductors, its instability prevents use at low temperature. Here we demonstrate the possibility of stabilizing δ-Bi2O3 using highly coherent interfaces of alternating layers of Er2O3-stabilized δ-Bi2O3 and Gd2O3-doped CeO2.

Tailoring the properties of ammine metal borohydrides for solid-state hydrogen storage.

A series of halide-free ammine manganese borohydrides, Mn(BH4 )2 ⋅nNH3 , n=1, 2, 3, and 6, a new bimetallic compound Li2 Mn(BH4 )4 ⋅6NH3 , and the first ammine metal borohydride solid solution Mg1-x Mnx (BH4 )2 ⋅6NH3 are presented. Four new crystal structures have been determined by synchrotron radiation powder X-ray diffraction and the thermal decomposition is systematically investigated for all the new compounds. The solid-gas reaction between Mn(BH4 )2 and NH3 provides Mn(BH4 )2 ⋅6NH3 .

Fine tunable aqueous solution synthesis of textured flexible SnS2 thin films and nanosheets.

Films and nanosheets of layered chalcogenides are currently under intense investigation owing to their application in thin film electronic, optoelectronic, and sensor devices. Here, aqueous solution processing of the environmentally benign thiostannate, (NH4)4Sn2S6·3H2O, and its subsequent thermal decomposition to form continuous highly textured SnS2 thin films are presented. We show how to control the film thickness, the coherent scattering domain size, and the crystallinity by changes in the processing parameters (i.

Optimized carbonation of magnesium silicate mineral for CO2 storage.

The global ambition of reducing the carbon dioxide emission makes sequestration reactions attractive as an option of storing CO2. One promising environmentally benign technology is based on forming thermodynamically stable carbonated minerals, with the drawback that these reactions usually have low conversion rates. In this work, the carbonation reaction of Mg rich olivine, Mg2SiO4, under supercritical conditions has been studied.

Charge density investigations on [2,2]-paracyclophane – in data we trust.

Four datasets on [2,2]-paracyclophane were collected in-house and at the Advanced Photon Source at two different temperatures for charge density investigation. Global data quality indicators such as high resolution, high I/σ(I) values, low merging R values and high multiplicity were matched for all four datasets. The structural parameters did not show significant differences, but the synchrotron data depicted deficiencies in the topological analysis.

In situ powder X-ray diffraction study of magnetic CoFe2O4 nanocrystallite synthesis.

The evolution of size and size distribution during hydrothermal synthesis of nanocrystalline CoFe2O4 has been studied by in situ synchrotron powder X-ray diffraction (PXRD). Varying synthesis temperature or [OH(-)] concentration in the precursor proves to have no significant effect on the final volume-weighted nanocrystallite sizes (∼12 nm) of CoFe2O4. However, analysis by whole powder pattern modeling of the [OH(-)] concentration series reveals a substantial difference in the number-weighted size distributions when varying the amount of base used.

Nuclear-weighted X-ray maximum entropy method - NXMEM.

Subtle structural features such as disorder and anharmonic motion may be accurately characterized from nuclear density distributions (NDDs). As a viable alternative to neutron diffraction, this paper introduces a new approach named the nuclear-weighted X-ray maximum entropy method (NXMEM) for reconstructing pseudo NDDs. It calculates an electron-weighted nuclear density distribution (eNDD), exploiting that X-ray diffraction delivers data of superior quality, requires smaller sample volumes and has higher availability.

Location of Cu(2+) in CHA zeolite investigated by X-ray diffraction using the Rietveld/maximum entropy method.

Accurate structural models of reaction centres in zeolite catalysts are a prerequisite for mechanistic studies and further improvements to the catalytic performance. The Rietveld/maximum entropy method is applied to synchrotron powder X-ray diffraction data on fully dehydrated CHA-type zeolites with and without loading of catalytically active Cu(2+) for the selective catalytic reduction of NO x with NH3. The method identifies the known Cu(2+) sites in the six-membered ring and a not previously observed site in the eight-membered ring.

Chemical bonding in a linear chromium metal string complex.

A combined experimental and theoretical electron density study of the shortest trichromium metal wire, Cr3(dpa)4Cl2·(C2H5OC2H5)(x)(CH2Cl2)(1-x) (1, dpa = bis(2-pyridyl)amido), is reported. High resolution X-ray diffraction data has been collected both at 100 K using a conventional X-ray source (DS1) and at 15 K using a synchrotron X-ray source (DS2). The linear chromium string is terminated by Cl(-) ions at both ends, and each Cr atom is also coordinated by four N atoms from bridging dpa ligands.