0000000000072730
AUTHOR
J. Purans
Disorder-induced Raman scattering in rhenium trioxide (ReO3)
Raman scattering in cubic metallic perovskite (ReO3) was studied at room temperature for well-crystallized monolith, polycrystalline powder and thin film samples. Defect-induced first-order Raman scattering was detected from the sub-surface region, given by the penetration depth of a 633 nm laser, and its origin was explained on the basis of a rigid-ion vibrational model for bulk ReO3. A quenching of the Raman intensity was observed in crystalline monolithic ReO3 upon increasing the temperature up to 250 °C and was related to crystal surface reconstruction/annealing.
Cu Polyimidazole Thioether Complexes : Comparison of RDF's Reconstructed from XAFS and XRD Data
Radial distribution functions (RDF) reconstructed from XAFS data (Cu K-edge at low and room temperatures) are compared with RDF's constructed from XRD crystallographic data of Cu polyimidazole thioether complexes. New EDA software package possibilities are used to reconstruct RDFs: (i) model independent RDF reconstruction, and (ii) multi shell - cumulant fitting. RDF's obtained from XRD data are broadened with Debye Waller factors calculated from XAFS. This way the structural disorder (set of distances) and thermal (vibrational) disorder are quantitatively taken into account in each RDF reconstruction approach. Within experimental error the three sets of RDF'S agree well with each other for…
<title>Quantum chemistry studies of the O K-edge x-ray absorption in WO<formula><inf><roman>3</roman></inf></formula> and AWO<formula><inf><roman>3</roman></inf></formula></title>
In this work we present an interpretation of experimental O K-edge x-ray absorption near edge structure (XANES) in perovskite-type WO3 and AWO3 compounds (A = H and Na) using three different first principles approaches: (i) fullmultiple- scattering (FMS) formalism (the real-space FEFF code), (ii) hybrid density functional theory (DFT) method with partial incorporation of exact Hartree-Fock exchange using formalism of the linear combination of atomic orbitals (LCAO) as implemented in the CRYSTAL code; (iii) plane-wave DFT method using formalism of the projectoraugmented waves (PAW) as implemented in the VASP code.
Raman study of the phase transitions sequence in pure WO3 at high temperature and in HxWO3 with variable hydrogen content
Abstract An extensive investigation of the temperature dependence of Raman spectra has been carried out on WO 3 powders from room temperature to 800°C. In particular the orthorhombic-to-tetragonal phase transition occurring at about 740°C has been studied for the first time. The Raman active mode at 710 cm −1 of the orthorhombic phase disappears from the spectrum at temperature below the phase transition point and the Raman activity in the tetragonal phase results very low. A comparative study of hydrogenated tungsten bronzes H x WO 3 ( x ≤0.23), where the same transition sequence is driven by an increase of the proton concentration from x =0 to 0.23, reveals similar behaviour of the high f…
Neural Network Approach for Characterizing Structural Transformations by X-Ray Absorption Fine Structure Spectroscopy
AIF acknowledge support by the US Department of Energy, Office of Basic Energy Sciences under Grant No. DE-FG02 03ER15476. AIF acknowledges support by the Laboratory Directed Research and Development Program through LDRD 18-047 of Brookhaven National Laboratory under U.S. Department of Energy Contract No. DE-SC0012704 for initiating his research in machine learning methods. The help of the beamline staff at ELETTRA (project 20160412) synchrotron radiation facility is acknowledged. RMC-EXAFS and MD-EXAFS simulations were performed on the LASC cluster-type computer at Institute of Solid State Physics of the University of Latvia.
Jahn-Teller distortion aroundFe4+inSr(FexTi1−x)O3−δfrom x-ray absorption spectroscopy, x-ray diffraction, and vibrational spectroscopy
$\mathrm{Sr}({\mathrm{Fe}}_{x}{\mathrm{Ti}}_{1\ensuremath{-}x}){\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$ perovskites (strontium titanate ferrite solid solution) with well-defined oxygen stoichiometry have been studied as a function of iron concentration by x-ray diffraction, Fe and Ti $K$-edge x-ray absorption spectroscopy (XAS), and vibrational (Raman and infrared) spectroscopy. In reduced $\mathrm{Sr}({\mathrm{Fe}}_{x}{\mathrm{Ti}}_{1\ensuremath{-}x}){\mathrm{O}}_{3\ensuremath{-}x∕2}$ samples, the analysis of the Fe $K$-edge extended x-ray absorption fine structure indicates the expected presence of oxygen vacancies ${\mathrm{V}}_{\mathrm{O}}^{∙∙}$ in the first coordination shell…
Structural characterization of mixed Ta–Re oxide films
Thin films of mixed Ta and Re oxides have been produced by reactive dc magnetron co-sputtering of pure Ta and Re metal targets in Ar–O2 atmosphere. The structural evolution of these films has been studied as a function of the composition, starting from a pure tantalum oxide film up to about 82% rhenium content. The composition and the structure of the films have been investigated by using X-ray diffraction and micro-Raman spectroscopy. For low Re content (20%), islands of a well crystallized phase, based on ReO4 groups, appear in the films still composed by pure amorphous tantalum oxide, while a mixed disordered solid phase is found for the highest Re concentration (82%). © 2006 Elsevier B.…
Proton presence and motion in rhenium-oxide films and their application to liquid-crystalline cells
Disordered solid phases, containing appreciable amounts of hydrogen ions, are grown at the surface of rhenium oxide crystals, because of the high reactivity of this compound with ambient moisture. To investigate such phenomena, a comparative study is performed on ground powder and thermally evaporated or sputtered films using x-ray diffraction and micro-Raman spectroscopy. Two types of solid phases were found in the films: HxReO3 distorted perovskite structures, based on corner-sharing ReO6 octahedra as in the bulk crystals, and ordered HReO4 crystalline structures, based on tetrahedral perrhenate ions. The complex impedance measurements on ReO3 films support the hypothesis of mobile hydrog…
Low-temperature polymorphism in tungsten trioxide powders and its dependence on mechanical treatments
The polymorphism of WO3 powder samples, resulting from mild mechanical treatments and from temperature changes between 30 K and room temperature, has been investigated by using Raman spectroscopy and X-ray di⁄raction. A transition from the monoclinic (I) c-phase to the triclinic d-phase after moderate mechanical treatments has been observed for untreated powder, just what happens when the same samples are rapidly cooled to low-temperature. Evidences of the low temperature monoclinic (II) polar e-phase have been found at room temperature in samples after a stronger milling treatment. The sequence of the low-temperature phase transitions appears to be strongly dependent on the mechanical hist…
Influence of hydrogen intercalation on the local structure around Re ions in perovskite‐type ReO 3
octahedra with the Re-O-Re angle equal to 169° and the Re-O distance of about 1.90 A [9]. More accurate information on the local atomic and electronic structure of the bronzes can be ob-tained using XAS, which is a structural method complimentary to diffraction. To our knowledge, no such works have been performed until now. In this work, we present the first results of the in-situ XAS study of hydrogen intercalation into ReO
EXAFS study of hydrogen intercalation into ReO 3 using the evolutionary algorithm.
In this study we have investigated the influence of hydrogen intercalation on the local atomic structure of rhenium trioxide using a new approach to EXAFS data analysis, based on the evolutionary algorithm (EA). The proposed EA-EXAFS method is an extension of the conventional reverse Monte Carlo approach but is computationally more efficient. It allows one to perform accurate analysis of EXAFS data from distant coordination shells, taking into account both multiple-scattering and disorder (thermal and static) effects. The power of the EA-EXAFS method is first demonstrated on an example of the model system, pure ReO3, and then it is applied to an in situ study of hydrogen bronze HxReO3 upon …
Local atomic and electronic structure of tungsten ions in AWO4 crystals of scheelite and wolframite types
Abstract X-ray absorption spectroscopy was used to study the local atomic and electronic structure of tungsten ions in polycrystalline scheelite CaWO4 and wolframite-type ZnWO4 and NiWO4. The W L1- and L3-edges X-ray absorption near edge structure (XANES) signals suggest tetrahedral coordination of tungsten ions in CaWO4 and strongly distorted octahedral coordination in ZnWO4 and NiWO4. Accurate analysis of the W L3-edge extended X-ray absorption fine structure (EXAFS) signals by the regularization procedure was performed to reconstruct the radial distribution functions within the first coordination shell around tungsten atoms in AWO4 crystals and polycrystalline WO3, which was utilized for…
Temperature and pH Dependence XAFS Study of Gd(DOTA)(-) and Gd(DTPA)(2)(-) Complexes: Solid State and Solution Structures.
We present an X-ray absorption spectroscopy study of the local structures of Gd(DTPA)(2)(-) and Gd(DOTA)(-) complexes in the crystalline state (at room and low temperatures) and in aqueous solutions exhibiting various pH values (0.15-7) at different temperatures (25-90 degrees C). Using X-ray absorption fine structure (XAFS) analysis procedures and ab initio multiple scattering calculations of XAFS spectra at the Gd L(3) edge, we reconstructed the Gd(3+) local environment, and compared it with existing structural models. From neutral pH to a value of 1.5, we found that the local environment and complex dynamics around the gadolinium ions were conserved up to 4.5 Å, and the structure agreed …
Full multiple scattering analysis of X-ray absorption near edge structure at the Eu L3-edge in EuO
Abstract X-ray absorption near edge structure (XANES) at the Eu L 3 -edge in crystalline EuO is interpreted within full multiple scattering (FMS) formalism. Our theoretical results, based on the ab initio self-consistent (SC) potential calculations, are in good agreement with experimental data. The main features in the experimental signal are reproduced taking into account a cluster of about five coordination shells, centred at the europium atom and having EuO structure. An addition of more distant coordination shells makes features only better resolved. The relatively high intensity of the peak, located just above the Eu L 3 -edge, indicates that 5d states are well localised. Comparative a…
Oxygen K-edge x-ray absorption near-edge structure in crystalline and amorphous molybdenum trioxides
X-ray absorption near-edge structure (XANES) signals at the oxygen K edge in polycrystalline α-MoO3 and amorphous a-MoO3 thin film were analysed within the full-multiple-scattering (FMS) formalism. Significantly different XANES signals were found for non-equivalent oxygen atoms in low-symmetry layered-type α-MoO3 structure. The obtained results are in agreement with the experimental data and allow us to interpret all XANES peaks for α-MoO3. Besides, the FMS XANES simulations, performed for several fragments of α-MoO3 structure, allowed us to explain the O K-edge XANES in amorphous a-MoO3 thin film. We found that although the crystallographic structures of α-MoO3 and a-MoO3 are strongly diff…
X-ray absorption spectroscopy study of local dynamics and thermal expansion in ReO3
The thermal expansion of polycrystalline ${\mathrm{ReO}}_{3}$ is studied in vacuum by x-ray diffraction from 300 to 600 K and by extended x-ray absorption fine structure (EXAFS) at the Re ${L}_{3}$ edge from 30 to 600 K. A detailed EXAFS analysis is presented up to the sixth coordination shell around Re. The crystal thermal expansion is weak throughout the explored range, negative below 100 K, positive from 150 to 500 K, and negative again above 500 K. The analysis of mean square relative displacements obtained by EXAFS and of mean square displacements available from x-ray and neutron diffraction measurements confirms the presence of significant static disorder in the investigated samples. …
Ab initio calculations of the Ni K ‐edge XANES in Ni c Mg 1‐c O solid solutions
An interpretation of the Ni K-edge X-ray absorption near edge structure (XANES) in pure NiO and NicMg1-cO solid solutions is given based on three types of ab initio theoretical calculations: the full-multiple-scattering (FMS) approach, the finite difference method (FDM) and the full potential linear muffin-tin orbital (FP-LMTO) method within the LSDA+U approach. The first two methods differ in the cluster potential approximation: the spherically symmetric muffin-tin potential is used in the FMS approach, whereas a non-muffin-tin numerical potential makes the core of the FDM. We found that the FMS and FDM techniques allow rather accurate description of the experimental XANES signal especiall…
Isotopic Effect In Extended X-Ray-Absorption Fine Structure of Germanium
Extended x-ray absorption fine structure has been measured on two powdered samples of 70Ge and 76Ge as a function of temperature from 20 to 300 K. The effect of isotopic mass difference on the amplitude of relative atomic vibrations is neatly evidenced by the temperature dependence of the difference of Debye-Waller factors. The isotopic effect is also detected on the difference of nearest-neighbor average ineratomic distances, thanks to a resolution better than 10 fm. (DOI: 10.1103/PhysRevLett.100.055901)
Temperature and pH Dependence of Gd-DOTA and Gd-DTPA Complexes Dissociation Studied by EXAFS
The Gd L3-edge of Gd(DTPA) 2- and Gd(DOTA) - complexes, in crystalline state and aqueous solutions presenting various pH (0.15-8) at different temperatures (25-90 °C), are investigated by XAFS experiments. For the Gd(DTPA) 2- . complexes we observe a strong pH (0.15-1.5) dependence of XAFS signals. On the other hand, the XAFS signals of Gd(DOTA) - complexes exhibit a light pH (1-1.5) dependence and for pH<1 we observe a ligand decomposition. Conceming both complexes, we note just a light temperature dependence. To obtain information about the short and medium range order (up to 5 A), multiple scattering calculation is performed. For the first coordination shell, we apply multi-shell fitting…
XAS, XRD, AFM and Raman studies of nickel tungstate electrochromic thin films
Abstract Systematic studies of nanocrystalline nickel tungstate, NiWO 4 , thin films were performed by several experimental techniques such as Ni K- and W L 1,3 -edges X-ray absorption spectroscopy, X-ray diffraction, Raman spectroscopy, atomic force microscopy and cyclic voltammetry measurements. We found that the NiWO 4 thin films exhibit electrochromic properties similar to that of amorphous tungsten trioxide films, but show better structural stability upon multiple colouring/bleaching cycling. It was observed that a nanocrystallinity of the thin films results in strong modifications of the NiO and WO interactions, which affect both local atomic and vibrational structures.