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Sample records for polarized cu k-edge

  1. Effect of atomic vibrations in XANES: polarization-dependent damping of the fine structure at the Cu K-edge of (creat)2CuCl4.

    PubMed

    Šipr, Ondřej; Vackář, Jiří; Kuzmin, Alexei

    2016-11-01

    Polarization-dependent damping of the fine structure in the Cu K-edge spectrum of creatinium tetrachlorocuprate [(creat)2CuCl4] in the X-ray absorption near-edge structure (XANES) region is shown to be due to atomic vibrations. These vibrations can be separated into two groups, depending on whether the respective atoms belong to the same molecular block; individual molecular blocks can be treated as semi-rigid entities while the mutual positions of these blocks are subject to large mean relative displacements. The effect of vibrations can be efficiently included in XANES calculations by using the same formula as for static systems but with a modified free-electron propagator which accounts for fluctuations in interatomic distances.

  2. On the origin of the differences in the Cu K-edge XANES of isostructural and isoelectronic compounds.

    PubMed

    Sipr, O; Rocca, F; Fornasini, P

    2009-06-24

    Cu K-edge x-ray absorption near-edge structure (XANES) spectra of trigonal (3R) CuScO(2) and CuLaO(2) and of hexagonal (2H) CuScO(2) were investigated experimentally and theoretically, in order to study differences between spectra of isostructural and isoelectronic compounds. Significant differences were found in the Cu K-edge XANES of 3R CuScO(2) and 3R CuLaO(2); these differences can be understood by considering the calculated polarization dependence of the XANES spectra and the differences between the phaseshifts of Sc and La. Spectra of the 3R and 2H polytypes of CuScO(2) differ only weakly and the difference originates from the long-range order. The pre-edge peak around 8980 eV is generated by the same mechanism as the pre-edge peak in Cu(2)O, i.e. involving scattering by the Cu atoms in the plane which is perpendicular to the O-Cu-O axis.

  3. Amyloid-β peptide active site: theoretical Cu K-edge XANES study

    NASA Astrophysics Data System (ADS)

    Chaynikov, A. P.; Soldatov, M. A.; Streltsov, V.; Soldatov, A. V.

    2013-04-01

    This article is dedicated to the local atomic structure analysis of the copper binding site in amyloid-β peptide. Here we considered two possible structural models that were previously obtained by means of EXAFS analysis and density functional theory simulations. We present the calculations of Cu K-edge XANES spectra for both models and make comparison of these spectra with experiment.

  4. Multiple pre-edge structures in Cu K -edge x-ray absorption spectra of high- Tc cuprates revealed by high-resolution x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Gougoussis, C.; Rueff, J.-P.; Calandra, M.; D'Astuto, M.; Jarrige, I.; Ishii, H.; Shukla, A.; Yamada, I.; Azuma, M.; Takano, M.

    2010-06-01

    Using high-resolution x-ray absorption spectroscopy and state-of-the-art electronic structure calculations we demonstrate that the pre-edge region at the Cu K edge of high- Tc cuprates is composed of several excitations invisible in standard x-ray absorption spectra. We consider in detail the case of Ca2-xCuO2Cl2 and show that the many pre-edge excitations (two for c -axis polarization, four for in-plane polarization and out-of-plane incident x-ray momentum) are dominated by off-site transitions and intersite hybridization. This demonstrates the relevance of approaches beyond the single-site model for the description of the pre edges of correlated materials. Finally, we show the occurrence of a doubling of the main edge peak that is most visible when the polarization is along the c axis. This doubling, that has not been seen in any previous absorption data in cuprates, is not reproduced by first-principles calculations. We suggest that this peak is due to many-body charge-transfer excitations while all the other visible far-edge structures are single particle in origin. Our work indicates that previous interpretations of the Cu K -edge x-ray absorption spectra in high- Tc cuprates can be profitably reconsidered.

  5. Local environment about O atoms in Pr-Y-Ba-Cu-O films studied by O K-edge XAFS

    SciTech Connect

    Krol, A.; Soo, Y. L.; Huang, S; Ming, Z. H.; Song, L. W.; Kao, Y. H.; Smith, G. C.

    1992-09-01

    The local environment about oxygen atoms in Pr{sub x}Y{sub 1-x}Ba{sub 2}Cu{sub 3}O{sub 7} films obtained by laser ablation has been investigated by means of the x-ray absorption fine structure (XAFS) spectroscopy at the O K-edge. It has been found that the Pr atoms do not substitute for the Cu atoms nor form interstitial defects in the CuO{sub 2} planes and that the presence of Pr dopant does not disturb the local environment of oxygen.

  6. K-edge EXAFS and XANES studies of Cu in CdTe thin-film solar cells

    NASA Astrophysics Data System (ADS)

    Liu, Xiangxin; Gupta, Akhlesh; Compaan, Alvin D.; Leyarovska, Nadia; Terry, Jeff

    2002-03-01

    Copper has been identified as a very important dopant element in CdTe thin-film solar cells. Cu is a deep acceptor in CdTe and is commonly used to obtain a heavily doped, low resistance back contact to polycrystalline CdTe. Cu also helps to increase the open circuit voltage of the cell. However, Cu is also a fast diffuser in CdTe, especially along grain boundaries, and can accumulate at the CdS/CdTe junction. It is suspected of leading to cell performance degradation in some cases. The present study is designed to help identify the lattice location of the Cu in CdTe. Cu K-edge, x-ray absorption (XAS) measurements were conducted on Cu in thin films of CdTe. Experiments were performed at the MR-CAT beamline at the Advanced Photon Source. The 3 mm CdTe layers were magnetron sputtered onto fused silica substrates. Some films were diffused with Cu from a 200 Å layer of evaporated Cu. XAS spectra were collected in fluorescence geometry with a 13 elements Ge detector. Quantitative fluorescence spectroscopy measurements were also performed. Details of the Cu environment and possible changes with time will be reported.

  7. Resonant inelastic X-ray scattering spectrometer with 25meV resolution at the Cu K -edge

    DOE PAGES

    Ketenoglu, Didem; Harder, Manuel; Klementiev, Konstantin; ...

    2015-06-27

    An unparalleled resolution is reported with an inelastic X-ray scattering instrument at the CuK-edge. Based on a segmented concave analyzer, featuring single-crystal quartz (SiO2) pixels, the spectrometer delivers a resolution near 25meV (FWHM) at 8981eV. Besides the quartz analyzer, the performance of the spectrometer relies on a four-bounce Si(553) high-resolution monochromator and focusing Kirkpatrick–Baez optics. The measured resolution agrees with the ray-tracing simulation of an ideal spectrometer. The performance of the spectrometer is demonstrated by reproducing the phonon dispersion curve of a beryllium single-crystal.

  8. Resonant inelastic X-ray scattering spectrometer with 25 meV resolution at the Cu K-edge

    PubMed Central

    Ketenoglu, Didem; Harder, Manuel; Klementiev, Konstantin; Upton, Mary; Taherkhani, Mehran; Spiwek, Manfred; Dill, Frank-Uwe; Wille, Hans-Christian; Yavaş, Hasan

    2015-01-01

    An unparalleled resolution is reported with an inelastic X-ray scattering instrument at the Cu K-edge. Based on a segmented concave analyzer, featuring single-crystal quartz (SiO2) pixels, the spectrometer delivers a resolution near 25 meV (FWHM) at 8981 eV. Besides the quartz analyzer, the performance of the spectrometer relies on a four-bounce Si(553) high-resolution monochromator and focusing Kirkpatrick–Baez optics. The measured resolution agrees with the ray-tracing simulation of an ideal spectrometer. The performance of the spectrometer is demonstrated by reproducing the phonon dispersion curve of a beryllium single-crystal. PMID:26134800

  9. Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

    DOE PAGES

    Frank, Patrick; Szilagyi, Robert K.; Gramlich, Volker; ...

    2017-01-09

    Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [MII(itao)(SO4)(H2O)0,1] (M = Co, Ni, Cu) and [Cu(Me6tren)(SO4)] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal–sulfur bond, while the XAS preedge of [Zn(itao)(SO4)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO4)] but not of [Cu(Me6tren)(SO4)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [MII(SO4)(H2O)] (M = Fe, Co, Ni, and Cu, but not Zn) and inmore » sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5–2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal–absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which extends across

  10. Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer.

    PubMed

    Frank, Patrick; Szilagyi, Robert K; Gramlich, Volker; Hsu, Hua-Fen; Hedman, Britt; Hodgson, Keith O

    2017-02-06

    Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M(II)(itao)(SO4)(H2O)0,1] (M = Co, Ni, Cu) and [Cu(Me6tren)(SO4)] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal-sulfur bond, while the XAS preedge of [Zn(itao)(SO4)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO4)] but not of [Cu(Me6tren)(SO4)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M(II)(SO4)(H2O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5-2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal-absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which extends across a

  11. Unraveling the nature of charge excitations in La2CuO4 with momentum-resolved Cu K-edge resonant inelastic X-ray scattering

    SciTech Connect

    Chen, Cheng-Chien

    2011-03-01

    Results of model calculations using exact diagonalization reveal the orbital character of states associated with different Raman loss peaks in Cu K-edge resonant inelastic X-ray scattering (RIXS) from La{sub 2}CuO{sub 4}. The model includes electronic orbitals necessary to highlight non-local Zhang-Rice singlet, charge transfer and d-d excitations, as well as states with apical oxygen 2p{sub z} character. The dispersion of these excitations is discussed with prospects for resonant final state wave-function mapping. A good agreement with experiments emphasizes the substantial multi-orbital character of RIXS profiles in the energy transfer range 1-6 eV.

  12. Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

    SciTech Connect

    Liu, Xiang; Cui, Shengsheng; Sun, Zijun; Ren, Yang; Zhang, Xiaoyi; Du, Pingwu

    2016-01-21

    Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onset potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.

  13. Cu K-edge X-ray Absorption Spectroscopy Reveals Differential Copper Coordimation Within Amyloid-beta Oligomers Compared to Amyloid-beta Monomers

    SciTech Connect

    J Shearer; P Callan; T Tran; V Szalai

    2011-12-31

    The fatal neurodegenerative disorder Alzheimer's disease (AD) has been linked to the formation of soluble neurotoxic oligomers of amyloid-{beta} (A{beta}) peptides. These peptides have high affinities for copper cations. Despite their potential importance in AD neurodegeneration few studies have focused on probing the Cu{sup 2+/1+} coordination environment within A{beta} oligomers. Herein we present a Cu K-edge X-ray absorption spectroscopic study probing the copper-coordination environment within oligomers of A{beta}(42) (sequence: DAEFRHDSGYEVHHQKLVFFAEDVGSNKGAIIGLMVGGVVIA). We find that the Cu{sup 2+} cation is contained within a square planar mixed N/O ligand environment within A{beta}(42) oligomers, which is similar to the copper coordination environment of the monomeric forms of {l_brace}Cu{sup II}A{beta}(40){r_brace} and {l_brace}Cu{sup II}A{beta}(16){r_brace}. Reduction of the Cu{sup 2+} cation within the A{beta}(42) oligomers to Cu{sup 1+} yields a highly dioxygen sensitive copper-species that contains Cu{sup 1+} in a tetrahedral coordination geometry. This can be contrasted with monomers of {l_brace}Cu{sup I}A{beta}(40){r_brace} and {l_brace}Cu{sup I}A{beta}(16){r_brace}, which contain copper in a dioxygen inert linear bis-histidine ligand environment [Shearer and Szalai, J. Am. Chem. Soc., 2008, 130, 17826]. The biological implications of these findings are discussed.

  14. Multivariate curve resolution analysis for interpretation of dynamic Cu K-edge X-ray absorption spectroscopy spectra for a Cu doped V(2)O(5) lithium battery.

    PubMed

    Conti, Paolo; Zamponi, Silvia; Giorgetti, Marco; Berrettoni, Mario; Smyrl, William H

    2010-05-01

    Vanadium pentoxide materials prepared through sol-gel processes act as excellent intercalation hosts for lithium as well as polyvalent cations. A chemometric approach has been applied to study the X-ray absorption near-edge structure (XANES) evolution during in situ scanning of the Cu(0.1)V(2)O(5) xerogel/Li ions battery. Among the more common techniques, the fixed size windows evolving factor analysis (FSWEFA) permits the number of species involved in the experiment to be determined and the range of existence of each of them. This result, combined with the constraints of the invariance of the total concentration and non-negativity of both concentrations and spectra, enabled us to obtain the spectra of the pure components using a multivariate curve resolution refined by an alternate least squares fitting procedure. This allowed the normalized concentration profile to be understood. This data treatment evidenced the occurrence, for the first time, of three species during the battery charging. This fact finds confirmation by comparison of the pure spectra with the experimental ones. Extended X-ray absorption fine structure (EXAFS) analysis confirms the occurrence of three different chemical environments of Cu during battery charging.

  15. K-edge densitometer (KED)

    SciTech Connect

    Sprinkle, J.K.; Hansen, W.J.

    1993-02-11

    In 1979, a K-edge densitometer (KED) was installed by the Safeguards Assay group from Los Alamos National Laboratory in the PNC reprocessing plant at Tokai-mura, Japan. It uses an active nondestructive assay technique, KED, to measure the plutonium concentration of the product solution. The measurement uncertainty of an assay depends on the count time chosen, but can be 0.5% or better. The computer hardware and software were upgraded in 1992. This manual describes the operation of the instrument, with an emphasis on the user interface to the software.

  16. Complex polarization propagator approach in the restricted open-shell, self-consistent field approximation: the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine.

    PubMed

    Linares, Mathieu; Stafström, Sven; Rinkevicius, Zilvinas; Ågren, Hans; Norman, Patrick

    2011-05-12

    A presentation of the complex polarization propagator in the restricted open-shell self-consistent field approximation is given. It rests on a formulation of a resonant-convergent, first-order polarization propagator approach that makes it possible to directly calculate the X-ray absorption cross section at a particular frequency without explicitly addressing the excited states. The quality of the predicted X-ray spectra relates only to the type of density functional applied without any separate treatment of dynamical relaxation effects. The method is applied to the calculation of the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine. Comparison is made between the spectra of the radicals and those of the corresponding cations and anions to assess the effect of the increase of electron charge in the frontier orbital. The method offers the possibility for unique assignment of symmetry-independent atoms. The overall excellent spectral agreement motivates the application of the method as a routine precise tool for analyzing X-ray absorption of large systems of technological interest.

  17. Full-Field Calcium K-Edge X-ray Absorption Near-Edge Structure Spectroscopy on Cortical Bone at the Micron-Scale: Polarization Effects Reveal Mineral Orientation.

    PubMed

    Hesse, Bernhard; Salome, Murielle; Castillo-Michel, Hiram; Cotte, Marine; Fayard, Barbara; Sahle, Christoph J; De Nolf, Wout; Hradilova, Jana; Masic, Admir; Kanngießer, Birgit; Bohner, Marc; Varga, Peter; Raum, Kay; Schrof, Susanne

    2016-04-05

    Here, we show results on X-ray absorption near edge structure spectroscopy in both transmission and X-ray fluorescence full-field mode (FF-XANES) at the calcium K-edge on human bone tissue in healthy and diseased conditions and for different tissue maturation stages. We observe that the dominating spectral differences originating from different tissue regions, which are well pronounced in the white line and postedge structures are associated with polarization effects. These polarization effects dominate the spectral variance and must be well understood and modeled before analyzing the very subtle spectral variations related to the bone tissue variations itself. However, these modulations in the fine structure of the spectra can potentially be of high interest to quantify orientations of the apatite crystals in highly structured tissue matrices such as bone. Due to the extremely short wavelengths of X-rays, FF-XANES overcomes the limited spatial resolution of other optical and spectroscopic techniques exploiting visible light. Since the field of view in FF-XANES is rather large the acquisition times for analyzing the same region are short compared to, for example, X-ray diffraction techniques. Our results on the angular absorption dependence were verified by both site-matched polarized Raman spectroscopy, which has been shown to be sensitive to the orientation of bone building blocks and by mathematical simulations of the angular absorbance dependence. As an outlook we further demonstrate the polarization based assessment of calcium-containing crystal orientation and specification of calcium in a beta-tricalcium phosphate (β-Ca3(PO4)2 scaffold implanted into ovine bone. Regarding the use of XANES to assess chemical properties of Ca in human bone tissue our data suggest that neither the anatomical site (tibia vs jaw) nor pathology (healthy vs necrotic jaw bone tissue) affected the averaged spectral shape of the XANES spectra.

  18. Zn K edge and O K edge x-ray absorption spectra of ZnO surfaces: implications for nanorods.

    PubMed

    Šipr, O; Rocca, F

    2011-08-10

    Zn K edge and O K edge x-ray absorption near-edge structure (XANES) spectra of ZnO surfaces are calculated. The difference between theoretical XANES for ZnO surfaces and ZnO bulk is then compared to the earlier observed differences between experimental XANES for ZnO nanostructures and ZnO bulk as taken from the literature. It follows from our calculations that the differences between the experimental XANES of bulk ZnO and nanocrystalline ZnO is not due to the enhanced role of the surfaces in nanostructures. Rather, the difference in XANES has to reflect differences in the local geometry around the photoabsorbing sites. The dependence of XANES of ZnO surfaces on the polarization of the incoming radiation is also investigated theoretically and found to be similar as in the bulk.

  19. Magnetic Nature of the 500 meV peak in La2−xSrxCuO4 Observed with Resonant Inelastic X-ray Scattering at the Cu K-edge

    SciTech Connect

    Hill, J.P.; Ellis, D.S.; Kim, J.; Wakimoto, S.; Birgeneau, R.J.; Shvyd’ko, Y.; Casa, D.; Gog, T.; Ishii, K.; Ikeuchi, K.; Paramekanti, A.; Kim, Y.-J.

    2010-02-15

    We present a comprehensive study of the temperature and doping dependence of the 500 meV peak observed at q = ({pi},0) in resonant inelastic x-ray scattering (RIXS) experiments on La{sub 2}CuO{sub 4}. The intensity of this peak persists above the Neel temperature (T{sub N} = 320 K), but decreases gradually with increasing temperature, reaching zero at around T = 500 K. The peak energy decreases with temperature in close quantitative accord with the behavior of the two-magnon B{sub 1g} Raman peak in La{sub 2}CuO{sub 4} and, with suitable rescaling, agrees with the Raman peak shifts in EuBa{sub 2}Cu{sub 3}O{sub 6} and K{sub 2}NiF{sub 4}. The overall dispersion of this excitation in the Brillouin zone is found to be in agreement with theoretical calculations for a two-magnon excitation. Upon doping, the peak intensity decreases analogous to the Raman mode intensity and appears to track the doping dependence of the spin-correlation length. Taken together, these observations strongly suggest that the 500 meV mode is magnetic in character and is likely a two-magnon excitation.

  20. Carbon K-edge Spectra of Carbonate Minerals

    SciTech Connect

    Brandes, J.; Wirick, S; Jacobsen, C

    2010-01-01

    Carbon K-edge X-ray spectroscopy has been applied to the study of a wide range of organic samples, from polymers and coals to interstellar dust particles. Identification of carbonaceous materials within these samples is accomplished by the pattern of resonances in the 280-320 eV energy region. Carbonate minerals are often encountered in the study of natural samples, and have been identified by a distinctive resonance at 290.3 eV. Here C K-edge and Ca L-edge spectra from a range of carbonate minerals are presented. Although all carbonates exhibit a sharp 290 eV resonance, both the precise position of this resonance and the positions of other resonances vary among minerals. The relative strengths of the different carbonate resonances also vary with crystal orientation to the linearly polarized X-ray beam. Intriguingly, several carbonate minerals also exhibit a strong 288.6 eV resonance, consistent with the position of a carbonyl resonance rather than carbonate. Calcite and aragonite, although indistinguishable spectrally at the C K-edge, exhibited significantly different spectra at the Ca L-edge. The distinctive spectral fingerprints of carbonates provide an identification tool, allowing for the examination of such processes as carbon sequestration in minerals, Mn substitution in marine calcium carbonates (dolomitization) and serpentinization of basalts.

  1. Three-dimensional analysis of the local structure of Cu on TiO2(110) by in situ polarization-dependent total-reflection fluorescence XAFS.

    PubMed

    Tanizawa, Y; Chun, W J; Shido, T; Asakura, K; Iwasawa, Y

    2001-03-01

    Cu K-edge XAFS of Cu/TiO2(110) was measured by polarization-dependent total-reflection fluorescence XAFS technique. XAFS of [001], [110], and [110] directions were measured to elucidate the three dimensional structure of Cu species on the TiO2(110) surface prepared by the deposition of Cu(DPM)2 followed by reduction with H2. Simulation of the EXAFS functions as well as conventional curve fitting analysis revealed that plane Cu3,4 small clusters with similar structure to Cu(111) plane were formed by the reduction at 363 K. The small clusters converted into spherical metallic Cu particles by the reduction at 473 K.

  2. An EXAFS study on Bi 2Sr 2Ca 1-xPr xCu 2O 8-δ single crystal using polarized synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Dalela, S.; Dalela, B.; D, Neena; Alvi, P. A.

    2011-03-01

    We have made polarization dependent Extended X-ray Absorption Fine Structure (EXAFS) measurements on a Bi 2Sr 2Ca 1-xPr xCu 2O 8-δ single crystal in the E// a, E// b and E// a^45° orientations. The results on Cu-K edge and Pr L III edge EXAFS have been discussed to explain the quenching of superconductivity due to the presence of Pr cation as it was known to destruct the superconductivity by disturbing the local environment around Ca.

  3. Energy and polarization dependence of resonant inelastic X-ray scattering in Nd{sub 2}CuO{sub 4}

    SciTech Connect

    Hill, J.P.; Kao, C.C.; Haemaelaeinen, K.

    1998-12-31

    The authors report the energy and polarization dependence of resonant inelastic x-ray scattering from Nd{sub 2}CuO{sub 4}. An energy loss feature at {approximately}6 eV is observed in the vicinity of the Cu K-edge. Numerical calculations based on the Anderson impurity model identify this as a charge transfer excitation to the anti-bonding state. The incident polarization is shown to select the intermediate states participating in the resonance process. Resonances are observed at 8,990 eV and 9,000 eV with the incident polarization perpendicular and parallel to the CuO planes, respectively. In contrast to the single-site model calculations, no resonances are observed associated with the {und 1s}3d{sup 10} {und L} intermediate states, suggesting non-local effects play a role.

  4. Polarized experimental and theoretical K-edge x-ray absorption studies of SO/sub 4//sup 2-/, ClO/sub 3//sup -/, S/sub 2/O/sub 3//sup 2-/, and S/sub 2/O/sub 6//sup 2-/

    SciTech Connect

    Tyson, T.A.; Roe, A.L.; Frank, P.; Hodgson, K.O.; Hedman, B.

    1989-04-01

    The first studies of the polarized sulfur and chlorine x-ray K-edge absorption spectra of the oxyanions SO/sub 4//sup 2-/ (sulfate), ClO/sub 3//sup -/ (chlorate), S/sub 2/O/sub 3//sup 2-/ (thiosulfate), and S/sub 2/O/sub 6//sup 2-/ (dithionate) are presented. To provide a basis for the interpretation of the experimental measurements, extended continuum multiple-scattering X..cap alpha.. computations were carried out. This approach enabled us to identify features in the absorption spectra both by symmetry and final-state type (final bound states or final continuum states). For the thiosulfate anion (which has two nonequivalent sulfur atoms) it proved possible to determine which sulfur atom is responsible for each of a series of well-resolved features in the polarized spectra. In addition, generalizing from the case of the chlorate anion, molecules in which the absorbing atom is not completely surrounded by ligands (''open clusters'') may have important contributions from the second shell of neighbors manifested as features in the continuum region of the spectrum.

  5. Production of Spin Polarized 58Cu and its Magnetic Moment

    NASA Astrophysics Data System (ADS)

    Mihara, Mototsugu; Ishibashi, Yoko; Abe, Yasushi; Kamisho, Yasuto; Morita, Yusuke; Ohno, Junichi; Tanaka, Masaomi; Shinozaki, Shinichi; Kanbe, Ryosuke; Fukuda, Mitsunori; Matsuta, Kensaku; Ozawa, Akira; Nagae, Daisuke; Inaba, Seiki; Okada, Shunsuke; Saito, Yuta; Ueno, Hideki; Yamada, Kazunari; Izumikawa, Takuji; Ohtsubo, Takashi; Momota, Sadao; Nishimura, Daiki; Suzuki, Takeshi; Yamaguchi, Takayuki; Kobayashi, Yoshio; Imamura, Kei; Yang, Xiaofei; Nagatomo, Takashi; Minamisono, Tadanori; Takechi, Maya; Ogura, Masako; Matsukawa, Kazuhito; Shirai, Koun; Fujimura, Takumi

    Spin polarization of short-lived β emitter 58Cu was generated through the charge exchange reaction of 58Ni on a Be target at 63 MeV/u and the β-NQR spectrum of 58Cu in Si was measured at 15 K. As a result, the 58Cu magnetic dipole moment μ [58Cu] was determined to be | μ [{}58Cu] | = (0.58 ± 0.01)μ N, which is in agreement with the recent result using collinear laser spectroscopy.

  6. In-plane polarization dependence of (Bi,Pb)2Sr2CaCu2O8+δ single crystals studied by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ghafari, A.; Ariffin, A. K.; Janowitz, C.; Dwelk, H.; Krapf, A.; Manzke, R.

    2014-06-01

    The effects of in-plane polarization change on the determination of the hole density of weakly under-doped (Bi, Pb)-2212 single crystals has been studied by x-ray absorption spectroscopy (XAS). The XAS signal at the CuL3 edge (925-940 eV) and O K edge (525 eV to 539 eV) were recorded under continuous rotation of the CuO2 plane from 0° to 180° with a minimum increment of 1.8°, yielding experimentally an in-plane polarization dependence for the absorption signals at the respective threshold. From that the in-plane angular dependence of the hole density (nH(φ) could be determined. Fermi's golden rule was then used for the evaluation of the in-plane polarization dependence showing the expected polarization independence in disaccord to the experimental observations. Possible scenarios to solve this issue are discussed. Our results propose that polarization dependence could be due to inhomogeneous distribution of holes in the CuO2 planes which is also supported by models. Second, the role of out of plane orbitals has to be taken into account for interpretation.

  7. The efficacy of K-edge filters in diagnostic radiology.

    PubMed

    Williamson, B D; van Doorn, T

    1994-12-01

    The application of K-edge filters in diagnostic radiology has been investigated by many workers for over twenty years. These investigations have analysed the effects of such filters on image quality and radiation dose as well as the practicalities of their application. This paper presents a synopsis of the published works and concludes that K-edge filters do not perceptibly improve image quality and make only limited reductions in patient dose. K-edge filters are also costly to purchase and potentially result in a reduction in the cost effectiveness of x-ray examinations by increasing the x-ray tube loading. Equivalent contrast enhancement and dose reductions can be achieved by the assiduous choice of non-selective filters.

  8. On the Structure of the Iron K-Edge

    NASA Technical Reports Server (NTRS)

    Palmeri, P.; Mendoza, C.; Kallman, T. R.; Bautista, M. A.; White, Nicholas E. (Technical Monitor)

    2002-01-01

    It is shown that the commonly held view of a sharp Fe K edge must be modified if the decay pathways of the series of resonances converging to the K thresholds are adequately taken into account. These resonances display damped Lorentzian profiles of nearly constant widths that are smeared to impose continuity across the threshold. By modeling the effects of K damping on opacities, it is found that the broadening of the K edge grows with the ionization level of the plasma, and the appearance at high ionization of a localized absorption feature at 7.2 keV is identified as the Kbeta unresolved transition array.

  9. ELNES investigations of the oxygen K-edge in spinels.

    PubMed

    Docherty, F T; Craven, A J; McComb, D W; Skakle, J

    2001-02-01

    The results of a systematic study of the oxygen K-edge electron energy-loss spectroscopy (ELNES) from a series of aluminium- and chromium-containing spinels are presented. Extra fine structure in the region up to 10 eV above the edge onset is observed for the chromium-containing compounds and is assigned to transitions to states created by mixing of oxygen 2p and metal 3d orbitals. The experimental data has been simulated using the multiple scattering code, FEFF8. Good agreement was obtained in the case of magnesium aluminate, but relatively poor agreement was obtained in the case of the chromites. The possible fingerprints in the oxygen K-edge ELNES corresponding to a high degree of inversion the spinel structure and to a tetragonal distortion of the cubic structure are discussed.

  10. Aluminium K-Edge XANES Study of Mica Preiswerkite

    SciTech Connect

    Wu, Z.; Marcelli, A.; Cibin, G.; Mottana, A.; Della Ventura, G.; /SLAC, SSRl

    2006-10-27

    We present the Al K-edge XANES spectrum of synthetic mica with mixed fourfold coordinated and sixfold coordinated Al (preiswerkite). Experimental analysis and multiple scattering simulations of XANES spectra demonstrate that octahedral contributions may overlap the tetrahedral ones so that the lower energy structures in mixed coordination compounds may be associated to Al octahedral site. This unexpected behavior can be explained as due to a large local distortion of the Al octahedral site.

  11. Spectral CT Using Multiple Balanced K-Edge Filters

    PubMed Central

    Rakvongthai, Yothin; Worstell, William; Fakhri, Georges El; Bian, Junguo; Lorsakul, Auranuch; Ouyang, Jinsong

    2015-01-01

    Our goal is to validate a spectral CT system design that uses a conventional X-ray source with multiple balanced K-edge filters. By performing a simultaneously synthetic reconstruction in multiple energy bins, we obtained a good agreement between measurements and model expectations for a reasonably complex phantom. We performed simulation and data acquisition on a phantom containing multiple rods of different materials using a NeuroLogica CT scanner. Five balanced K-edge filters including Molybdenum, Cerium, Dysprosium, Erbium, and Tungsten were used separately proximal to the X-ray tube. For each sinogram bin, measured filtered vector can be defined as a product of a transmission matrix, which is determined by the filters and is independent of the imaging object, and energy-binned intensity vector. The energy-binned sinograms were then obtained by inverting the transmission matrix followed by a multiplication of the filter measurement vector. For each energy bin defined by two consecutive K-edges, a synthesized energy-binned attenuation image was obtained using filtered back-projection reconstruction. The reconstructed attenuation coefficients for each rod obtained from the experiment was in good agreement with the corresponding simulated results. Furthermore, the reconstructed attenuation coefficients for a given energy bin, agreed with National Institute of Standards and Technology reference values when beam hardening within the energy bin is small. The proposed cost-effective system design using multiple balanced K-edge filters can be used to perform spectral CT imaging at clinically relevant flux rates using conventional detectors and integrating electronics. PMID:25252276

  12. Measurement of an inverse Compton scattering source local spectrum using k-edge filters

    SciTech Connect

    Golosio, Bruno; Oliva, Piernicola; Carpinelli, Massimo; Endrizzi, Marco; Delogu, Pasquale; Pogorelsky, Igor; Yakimenko, Vitaly

    2012-04-16

    X-ray sources based on the inverse Compton scattering process are attracting a growing interest among scientists, due to their extremely fast pulse, quasi-monochromatic spectrum, and relatively high intensity. The energy spectrum of the x-ray beam produced by inverse Compton scattering sources in a fixed observation direction is a quasi-monochromatic approximately Gaussian distribution. The mean value of this distribution varies with the scattering polar angle between the electron beam direction and the x-ray beam observation direction. Previous works reported experimental measurements of the mean energy as a function of the polar angle. This work introduces a method for the measurement of the whole local energy spectrum (i.e., the spectrum in a fixed observation direction) of the x-ray beam yielded by inverse Compton scattering sources, based on a k-edge filtering technique.

  13. K-Edge Subtraction Angiography with Synchrotron X-Rays

    SciTech Connect

    Giacomini, John C.

    1996-12-31

    The purpose of this project was to utilize dual energy, monochromatic X-rays produced from synchrotrons radiation in order to obtain noninvasive medical imaging. The application of synchrotrons radiation to medical imaging is based on the principle of iodine dichromography, first described by Bertil Jacobson of the Karolinska Institute in 1953. Medical imaging using synchrotrons radiation and K-edge dichromography was pioneered at Stanford University under the leadership of Dr. Ed Rubenstein, and the late Nobel Laureate in Physics, Dr. Robert Hofstadter. With progressive refinements in hardware, clinical-quality images were obtained of human coronary arteries utilizing peripheral injections of iodinated contrast agent. These images even now are far superior to those being presented by investigators using MRI as an imaging tool for coronary arteries. However, new supplies and instruments in the cardiac catheterization laboratory have served to transform coronary angiography into an outpatient procedure, with relatively little morbidity. We extended the principles learned with coronary angiography to noninvasive imaging of the human bronchial tree. For these images, we utilized xenon as the contrast agent, as it has a K-edge very similar to that of iodine. In this case, there is no true competing diagnostic test, and pulmonary neoplasm is an enormous public health concern. In early experiments, we demonstrated remarkably clear images of the human bronchial tree. These images have been shown internationally; however, funding difficulties primarily with the Department of Energy have not allowed for progression of this promising avenue of research. One potential criticism of the project is that in order to obtain these images, we utilized national laboratories. Some have questioned whether this would lead to a practical imaging modality. However, we have shown that the technology exists to allow for construction of a miniature storage ring, with a superconducting

  14. Portable X-Ray, K-Edge Heavy Metal Detector

    SciTech Connect

    Fricke, V.

    1999-10-25

    The X-Ray, K-Edge Heavy Metal Detection System was designed and built by Ames Laboratory and the Center for Nondestructive Evaluation at Iowa State University. The system uses a C-frame inspection head with an X-ray tube mounted on one side of the frame and an imaging unit and a high purity germanium detector on the other side. the inspection head is portable and can be easily positioned around ventilation ducts and pipes up to 36 inches in diameter. Wide angle and narrow beam X-ray shots are used to identify the type of holdup material and the amount of the contaminant. Precise assay data can be obtained within minutes of the interrogation. A profile of the containerized holdup material and a permanent record of the measurement are immediately available.

  15. High spin polarization and the origin of unique ferromagnetic ground state in CuFeSb

    SciTech Connect

    Sirohi, Anshu; Saha, Preetha; Gayen, Sirshendu; Gaurav, Abhishek; Jyotsna, Shubhra; Sheet, Goutam; Singh, Chandan K.; Kabir, Mukul; Thakur, Gohil S.; Haque, Zeba; Gupta, L. C.; Ganguli, Ashok K.

    2016-06-13

    CuFeSb is isostructural to the ferro-pnictide and chalcogenide superconductors and it is one of the few materials in the family that are known to stabilize in a ferromagnetic ground state. Majority of the members of this family are either superconductors or antiferromagnets. Therefore, CuFeSb may be used as an ideal source of spin polarized current in spin-transport devices involving pnictide and the chalcogenide superconductors. However, for that the Fermi surface of CuFeSb needs to be sufficiently spin polarized. In this paper we report direct measurement of transport spin polarization in CuFeSb by spin-resolved Andreev reflection spectroscopy. From a number of measurements using multiple superconducting tips we found that the intrinsic transport spin polarization in CuFeSb is high (∼47%). In order to understand the unique ground state of CuFeSb and the origin of large spin polarization at the Fermi level, we have evaluated the spin-polarized band structure of CuFeSb through first principles calculations. Apart from supporting the observed 47% transport spin polarization, such calculations also indicate that the Sb-Fe-Sb angles and the height of Sb from the Fe plane are strikingly different for CuFeSb than the equivalent parameters in other members of the same family thereby explaining the origin of the unique ground state of CuFeSb.

  16. Fragmentation of HCl following excitation at the chlorine K edge

    SciTech Connect

    Hansen, D.L.; Arrasate, M.E.; Cotter, J.P.

    1997-04-01

    A space-focused time-of-flight (TOF) mass spectrometer was used to study the relaxation dynamics of HCl following excitation in the vicinity of the Cl-K edge ({approximately}2.8 keV) using x-rays from B.L. 9.3.1. At the lowest resonant excitation to a {sigma}{sup *} antibonding orbital (1{sigma} {r_arrow} 6{sigma}), a significant fraction of the excited molecules decay by emission of a neutral H atom. While neutral-H emission has been observed for shallow core levels (e.g., Cl 2p in HCl), the authors believe this to be the first observation of neutral-atom emission as a significant decay channel following resonant excitation of a deep core hole. The dissociation of neutral hydrogen atoms raises the issue of how effectively dissociation competes with Auger decay in the relaxation of these deep core levels (i.e., Cl 1s). Graphical evidence is presented to support the dissociation agrument. In addition, trends in fractional ion yields from Photo-Ion Photo-Ion COincidence (PIPICO) spectra suggest the presence of post-collision interaction (PCI). While, electron spectroscopy studies are required to confirm the observation of this effect, the authors believe this to be the first evidence of PCI moderated dissociation in molecules.

  17. Phosphorus K-edge XANES spectroscopy of mineral standards

    PubMed Central

    Ingall, Ellery D.; Brandes, Jay A.; Diaz, Julia M.; de Jonge, Martin D.; Paterson, David; McNulty, Ian; Elliott, W. Crawford; Northrup, Paul

    2011-01-01

    Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was performed on phosphate mineral specimens including (a) twelve specimens from the apatite group covering a range of compositional variation and crystallinity; (b) six non-apatite calcium-rich phosphate minerals; (c) 15 aluminium-rich phosphate minerals; (d) ten phosphate minerals rich in either reduced iron or manganese; (e) four phosphate minerals rich in either oxidized iron or manganese; (f) eight phosphate minerals rich in either magnesium, copper, lead, zinc or rare-earth elements; and (g) four uranium phosphate minerals. The identity of all minerals examined in this study was independently confirmed using X-ray powder diffraction. Minerals were distinguished using XANES spectra with a combination of pre-edge features, edge position, peak shapes and post-edge features. Shared spectral features were observed in minerals with compositions dominated by the same specific cation. Analyses of apatite-group minerals indicate that XANES spectral patterns are not strongly affected by variations in composition and crystallinity typical of natural mineral specimens. PMID:21335905

  18. Phosphorus K-edge XANES Spectroscopy of Mineral Standards

    SciTech Connect

    E Ingall; J Brandes; J Diaz; M de Jonge; D Paterson; I McNulty; C Elliott; P Northrup

    2011-12-31

    Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was performed on phosphate mineral specimens including (a) twelve specimens from the apatite group covering a range of compositional variation and crystallinity; (b) six non-apatite calcium-rich phosphate minerals; (c) 15 aluminium-rich phosphate minerals; (d) ten phosphate minerals rich in either reduced iron or manganese; (e) four phosphate minerals rich in either oxidized iron or manganese; (f) eight phosphate minerals rich in either magnesium, copper, lead, zinc or rare-earth elements; and (g) four uranium phosphate minerals. The identity of all minerals examined in this study was independently confirmed using X-ray powder diffraction. Minerals were distinguished using XANES spectra with a combination of pre-edge features, edge position, peak shapes and post-edge features. Shared spectral features were observed in minerals with compositions dominated by the same specific cation. Analyses of apatite-group minerals indicate that XANES spectral patterns are not strongly affected by variations in composition and crystallinity typical of natural mineral specimens.

  19. Mn K-edge XANES study of the La1-xCaxMnO3 colossal magnetoresistive manganites

    NASA Astrophysics Data System (ADS)

    Ignatov, A. Yu.; Ali, N.; Khalid, S.

    2001-07-01

    We report Mn K-edge x-ray absorption near edge structure (XANES) calculations of the La1-xCaxMnO3 manganites considering three pair correlations, according to the three fundamental degrees of freedom governing their unusual electronic properties, namely, the electronic structure of the unoccupied states probed by the Mn K-edge profile versus (i) local atomic distortions; (ii) local magnetic ordering; and (iii) the charge-transfer nature of the Mn-O bonds. The calculations are accompanied by Mn K-edge XANES measurements in the temperature range 30-300 K. The main features of the absorption edge can be qualitatively reproduced in terms of single-electron multiple-scattering calculations for an 87-atom cluster. Lattice polaronic distortions in La0.7Ca0.3MnO3 are simulated assuming a strongly distorted orthorhombic structure above and an almost undistorted rhombohedral structure below Tc. The results roughly reproduce the energy ``shift'' across Tc observed experimentally. Mn K-edge spin-polarized XANES spectra of the x=0, 0.3, and 1 samples are presented. An energy splitting between the majority- and minority-spin spectra of 0.5-1.1 eV contributes to the total XANES broadening below the Néel (Curie) temperature. A small feature B3 standing approximately 6 eV above the main absorption peak is beyond the scope of single-electron calculations; it is assigned to a shake-up transition. To illustrate, the calculated Mn K edge is obtained as the convolution product of the single-electron XANES and the spectrum of many-body excitations in the Mn-O electronic states upon the sudden switching on of the Mn 1s core hole. We investigate the charge-transfer (CT) versus. Mott-Hubbard-type ground state using the Ud, Δ, and the Tdp parameters determined by previous Mn 2p x-ray photoemission spectroscopy measurements and find that LaMnO3 should be viewed as a CT-type insulator with a substantial O 2p component in the ground state. In light of these results the controversial issue of

  20. Influence of Optical Properties on the Spin Polarization of Cu3P Photoelectrons

    NASA Astrophysics Data System (ADS)

    Chassé, A.; Niebergall, L.

    We have investigated the influence of optical properties of Cu(001) on the spin polarization in Cu3p photoelectron diffraction patterns. The refraction and absorption of light have been taken into account in the calculation of the dipole transition matrix element. Therefore, a general polarization vector of light is defined within a macroscopic theory of electromagnetic fields. Results are shown and discussed for Cu3p photoelectrons excited by linearly or circularly polarized light, respectively. It is shown that the optical behavior of crystals may cause a symmetry breaking in the angular dependence of the photoelectron intensity. Besides, there are strong quantitative changes in the related spin polarization of Cu3p photoelectrons.

  1. Spin polarization gives rise to Cu precipitation in Fe-matrix.

    PubMed

    Song, Wen-xiong; Zhao, Shi-jin

    2014-04-28

    This article tries to uncover the physical reason of Cu precipitation from an Fe matrix at the electronic level. The general rule is obtained that the more bonds among Cu atoms, the more stable the system is. It was shown that Cu would precipitate from the matrix with Fe spin-polarization but not without spin-polarization. The partial density of states (PDOS) analysis illustrated that the d states of Fe near the Fermi level potentially have strong interaction with other atoms, but Cu d states below the Fermi level lack this potential, which results in weak covalent d orbital interaction between Fe and Cu. Furthermore, the charge density difference also confirmed the weaker bond between Fe and Cu with spin-polarization compared to without spin-polarization, due to the decreased charge between them. In addition, the {110} interface energy between Fe and Cu, estimated by the "dangling bond", is 676.3 mJ m(-2), which agrees with the DFT calculation, 414.2 mJ m(-2). Finally, this study also revealed that Ni atoms can reduce the "dangling bond" when it locates at the interface and separates Fe and Cu.

  2. Optical XAFS of ZnO Nanowires at the Zn K-Edge and Related Phenomena

    SciTech Connect

    Heigl, F.; Sun, X.H.J; Lam, S.; Sham, T.K.; Gordon, R.; Brewe, D.; Rosenberg, R.; Shenoy, G.; Yablonskikh, M.; MacNaughton, J.; Moewes, A.

    2008-10-06

    We report x-ray excited optical luminescence (XEOL) from one-dimensional nanostructures of ZnO excited with photon energies across the Zn K-edge. The optical luminescence shows an UV and a green emission band characteristic of near band edge and defect emission, respectively. The optical channels were used in turn to monitor the Zn K-edge XAFS to high k values. The densities of states of oxygen character in the valence band were also studied with x-ray emission spectroscopy (XES). The Zn K-edge decay dynamics was examined with time-resolved x-ray excited optical luminescence.

  3. Application of X-ray K-edge densitometry in D and D operations

    SciTech Connect

    Jensen, T.; Aljundi, T.; Gray, J.N. |

    1998-12-31

    K-edge densitometry is a nondestructive assay technique which provides accurate measurement of heavy metal contamination in pipes, containers, and other items encountered in D and D operations. A prototype mobile K-edge instrument has been built and demonstrated in several applications. Results from measurements of uranium in pipes and spent reactor fuel plates, and quantification of mercury and lead in waste drums are presented. In this report the authors briefly describe the theory behind K-edge densitometry. They follow that with a description of the prototype system they have developed, and a presentation of results from demonstrations of this system. They conclude with a discussion of the potential for application of K-edge analysis in D and D operations.

  4. Simultaneous x-ray fluorescence and K-edge CT imaging with photon-counting detectors

    NASA Astrophysics Data System (ADS)

    Li, Liang; Li, Ruizhe; Zhang, Siyuan; Chen, Zhiqiang

    2016-10-01

    Rapid development of the X-ray phonon-counting detection technology brings tremendous research and application opportunities. In addition to improvements in conventional X-ray imaging performance such as radiation dose utilization and beam hardening correction, photon-counting detectors allows significantly more efficient X-ray fluorescence (XRF) and K-edge imaging, and promises a great potential of X-ray functional, cellular and molecular imaging. XRF is the characteristic emission of secondary X-ray photons from a material excited by initial X-rays. The phenomenon is widely used for chemical and elemental analysis. K-edge imaging identifies a material based on its chemically-specific absorption discontinuity over X-ray photon energy. In this paper, we try to combine XRF and K-edge signals from the contrast agents (e.g., iodine, gadolinium, gold nanoparticles) to simultaneously realize XFCT and K-edge CT imaging for superior image performance. As a prerequisite for this dual-modality imaging, the accurate energy calibration of multi-energy-bin photon-counting detectors is critically important. With the measured XRF data of different materials, we characterize the energy response function of a CZT detector for energy calibration and spectrum reconstruction, which can effectively improve the energy resolution and decrease the inconsistence of the photon counting detectors. Then, a simultaneous K-edge and X-ray fluorescence CT imaging (SKYFI) experimental setup is designed which includes a cone-beam X-ray tube, two separate photon counting detector arrays, a pin-hole collimator and a rotation stage. With a phantom containing gold nanoparticles the two types of XFCT and K-edge CT datasets are collected simultaneously. Then, XFCT and K-edge CT images are synergistically reconstructed in a same framework. Simulation results are presented and quantitative analyzed and compared with the separate XFCT and K-edge CT results.

  5. Interpretation of O K-edge EELS in zircon using a structural variation approach

    SciTech Connect

    Spence, John C.H; Jiang, Nan

    2009-12-01

    This work describes an approach to interpret the near-edge fine structure of electron energy-loss spectroscopy (EELS) of O K-edge in zircon using a structural variation method. The positions and intensities of several peaks in the O K-edge EELS spectrum are assigned to specific structural parameters. It suggests that the near-edge structures in EELS can be used to measure atomic structure changes.

  6. Interpretation of O K-edge EELS in zircon using a structural variation approach.

    PubMed

    Jiang, Nan; Spence, John C H

    2009-12-01

    This work describes an approach to interpret the near-edge fine structure of electron energy-loss spectroscopy (EELS) of O K-edge in zircon using a structural variation method. The positions and intensities of several peaks in the O K-edge EELS spectrum are assigned to specific structural parameters. It suggests that the near-edge structures in EELS can be used to measure atomic structure changes.

  7. Field demonstration of a portable, X-ray, K-edge heavy-metal detector

    SciTech Connect

    Jensen, T.; Aljundi, T.; Whitmore, C.; Zhong, H.; Gray, J.N.

    1997-03-31

    Under the Characterization, Monitoring, and Sensor Technology Crosscutting Program, the authors have designed and built a K-edge heavy metal detector that measures the level of heavy metal contamination inside closed containers in a nondestructive, non-invasive way. The device employs a volumetric technique that takes advantage of the X-ray absorption characteristics of heavy elements, and is most suitable for characterization of contamination inside pipes, processing equipment, closed containers, and soil samples. The K-edge detector is a fast, efficient, and cost-effective in situ characterization tool. More importantly, this device will enhance personnel safety while characterizing radioactive and toxic waste. The prototype K-edge system was operated at the Materials and Chemistry Laboratory User Facility at the Oak Ridge K-25 Site during February 1997. Uranium contaminated pipes and valves from a UF{sub 6} feed facility were inspected using the K-edge technique as well as a baseline nondestructive assay method. Operation of the K-edge detector was demonstrated for uranium contamination ranging from 10 to 6,000 mg/cm{sup 2} and results from the K-edge measurements were found to agree very well with nondestructive assay measurements.

  8. Strong excitonic interactions in the oxygen K-edge of perovskite oxides.

    PubMed

    Tomita, Kota; Miyata, Tomohiro; Olovsson, Weine; Mizoguchi, Teruyasu

    2017-07-01

    Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO3, SrTiO3, and BaTiO3, together with reference oxides, MgO, CaO, SrO, BaO, and TiO2, were investigated using a first-principles Bethe-Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti-O-Ti bonds. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Temperature and radiation effects at the fluorine K-edge in LiF

    DOE PAGES

    Schwartz, Craig P.; Ponce, Francisco; Friedrich, Stephan; ...

    2017-05-30

    Here, the fluorine K-edge of LiF is studied both experimentally and theoretically as a function of temperature. Instantaneous thermal fluctuations in atomic positions are shown in molecular dynamics simulations to increase in amplitude from 0.029 to 0.064 nm in the temperature range from 40 to 298 K. This is sufficient to cause instantaneous deviations from local octahedral atomic symmetry in this rock-salt crystal, resulting in altered electronic structure. The lowered symmetry of the lowest core-excited states of fluorine atoms is evident in X-ray absorption spectra at the F K-edge. In addition, sufficient radiation exposure produces a new X-ray absorption peak,more » below the F K-edge of LiF, which is assigned to defects in LiF based on both calculations and comparison to previous experiments.« less

  10. K-edge ratio method for identification of multiple nanoparticulate contrast agents by spectral CT imaging

    PubMed Central

    Ghadiri, H; Ay, M R; Shiran, M B; Soltanian-Zadeh, H

    2013-01-01

    Objective: Recently introduced energy-sensitive X-ray CT makes it feasible to discriminate different nanoparticulate contrast materials. The purpose of this work is to present a K-edge ratio method for differentiating multiple simultaneous contrast agents using spectral CT. Methods: The ratio of two images relevant to energy bins straddling the K-edge of the materials is calculated using an analytic CT simulator. In the resulting parametric map, the selected contrast agent regions can be identified using a thresholding algorithm. The K-edge ratio algorithm is applied to spectral images of simulated phantoms to identify and differentiate up to four simultaneous and targeted CT contrast agents. Results: We show that different combinations of simultaneous CT contrast agents can be identified by the proposed K-edge ratio method when energy-sensitive CT is used. In the K-edge parametric maps, the pixel values for biological tissues and contrast agents reach a maximum of 0.95, whereas for the selected contrast agents, the pixel values are larger than 1.10. The number of contrast agents that can be discriminated is limited owing to photon starvation. For reliable material discrimination, minimum photon counts corresponding to 140 kVp, 100 mAs and 5-mm slice thickness must be used. Conclusion: The proposed K-edge ratio method is a straightforward and fast method for identification and discrimination of multiple simultaneous CT contrast agents. Advances in knowledge: A new spectral CT-based algorithm is proposed which provides a new concept of molecular CT imaging by non-iteratively identifying multiple contrast agents when they are simultaneously targeting different organs. PMID:23934964

  11. SR high-speed K-edge subtraction angiography in the small animal (abstract)

    NASA Astrophysics Data System (ADS)

    Takeda, T.; Akisada, M.; Nakajima, T.; Anno, I.; Ueda, K.; Umetani, K.; Yamaguchi, C.

    1989-07-01

    To assess the ability of the high-speed K-edge energy subtraction system which was made at beamline 8C of Photon Factory, Tsukuba, we performed an animal experiment. Rabbits were used for the intravenous K-edge subtraction angiography. In this paper, the actual images of the artery obtained by this system, are demonstrated. The high-speed K-edge subtraction system consisted of movable silicon (111) monocrystals, II-ITV, and digital memory system. Image processing was performed by 68000-IP computer. The monochromatic x-ray beam size was 50×60 mm. Photon energy above and below iodine K edge was changed within 16 ms and 32 frames of images were obtained sequentially. The rabbits were anaesthetized by phenobarbital and a 5F catheter was inserted into inferior vena cava via the femoral vein. 1.5 ml/kg of contrast material (Conlaxin H) was injected at the rate of 0.5 ml/kg/s. TV images were obtained 3 s after the starting point of injection. By using this system, the clear K-edge subtracted images were obtained sequentially as a conventional DSA system. The quality of the images were better than that obtained by DSA. The dynamical blood flow was analyzed, and the best arterial image could be selected from the sequential images. The structures of aortic arch, common carotid arteries, right subclavian artery, and internal thoracic artery were obtained at the chest. Both common carotid arteries and vertebral arteries were recorded at the neck. The diameter of about 0.3-0.4 mm artery could be clearly revealed. The high-speed K-edge subtraction system demonstrates the very sharp arterial images clearly and dynamically.

  12. The enhanced spontaneous dielectric polarization in Ga doped CuFeO{sub 2}

    SciTech Connect

    Shi, Liran; Wei, Meng; Huang, Junwei; Chen, Borong; Shang, Cui; Xia, Zhengcai Long, Zhuo; Ouyang, Zhongwen; Xia, Nianming

    2014-11-07

    The magnetic and dielectric polarization properties of the single crystal samples of CuFe{sub 1−x}Ga{sub x}O{sub 2} (x = 0 and 0.02) are investigated. Experimental results show that the magnetization and dielectric polarizations are anisotropy and coupled together. Compared with pure CuFeO{sub 2}, in the case with the magnetic field parallel to the c axis, a field-induced phase transition with a hysteresis is clearly observed between the five-sublattice (5SL) and three-sublattice (3SL) phases. Specially, an obvious spontaneous dielectric polarization is observed in CuFe{sub 0.98}Ga{sub 0.02}O{sub 2} in a lower magnetic field region, indicating that the Ga doping has an effect on the enhancement of spontaneous dielectric polarization. Based on the dilution effect, change of exchange interaction, and partial release of the spin frustration due to the structural modulation of the Ga ion dopant, the origin of the magnetization, and spontaneous polarization characteristics are discussed and the complete dielectric polarization diagrams are assumed.

  13. Mammographic x-ray unit kilovoltage test tool based on k-edge absorption effect.

    PubMed

    Napolitano, Mary E; Trueblood, Jon H; Hertel, Nolan E; David, George

    2002-09-01

    A simple tool to determine the peak kilovoltage (kVp) of a mammographic x-ray unit has been designed. Tool design is based on comparing the effect of k-edge discontinuity of the attenuation coefficient for a series of element filters. Compatibility with the mammography accreditation phantom (MAP) to obtain a single quality control film is a second design objective. When the attenuation of a series of sequential elements is studied simultaneously, differences in the absorption characteristics due to the k-edge discontinuities are more evident. Specifically, when the incident photon energy is higher than the k-edge energy of a number of the elements and lower than the remainder, an inflection may be seen in the resulting attenuation data. The maximum energy of the incident photon spectra may be determined based on this inflection point for a series of element filters. Monte Carlo photon transport analysis was used to estimate the photon transmission probabilities for each of the sequential k-edge filter elements. The photon transmission corresponds directly to optical density recorded on mammographic x-ray film. To observe the inflection, the element filters chosen must have k-edge energies that span a range greater than the expected range of the end point energies to be determined. For the design, incident x-ray spectra ranging from 25 to 40 kVp were assumed to be from a molybdenum target. Over this range, the k-edge energy changes by approximately 1.5 keV between sequential elements. For this design 21 elements spanning an energy range from 20 to 50 keV were chosen. Optimum filter element thicknesses were calculated to maximize attenuation differences at the k-edge while maintaining optical densities between 0.10 and 3.00. Calculated relative transmission data show that the kVp could be determined to within +/-1 kV. To obtain experimental data, a phantom was constructed containing 21 different elements placed in an acrylic holder. MAP images were used to determine

  14. Magnetic circular x-ray dichroisms of Fe-Ni alloys at K edge.

    SciTech Connect

    Freeman, A. J.; Gofron, K. J.; Kimball, C. W.; Lee, P. L.; Montano, P. A.; Rao, F.; Wang, X.

    1997-04-03

    Magnetic Circular X-ray Dichroism (MCXD) studies at K edges of Fe-Ni alloys reveal changes of the MCXD signal with composition and crystal structure. We observe that the signal at the invar composition is of comparable strength as other compositions. Moreover, the edge position is strongly dependent on lattice constant. First principles calculations demonstrate that the shape and strength of the signal strongly depends on the crystal orientation, composition, and lattice constant. We find direct relation between the MCXD signal and the p DOS. We find that the MCXD at K edge probes the magnetism due to itinerant electrons.

  15. Dispersion corrections of the copper K edge measured by Fresnel diffraction.

    PubMed

    Lee, Wah-Keat; Cloetens, Peter; Schlenker, Michel

    2004-01-01

    Dispersion corrections to the atomic scattering factors for the copper K edge have been measured by a new technique, Fresnel diffraction. Fresnel diffraction fringes were measured at several sample-detector distances as a function of energy across the copper K-absorption edge. The dispersion corrections were obtained from optimizing a least-squares fit of Fresnel fringe simulations to the measured data.

  16. Ion yields for tetramethylgermane exposed to x-rays near the Ge K-edge

    SciTech Connect

    Holroyd, R.A.; Preses, J.M.; Sham, T.K.

    2000-03-30

    Free ion yields were measured for tetramethylgermane (TMG) in both the liquid and vapor phase and for Kr gas exposed to X-rays. The X-ray energy was varied across the K-edges of Ge and Kr, respectively. In Kr the relative W value increases slightly at the K-edge, which is at 14.3 keV. In liquid TMG the observed ion yield drops at the Ge K-edge (11.1 keV) and shows two minima separated by 10 eV. This ion-yield spectrum is a mirror image of the absorption spectrum, as represented by the gas-phase ion-yield spectrum. The observation of such an inverted spectrum in liquids is shown to be due in large part to inefficiency of collection of charges. This is a consequence of the large Ge cross sections above the edge which concentrates the region of irradiation near the entrance window, increasing the local dose rate and enhancing recombination. The yield of excited states in mixtures of TMG and toluene drops at the Ge K-edge by the amount expected considering the large X-ray fluorescence yield.

  17. Depth Profile of Induced Magnetic Polarization in Cu Layers of Co/Cu(111) Metallic Superlattices by Resonant X-ray Magnetic Scattering at the Cu K Absorption Edge

    NASA Astrophysics Data System (ADS)

    Uegaki, Shin; Yoshida, Akihiro; Hosoito, Nobuyoshi

    2015-03-01

    We investigated induced spin polarization of 4p conduction electrons in Cu layers of antiferromagnetically (AFM) and ferromagnetically (FM) coupled Co/Cu(111) metallic superlattices by resonant X-ray magnetic scattering at the Cu K absorption edge. Magnetic reflectivity profiles of the two superlattices were measured in the magnetic saturation state with circularly polarized synchrotron radiation X-rays at 8985 eV. Depth profiles of the resonant magnetic scattering length of Cu, which corresponds to the induced spin polarization of Cu, were evaluated in the two Co/Cu superlattices by analyzing the observed magnetic reflectivity profiles. We demonstrated that the spin polarization induced in the Cu layer was distributed around the Co/Cu interfaces with an attenuation length of several Å in both AFM and FM coupled superlattices. The uniform component, which exists in Au layers of Fe/Au(001) superlattices, was not found in the depth distribution of induced magnetic polarization in the Cu layers of Co/Cu(111) superlattices.

  18. Self-Assembly of Glycine on Cu (001): The tale of Temperature and Polarity

    NASA Astrophysics Data System (ADS)

    Xu, Lifang; Xu, Jing; Lin, Zheshuai; Meng, Sheng; Wang, Enge

    Glycine on Cu(001) is used as an example to illustrate the critical role of molecular polarity and finite temperature effect in self-assembly of bio-molecules at a metal surface. A unified picture for glycine self-assembly on Cu(001) is derived based on full polarity compensation considerations. Temperature plays a non-trivial role: the ground-state structure at 0 K is absent at room temperature, where intermolecular hydrogen bonding overweighs competing molecule-substrate interactions. The unique p(2×4) structure predicted as the most stable structure was confirmed by ab initio molecular dynamics simulations, whose scanning tunneling microscopy images and anisotropic free-electron-like dispersion are in excellent agreement with experiments. Moreover, the rich self-assembling patterns including the heterochiral and homochiral phases, and their interrelationships are entirely governed by the same mechanism.

  19. Photon counting spectral CT: improved material decomposition with K-edge-filtered x-rays

    NASA Astrophysics Data System (ADS)

    Shikhaliev, Polad M.

    2012-03-01

    Photon counting spectral computed tomography (PCSCT) provides material selective CT imaging at a single CT scan and fixed tube voltage. The PCSCT data are acquired in several energy ranges (bins) arranged over the x-ray spectrum. The quasi-monoenergetic CT images are acquired in these energy bins and are used for material decomposition. The PCSCT exhibits inherent limitations when material decomposition is performed using energy bins. For effective material decomposition, the energy bins used for material decomposition should be sufficiently narrow and well separated. However, when narrow bins are used, a large fraction of the detected x-ray counts is lost and statistical noise is increased. Alternatively, the x-ray spectrum can be split into a few larger bins with no gap in between and all detected x-ray photons can be used for material decomposition. However, in this case the energy bins are too wide and not well separated, which results in suboptimal material decomposition. The above contradictory requirements can be resolved if the x-ray photons are physically removed from the regions of the energy spectrum between the energy bins. Such a selective removal can be performed using filtration of the x-ray beam by high-Z filter materials with appropriate positions of K-edge energies. The K-edge filtration of x-rays can, therefore, provide necessary gaps between the energy bins with no dose penalty to the patient. In the current work, we proposed using selective K-edge filtration of x-rays in PCSCT and performed the first experimental investigation of this approach. The PCSCT system included a cadmium zinc telluride semiconductor detector with 2 × 256 pixels and 1 × 1 mm2 pixel size, and five energy bins. The CT phantom had 14 cm diameter and included contrast elements of iodine, gold and calcifications with clinically relevant concentrations. The tube voltages of 60, 90 and 120 kVp were used. K-edge filters based on Ba (Ek = 37.44 keV) were used for a 60 kVp tube

  20. Real time /ital K/-edge subtraction x-ray imaging

    SciTech Connect

    Fukagawa, H.; Noda, C.; Suzuki, Y.; Hasegawa, S.; Ando, M.; Hyodo, K.; Nishimura, K.; Akisada, M.; Takenaka, E.; Hosaka, R.; and others

    1989-07-01

    This paper describes an x-ray /ital K/-edge subtraction television system for noninvasive angiography utilizing synchrotron radiation. The phantom, including contrast material (iodine), is irradiated by monochromatized dual-energy x-ray flux, alternately, using a high speed monochromator. The monochromator consists of a silicon crystal plate vibrating at 15 Hz so that the phantom is irradiated by the x-ray flux of 150 eV above and below the /ital K/-edge photon energy of iodine, 15 times per second. As an x-ray detector, TV cameras optically coupled to an x-ray image intensifier are used and the video signal is processed to display the subtraction image of pairs of successive images in real time. This system was fully implemented and moving phantoms were examined. Both the time interval between the energy change and the exposure time of each image has been shortened to 2 ms.

  1. Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

    PubMed Central

    2014-01-01

    Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodology to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed. PMID:25492398

  2. Photon counting spectral CT: improved material decomposition with K-edge-filtered x-rays.

    PubMed

    Shikhaliev, Polad M

    2012-03-21

    Photon counting spectral computed tomography (PCSCT) provides material selective CT imaging at a single CT scan and fixed tube voltage. The PCSCT data are acquired in several energy ranges (bins) arranged over the x-ray spectrum. The quasi-monoenergetic CT images are acquired in these energy bins and are used for material decomposition. The PCSCT exhibits inherent limitations when material decomposition is performed using energy bins. For effective material decomposition, the energy bins used for material decomposition should be sufficiently narrow and well separated. However, when narrow bins are used, a large fraction of the detected x-ray counts is lost and statistical noise is increased. Alternatively, the x-ray spectrum can be split into a few larger bins with no gap in between and all detected x-ray photons can be used for material decomposition. However, in this case the energy bins are too wide and not well separated, which results in suboptimal material decomposition. The above contradictory requirements can be resolved if the x-ray photons are physically removed from the regions of the energy spectrum between the energy bins. Such a selective removal can be performed using filtration of the x-ray beam by high-Z filter materials with appropriate positions of K-edge energies. The K-edge filtration of x-rays can, therefore, provide necessary gaps between the energy bins with no dose penalty to the patient. In the current work, we proposed using selective K-edge filtration of x-rays in PCSCT and performed the first experimental investigation of this approach. The PCSCT system included a cadmium zinc telluride semiconductor detector with 2 × 256 pixels and 1 × 1 mm(2) pixel size, and five energy bins. The CT phantom had 14 cm diameter and included contrast elements of iodine, gold and calcifications with clinically relevant concentrations. The tube voltages of 60, 90 and 120 kVp were used. K-edge filters based on Ba (E(k) = 37.44 keV) were used for a 60 k

  3. Hybrid-K-edge/X-ray Fluorescense Densitometry with Laser-Compton Scattered X-rays

    SciTech Connect

    Dr. Khalid Chouffani El Fassi

    2010-08-29

    The quantitative verification of the accountancy of fissile nuclear materials through independent measurements represents one of the key elements of nuclear materials Safeguards. Elemental probes of materials of interest to non-proliferation are critical to research strategy in order to identify sensitive advanced instrumentation detection technologies. Advanced instrumentation for material detection and accountability are needed for use in fuel cycle facilities for real-time in-process monitoring of separations-partitioning, fuels fabrication as well as for traditional safeguards activities. Radiation-based NDA (non-destructive analysis) techniques can provide some vital information about nuclear materials much more quickly, cheaply and safely than chemical or radio chemical analysis. Hybrid K-edge densitometry (HKED) is currently the most accurate nondestructive inspection technique that provides sensitive quantification of heavy metal contamination. HKED in a technique that exploits both K-edge absorption and X-ray fluorescence (XRF) and allows simultaneously greater elemental specificity and lower detection limits

  4. Phosphorus Speciation of Forest-soil Organic Surface Layers using P K-edge XANES Spectroscopy

    SciTech Connect

    J Prietzel; J Thieme; D Paterson

    2011-12-31

    The phosphorus (P) speciation of organic surface layers from two adjacent German forest soils with different degree of water-logging (Stagnosol, Rheic Histosol) was analyzed by P K-edge XANES and subsequent Linear Combination Fitting. In both soils, {approx}70% of the P was inorganic phosphate and {approx}30% organic phosphate; reduced P forms such as phosphonate were absent. The increased degree of water-logging in the Histosol compared to the Stagnosol did not affect P speciation.

  5. Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

    DOE PAGES

    Martin-Diaconescu, Vlad; Gennari, Marcello; Gerey, Bertrand; ...

    2014-12-10

    Calcium K-edge pre-edges coupled with TD-DFT theoretical calculation of spectra provide a powerful approach for the characterization of complex calcium centers in inorganic and bioinorganic chemistry. Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodologymore » to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.« less

  6. Standard Protocol and Quality Assessment of Soil Phosphorus Speciation by P K-Edge XANES Spectroscopy.

    PubMed

    Werner, Florian; Prietzel, Jörg

    2015-09-01

    Phosphorus (P) in soils is most often bound as phosphate to one or more of the following four elements or compounds: calcium, aluminum, iron, and soil organic matter. A promising method for direct P speciation in soils is synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy at the K-edge of P. However, the quality of this method is debated controversially, partly because a standard protocol for reproducible spectrum deconvolution is lacking and minor modifications of the applied deconvolution procedure can lead to considerable changes in the P speciation results. On the basis of the observation that appropriate baseline correction and edge-step normalization are crucial for correct linear combination (LC) fitting results, we established a standard protocol for the deconvolution and LC fitting of P K-edge XANES spectra. We evaluated the quality of LC fits obtained according to this standard protocol with 16 defined dilute (2 mg P g(-1)) ternary mixtures of aluminum phosphate, iron phosphate, hydroxyapatite, and phytic acid in a quartz matrix. The LC fitting results were compared with the contribution of the different P compounds to total P in the various mixtures. Compared to using a traditional LC fitting procedure, our standard protocol reduced the fitting error by 6% (absolute). However, P portions smaller than 5% should be confirmed with other methods or excluded from the P speciation results. A publicly available database of P K-edge XANES reference spectra was initiated.

  7. Energy-Discriminating Gadolinium K-Edge X-ray Computed Tomography System

    NASA Astrophysics Data System (ADS)

    Matsukiyo, Hiroshi; Watanabe, Manabu; Sato, Eiichi; Osawa, Akihiro; Enomoto, Toshiyuki; Nagao, Jiro; Abderyim, Purkhet; AIzawa, Katsuo; Hitomi, Keitaro; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Ogawa, Akira; Takahashi, Kiyomi; Sato, Shigehiro; Onagawa, Jun

    2010-02-01

    An energy-discriminating K-edge X-ray computed tomography (CT) system is useful for increasing the contrast resolution of a target region utilizing contrast media and for reducing the absorbed dose for patients. The CT system is of the first-generation type of detector using cadmium telluride (CdTe). CT is performed by repeated translations and rotations of an object. Penetrating X-ray photons from the object are detected by a CdTe detector, and event signals of X-ray photons are produced using charge-sensitive and shaping amplifiers. Both photon energy and energy width are selected out using a multichannel analyzer, and the number of photons is counted by a countercard. To perform energy discrimination, a low-dose-rate X-ray generator for photon counting was developed. Its maximum tube voltage and minimum tube current were 110 kV and 1 µA, respectively. In energy-discriminating CT, the tube voltage and tube current were 100 kV and 20 µA, respectively, and the X-ray intensity was 2.98 µGy/s at a distance of 1.0 m from the source and a tube voltage of 100 kV. The demonstration of enhanced gadolinium K-edge X-ray CT was carried out by selecting photons with energies just beyond the gadolinium K-edge energy of 50.3 keV.

  8. Energy-Discriminating Gadolinium K-Edge X-ray Computed Tomography System

    NASA Astrophysics Data System (ADS)

    Hiroshi Matsukiyo,; Manabu Watanabe,; Eiichi Sato,; Akihiro Osawa,; Toshiyuki Enomoto,; Jiro Nagao,; Purkhet Abderyim,; Katsuo AIzawa,; Keitaro Hitomi,; Etsuro Tanaka,; Hidezo Mori,; Toshiaki Kawai,; Akira Ogawa,; Kiyomi Takahashi,; Shigehiro Sato,; Jun Onagawa,

    2010-02-01

    An energy-discriminating K-edge X-ray computed tomography (CT) system is useful for increasing the contrast resolution of a target region utilizing contrast media and for reducing the absorbed dose for patients. The CT system is of the first-generation type of detector using cadmium telluride (CdTe). CT is performed by repeated translations and rotations of an object. Penetrating X-ray photons from the object are detected by a CdTe detector, and event signals of X-ray photons are produced using charge-sensitive and shaping amplifiers. Both photon energy and energy width are selected out using a multichannel analyzer, and the number of photons is counted by a countercard. To perform energy discrimination, a low-dose-rate X-ray generator for photon counting was developed. Its maximum tube voltage and minimum tube current were 110 kV and 1 μA, respectively. In energy-discriminating CT, the tube voltage and tube current were 100 kV and 20 μA, respectively, and the X-ray intensity was 2.98 μGy/s at a distance of 1.0 m from the source and a tube voltage of 100 kV. The demonstration of enhanced gadolinium K-edge X-ray CT was carried out by selecting photons with energies just beyond the gadolinium K-edge energy of 50.3 keV.

  9. K-edge x-ray absorption spectra of Cs and Xe

    SciTech Connect

    Gomilsek, J. Padeznik; Kodre, A.; Arcon, I.; Hribar, M.

    2003-10-01

    X-ray absorption spectrum of cesium vapor in the K-edge region is measured in a stainless steel cell. The spectrum is free of the x-ray absorption fine structure signal and shows small features analogous to those in the spectrum of the neighbor noble gas Xe. Although the large natural width of the K vacancy (>10 eV) washes out most of the details, fingerprints of multielectron excitations can be recognized at energies close to Dirac-Fock estimates of doubly excited states 1s4(d,p,s) and 1s3(d,p). Among these, the 1s3p excitation 1000 eV above the K edge in both spectra is the deepest double excitation observed so far. Within the K-edge profile, some resolution is recovered with numerical deconvolution of the spectra, revealing the coexcitation of the 5(p,s) electrons, and even the valence 6s electron in Cs. As in homologue elements, three-electron excitations, either as separate channels or as configuration admixtures are required to explain some spectral features in detail.

  10. Polarization memory in the nonpolar magnetic ground state of multiferroic CuFeO2

    NASA Astrophysics Data System (ADS)

    Beilsten-Edmands, J.; Magorrian, S. J.; Foronda, F. R.; Prabhakaran, D.; Radaelli, P. G.; Johnson, R. D.

    2016-10-01

    We investigate polarization memory effects in single-crystal CuFeO2, which has a magnetically induced ferroelectric phase at low temperatures and applied B fields between 7.5 and 13 T. Following electrical poling of the ferroelectric phase, we find that the nonpolar collinear antiferromagnetic ground state at B =0 T retains a strong memory of the polarization magnitude and direction, such that upon reentering the ferroelectric phase a net polarization of comparable magnitude to the initial polarization is recovered in the absence of external bias. This memory effect is very robust: in pulsed-magnetic-field measurements, several pulses into the ferroelectric phase with reverse bias are required to switch the polarization direction, with significant switching only seen after the system is driven out of the ferroelectric phase and ground state either magnetically (by application of B >13 T) or thermally. The memory effect is also largely insensitive to the magnetoelastic domain composition, since no change in the memory effect is observed for a sample driven into a single-domain state by application of stress in the [1 1 ¯0 ] direction. On the basis of Monte Carlo simulations of the ground-state spin configurations, we propose that the memory effect is due to the existence of helical domain walls within the nonpolar collinear antiferromagnetic ground state, which would retain the helicity of the polar phase for certain magnetothermal histories.

  11. Polarization dependent ferroelectric photovoltaic effects in BFTO/CuO thin films

    NASA Astrophysics Data System (ADS)

    Zhu, Mingsai; Zheng, Haiwu; Zhang, Ju; Yuan, Guoliang; Wang, Ke; Yue, Gentian; Li, Fengzhu; Chen, Yuanqing; Wu, Mengjun; Zhang, Weifeng

    2017-07-01

    Bi5FeTi3O15 (BFTO) and BFTO/CuO films were deposited by a sol-gel technique, which exhibited macroscopic ferroelectric properties. It was found that the BFTO/CuO films showed a short circuit photocurrent density (Jsc) enhanced by nearly 10 times and power conversion efficiency increased by 13-fold compared to those of the BFTO film. The significant increase in the photovoltaic (PV) response may be attributed to the p-n junction internal electric field acting as the driving force of photogenerated carriers. Furthermore, both BFTO and BFTO/CuO films indicated a switchable PV response in both polarities. The open circuit voltage (Voc) and Jsc for BFTO and BFTO/CuO were observed to be -0.59 V and +43.88 μA /cm2 and -0.23 V and +123.16 μA /cm2, respectively, after upward poling, whereas after downward poling, +0.11 V and -6.26 μA /cm2 and +0.17 V and -83.21 μA /cm2 for BFTO and BFTO/CuO were observed, respectively. The switchable PV responses were explained by the ferroelectric depolarization field, whose direction could be altered with the variation in the applied poling field. This work provides an efficient approach to developing ferroelectric film based PV devices with low cost.

  12. Communication: Near edge x-ray absorption fine structure spectroscopy of aqueous adenosine triphosphate at the carbon and nitrogen K-edges.

    PubMed

    Kelly, Daniel N; Schwartz, Craig P; Uejio, Janel S; Duffin, Andrew M; England, Alice H; Saykally, Richard J

    2010-09-14

    Near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the nitrogen and carbon K-edges was used to study the hydration of adenosine triphosphate in liquid microjets. The total electron yield spectra were recorded as a function of concentration, pH, and the presence of sodium, magnesium, and copper ions (Na(+)/Mg(2+)/Cu(2+)). Significant spectral changes were observed upon protonation of the adenine ring, but not under conditions that promote π-stacking, such as high concentration or presence of Mg(2+), indicating that NEXAFS is insensitive to the phenomenon. Intramolecular inner-sphere association of Cu(2+) did create observable broadening of the nitrogen spectrum, whereas outer-sphere association with Mg(2+) did not.

  13. Parameters Influencing Sulfur Speciation in Environmental Samples Using Sulfur K-Edge X-Ray Absorption Near-Edge Structure

    PubMed Central

    Pongpiachan, Siwatt; Thumanu, Kanjana; Kositanont, Charnwit; Schwarzer, Klaus; Prietzel, Jörg; Hirunyatrakul, Phoosak; Kittikoon, Itthipon

    2012-01-01

    This paper aims to enhance the credibility of applying the sulfur K-edge XANES spectroscopy as an innovative “fingerprint” for characterizing environmental samples. The sensitivities of sulfur K-edge XANES spectra of ten sulfur compound standards detected by two different detectors, namely, Lytle detector (LyD) and Germanium detector (GeD), were studied and compared. Further investigation on “self-absorption” effect revealed that the maximum sensitivities of sulfur K-edge XANES spectra were achieved when diluting sulfur compound standards with boron nitride (BN) at the mixing ratio of 0.1%. The “particle-size” effect on sulfur K-edge XANES spectrum sensitivities was examined by comparing signal-to-noise ratios of total suspended particles (TSP) and particulate matter of less than 10 millionths of a meter (PM10) collected at three major cities of Thailand. The analytical results have demonstrated that the signal-to-noise ratios of sulfur K-edge XANES spectra were positively correlated with sulfate content in aerosols and negatively connected with particle sizes. The combination of hierarchical cluster analysis (HCA) and principal component analysis (PCA) has proved that sulfur K-edge XANES spectrum can be used to characterize German terrestrial soils and Andaman coastal sediments. In addition, this study highlighted the capability of sulfur K-edge XANES spectra as an innovative “fingerprint” to distinguish tsunami backwash deposits (TBD) from typical marine sediments (TMS). PMID:23193498

  14. Spectral line shapes of U M2 - and As K -edge resonant x-ray scattering in the two antiferromagnetic phases of UAs

    NASA Astrophysics Data System (ADS)

    Normile, P. S.; Wilkins, S. B.; Detlefs, B.; Mannix, D.; Blackburn, E.; Bouchenoire, L.; Bernhoeft, N.; Lander, G. H.

    2007-05-01

    We present resonant x-ray scattering measurements on uranium arsenide at the U M2 and As K absorption edges. The studies at both edges relate to aspects of the hybridization (involving the 5f states) in UAs. At the U M2 edge, the spectral line shapes are found to differ between the two antiferromagnetic phases of UAs. In the “type-I” phase, the line shapes may be fitted using a single resonant component, whereas in the “type-IA” phase, a second resonant component, 3.5eV above the first component, is required to fit the line shapes in the rotated polarization (σ→π) scattering channel. The possibility that the single (first) component in the type-I (type-IA) phase corresponds to E2 scattering due to the ordered 5f magnetic-dipole moments and that in the type-IA phase the second component represents an E1 process involving polarized 6d (U) states is considered. Similar line shapes are observed for the two antiferromagnetic phases at the As K edge, a result which is in discordance with a recent theoretical prediction. The experimentally observed As K -edge line shape has an asymmetrical form in both phases, which possibly relates to As 4p -band effects unaccounted for in the theory.

  15. Photon counting x-ray imaging with K-edge filtered x-rays: A simulation study.

    PubMed

    Atak, Haluk; Shikhaliev, Polad M

    2016-03-01

    In photon counting (PC) x-ray imaging and computed tomography (CT), the broad x-ray spectrum can be split into two parts using an x-ray filter with appropriate K-edge energy, which can improve material decomposition. Recent experimental study has demonstrated substantial improvement in material decomposition with PC CT when K-edge filtered x-rays were used. The purpose of the current work was to conduct further investigations of the K-edge filtration method using comprehensive simulation studies. The study was performed in the following aspects: (1) optimization of the K-edge filter for a particular imaging configuration, (2) effects of the K-edge filter parameters on material decomposition, (3) trade-off between the energy bin separation, tube load, and beam quality with K-edge filter, (4) image quality of general (unsubtracted) images when a K-edge filter is used to improve dual energy (DE) subtracted images, and (5) improvements with K-edge filtered x-rays when PC detector has limited energy resolution. The PC x-ray images of soft tissue phantoms with 15 and 30 cm thicknesses including iodine, CaCO3, and soft tissue contrast materials, were simulated. The signal to noise ratio (SNR) of the contrast elements was determined in general and material-decomposed images using K-edge filters with different atomic numbers and thicknesses. The effect of the filter atomic number and filter thickness on energy separation factor and SNR was determined. The boundary conditions for the tube load and halfvalue layer were determined when the K-edge filters are used. The material-decomposed images were also simulated using PC detector with limited energy resolution, and improvements with K-edge filtered x-rays were quantified. The K-edge filters with atomic numbers from 56 to 71 and K-edge energies 37.4-63.4 keV, respectively, can be used for tube voltages from 60 to 150 kVp, respectively. For a particular tube voltage of 120 kVp, the Gd and Ho were the optimal filter materials

  16. Polarized Raman spectroscopy of Cu-poor and Zn-rich single-crystal Cu2ZnSnSe4

    NASA Astrophysics Data System (ADS)

    Nam, Dahyun; Kim, Jungcheol; Lee, Jae-Ung; Nagaoka, Akira; Yoshino, Kenji; Cha, Wonsuk; Kim, Hyunjung; Hwang, In Chul; Yoon, Kyung Byung; Cheong, Hyeonsik

    2014-10-01

    Cu2ZnSnSe4 (CZTSe) is a p-type semiconductor which has been developed as an absorber layer of polycrystalline thin film solar cells. Generally, Cu-poor and Zn-rich compositions tend to give the highest solar conversion efficiencies. Raman spectroscopy has been used to detect secondary phases such as ZnSe and Cu2SnSe3 in CZTSe thin films. However, the fundamental phonon modes in single-crystal CZTSe with a composition matching that of high-efficiency thin film solar cells have not yet been fully understood. We performed polarized Raman measurements on Cu-poor and Zn-rich single-crystal CZTSe and identified 12 peaks, including two low-frequency peaks. By comparing the polarization dependence of the Raman peaks with a group theoretical analysis, we concluded that the crystal structure of CZTSe single-crystal is kesterite and made appropriate peak assignments.

  17. Comparison of iodine K-edge subtraction and fluorescence subtraction imaging in an animal system

    NASA Astrophysics Data System (ADS)

    Zhang, H.; Zhu, Y.; Bewer, B.; Zhang, L.; Korbas, M.; Pickering, I. J.; George, G. N.; Gupta, M.; Chapman, D.

    2008-09-01

    K-Edge Subtraction (KES) utilizes the discontinuity in the X-ray absorption across the absorption edge of the selected contrast element and creates an image of the projected density of the contrast element from two images acquired just above and below the K-edge of the contrast element. KES has proved to be powerful in coronary angiography, micro-angiography, bronchography, and lymphatic imaging. X-ray fluorescence imaging is a successful technique for the detection of dilute quantities of elements in specimens. However, its application at high X-ray energies (e.g. at the iodine K-edge) is complicated by significant Compton background, which may enter the energy window set for the contrast material's fluorescent X-rays. Inspired by KES, Fluorescence Subtraction Imaging (FSI) is a technique for high-energy (>20 keV) fluorescence imaging using two different incident beam energies just above and below the absorption edge of a contrast element (e.g. iodine). The below-edge image can be assumed as a "background" image, which includes Compton scatter and fluorescence from other elements. The above-edge image will contain nearly identical spectral content as the below-edge image but will contain the additional fluorescence of the contrast element. This imaging method is especially promising with thick objects with dilute contrast materials, significant Compton background, and/or competing fluorescence lines from other materials. A quality factor is developed to facilitate the comparison. The theoretical value of the quality factor sets the upper limit that an imaging method can achieve when the noise is Poisson limited. The measured value of this factor makes two or more imaging methods comparable. Using the Hard X-ray Micro-Analysis (HXMA) beamline at the Canadian Light Source (CLS), the techniques of FSI and KES were critically compared, with reference to radiation dose, image acquisition time, resolution, signal-to-noise ratios, and quality factor.

  18. A Bremsstrahlung Spectrometer using k-edge and Differential Filters with Image plate dosimeters

    SciTech Connect

    Chen, C; Mackinnon, A; Beg, F; Chen, H; Key, M; King, J A; Link, A; MacPhee, A; Patel, P; Porkolab, M; Stephens, R; VanWoerkom, L; Akli, K; Freeman, R

    2008-05-02

    A Bremsstrahlung spectrometer using k-edge and differential filtering has been used with Image Plate dosimeters to measure the x-ray fluence from short-pulse laser/target interactions. An electron spectrometer in front of the Bremsstrahlung spectrometer deflects electrons from the x-ray line of sight and simultaneously measures the electron spectrum. The response functions were modeled with the Monte Carlo code Integrated Tiger Series 3.0 and the dosimeters calibrated with radioactive sources. Electron distributions with slope temperatures in the MeV range are inferred from the Bremsstrahlung spectra.

  19. A Bremsstrahlung spectrometer using k-edge and differential filters with image plate dosimeters

    SciTech Connect

    Chen, C. D.; Porkolab, M.; King, J. A.; Beg, F. N.; Key, M. H.; Chen, H.; Mackinnon, A. J.; MacPhee, A. G.; Patel, P. K.; Akli, K. U.; Stephens, R. B.; Freeman, R. R.; Link, A.; Van Woerkom, L. D.

    2008-10-15

    A Bremsstrahlung spectrometer using k-edge and differential filtering has been used with image plate dosimeters to measure the x-ray fluence from short-pulse laser/target interactions. An electron spectrometer in front of the Bremsstrahlung spectrometer deflects electrons from the x-ray line of sight and simultaneously measures the electron spectrum. The response functions were modeled with the Monte Carlo code INTEGRATED TIGER SERIES 3.0 and the dosimeters calibrated with radioactive sources. An electron distribution with a slope temperature of 1.3 MeV is inferred from the Bremsstrahlung spectra.

  20. X-ray, K-edge measurement of uranium concentration in reactor fuel plates

    SciTech Connect

    Jensen, T.; Aljundi, T.; Whitmore, C.; Zhong, H.; Gray, J.N.

    1997-11-26

    Under the Characterization, Monitoring, and Sensor Technology Crosscutting Program, the authors have designed and built a K-edge heavy-metal detector that measures the level of heavy-metal content inside closed containers in a nondestructive, non-invasive way. They have applied this technique to measurement of the amount of uranium in stacks of reactor fuel plates containing nuclear materials of different enrichments and alloys. They have obtained good agreement with expected uranium concentrations ranging from 60 mg/cm{sup 2} to 3,000 mg/cm{sup 2}, and have demonstrated that the instrument can operate in a high radiation field (> 200 mR/hr).

  1. Performance of the HERMES beamline at the carbon K-edge

    NASA Astrophysics Data System (ADS)

    Swaraj, S.; Belkhou, R.; Stanescu, S.; Rioult, M.; Besson, A.; Hitchcock, A. P.

    2017-06-01

    Contamination of soft X-rays beamline optics due to carbon cracking and deposition under X- ray irradiation is especially critical for spectromicroscopy operations near the carbon K-absorption edge from organic materials, polymers and nanoparticles. In this paper we present the strategy and procedure followed on the HERMES beamline (Synchrotron SOLEIL) to minimize carbon contamination of the beamline optics. Measurements on a complex organic test sample are reported to demonstrate the performance of the beamline at the carbon K-edge in imaging, spectroscopy and spectromicroscopy modes.

  2. Neutral dissociation of hydrogen following photoexcitation of HCl at the chlorine K edge

    SciTech Connect

    Hansen, D.L.; Arrasate, M.E.; Martin, R.; Vanderford, B.; Lindle, D.W.; Cotter, J.; Neill, P.; Fisher, G.R.; Perera, R.C.; Leung, K.T.; Levin, J.C.; Sellin, I.A.; Simon, M.; Simon, M.; Uehara, Y.; Whitfield, S.B.

    1998-04-01

    Time-of-flight mass spectroscopy was used to study the relaxation dynamics of HCl following photoexcitation in the vicinity of the Cl K edge ({approximately}2.8keV) using monochromatic synchrotron radiation. At the lowest resonant excitation to the 6{sigma}{sup {asterisk}} antibonding orbital, almost half of the excited molecules decay by emission of a neutral H atom, mostly in coincidence with a highly charged Cl{sup n+} ion. The present work demonstrates that neutral-atom emission can be a significant decay channel for excited states with very short lifetimes (1 fs). {copyright} {ital 1998} {ital The American Physical Society}

  3. Sensitivity of photon-counting based K-edge imaging in X-ray computed tomography.

    PubMed

    Roessl, Ewald; Brendel, Bernhard; Engel, Klaus-Jürgen; Schlomka, Jens-Peter; Thran, Axel; Proksa, Roland

    2011-09-01

    The feasibility of K-edge imaging using energy-resolved, photon-counting transmission measurements in X-ray computed tomography (CT) has been demonstrated by simulations and experiments. The method is based on probing the discontinuities of the attenuation coefficient of heavy elements above and below the K-edge energy by using energy-sensitive, photon counting X-ray detectors. In this paper, we investigate the dependence of the sensitivity of K-edge imaging on the atomic number Z of the contrast material, on the object diameter D , on the spectral response of the X-ray detector and on the X-ray tube voltage. We assume a photon-counting detector equipped with six adjustable energy thresholds. Physical effects leading to a degradation of the energy resolution of the detector are taken into account using the concept of a spectral response function R(E,U) for which we assume four different models. As a validation of our analytical considerations and in order to investigate the influence of elliptically shaped phantoms, we provide CT simulations of an anthropomorphic Forbild-Abdomen phantom containing a gold-contrast agent. The dependence on the values of the energy thresholds is taken into account by optimizing the achievable signal-to-noise ratios (SNR) with respect to the threshold values. We find that for a given X-ray spectrum and object size the SNR in the heavy element's basis material image peaks for a certain atomic number Z. The dependence of the SNR in the high- Z basis-material image on the object diameter is the natural, exponential decrease with particularly deteriorating effects in the case where the attenuation from the object itself causes a total signal loss below the K-edge. The influence of the energy-response of the detector is very important. We observed that the optimal SNR values obtained with an ideal detector and with a CdTe pixel detector whose response, showing significant tailing, has been determined at a synchrotron differ by factors of

  4. Theoretical calculations of x-ray-absorption spectra of copper in La2CuO4 and related oxide compounds

    NASA Astrophysics Data System (ADS)

    Guo, J.; Ellis, D. E.; Goodman, G. L.; Alp, E. E.; Soderholm, L.; Shenoy, G. K.

    1990-01-01

    We report the results of theoretical calculations of copper K-edge x-ray-absorption near-edge spectra (XANES) in La2CuO4 and related oxides Cu2O, CuO, and KCuO2. The final bound states were obtained from the self-consistent-field discrete-variational Xα method (SCF DV Xα), and continuum states were found by the multiple-scattering method using the muffin-tin truncation of the SCF DV Xα potentials. Composition of the final-state wave functions was analyzed. The 1s ionization potentials of the three reference compounds obtained from the SCF DV Xα transition-state calculations were used to set up the relative energy scale for the calculated cross section. The principal features of measured Cu K-edge XANES for Cu2O, CuO, and KCuO2 were reproduced satisfactorily by our calculations along with their relative energy positions. Our calculated polarized XANES of La2CuO4 were compared with measured spectra, and two shakeup features were identified with radiation polarized along the crystal c axis. By quantitatively comparing the measured spectra with a model based on our calculated cross sections, their intensities were found to be ~24% and 10% of the main transition with shakeup energies of 5.7 and 9.5 eV, respectively. We suggest that these multielectron excitation features involve Cu 3d-->4p transitions.

  5. Unoccupied-band narrowing in Na and its effect on the x-ray-absorption K edge

    SciTech Connect

    Citrin, P.H.; Wertheim, G.K.; Hashizume, T.; Sette, F.; MacDowell, A.A.; Comin, F.

    1988-08-22

    The first Na K-edge absorption measurements are reported. The data reveal a narrowing of the unfilled density of states analogous to that observed in a recent photoemission study of the conduction band and in very good agreement with new band-structure calculations. The narrowing is found to be essential for obtaining compatibility among the K-edge threshold exponent, the L/sub 2,3/-edge exponent, and the singularity index in core-level photoemission.

  6. K-edge eliminated material decomposition method for dual-energy X-ray CT.

    PubMed

    Zhao, Tiao; Li, Liang; Chen, Zhiqiang

    2017-09-01

    In medical dual-energy CT, projection-domain decomposition is typically used to process the acquired two projection datasets. However, when a high atomic-number contrast-agent is introduced, its K-edge discontinuity challenges this method. In this work, we take advantage of the fact that the contrast agent and its solvent are known in advance and propose to first decompose the attenuation coefficient functions of the contrast agent and its solvent to estimate the attenuation contribution of the K-shell photoelectric. Then, the contribution of the K-edge attenuation to the projection data is eliminated and the problem is decomposed to determine the attenuation coefficient functions of the other biological materials. Numerical experiments are shown to verify that the proposed method can give better results with less artifacts than the result of the direct projection-domain decomposition. Moreover, the variances of the decomposition coefficients, which is the index of the noise level of the decomposition coefficient image on the contrast regions, are smaller. Copyright © 2017. Published by Elsevier Ltd.

  7. Second Generation Gold Nanobeacons for Robust K-Edge Imaging with Multi-Energy CT

    PubMed Central

    Schirra, Carsten O.; Senpan, Angana; Roessl, Ewald; Thran, Axel; Stacy, Allen J.; Wu, Lina; Proska, Roland; Pan, Dipanjan

    2012-01-01

    Spectral CT is the newest advancement in CT imaging technology, which enhances traditional CT images with the capability to image and quantify certain elements based on their distinctive K-edge energies. K-edge imaging feature recognizes high accumulations of targeted elements and presents them as colorized voxels against the normal grayscale X-ray background offering promise to overcome the relatively low inherent contrast within soft tissue and distinguish the high attenuation of calcium from contrast enhanced targets. Towards this aim, second generation gold nanobeacons (GNB2), which incorporate at least five times more metal than the previous generation was developed. The particles were synthesized as lipid-encapsulated, vascularly constrained (>120 nm) nanoparticle incorporating tiny gold nanoparticles (2–4 nm) within a polysorbate core. The choice of core material dictated to achieve a higher metal loading. The particles were thoroughly characterized by physicochemical techniques. This study reports one of the earlier examples of spectral CT imaging with gold nanoparticles demonstrating the potential for targeted in vitro and in vivo imaging and eliminates calcium interference with CT. The use of statistical image reconstruction shows high SNR may allow dose reduction and/or faster scan times. PMID:23185109

  8. Investigation of X-ray fluorescence computed tomography (XFCT) and K-edge imaging.

    PubMed

    Bazalova, Magdalena; Kuang, Yu; Pratx, Guillem; Xing, Lei

    2012-08-01

    This work provides a comprehensive Monte Carlo study of X-ray fluorescence computed tomography (XFCT) and K-edge imaging system, including the system design, the influence of various imaging components, the sensitivity and resolution under various conditions. We modified the widely used EGSnrc/DOSXYZnrc code to simulate XFCT images of two acrylic phantoms loaded with various concentrations of gold nanoparticles and Cisplatin for a number of XFCT geometries. In particular, reconstructed signal as a function of the width of the detector ring, its angular coverage and energy resolution were studied. We found that XFCT imaging sensitivity of the modeled systems consisting of a conventional X-ray tube and a full 2-cm-wide energy-resolving detector ring was 0.061% and 0.042% for gold nanoparticles and Cisplatin, respectively, for a dose of ∼ 10 cGy. Contrast-to-noise ratio (CNR) of XFCT images of the simulated acrylic phantoms was higher than that of transmission K-edge images for contrast concentrations below 0.4%.

  9. Animal experiments by K-edge subtraction angiography by using SR (abstract)

    NASA Astrophysics Data System (ADS)

    Anno, I.; Akisada, M.; Takeda, T.; Sugishita, Y.; Kakihana, M.; Ohtsuka, S.; Nishimura, K.; Hasegawa, S.; Takenaka, E.; Hyodo, K.; Ando, M.

    1989-07-01

    Ischemic heart disease is one of the most popular and lethal diseases for aged peoples in the world, and is usually diagnosed by transarterial selective coronary arteriography. However, it is rather invasive and somewhat dangerous, so that the selective coronary arteriography is not feasible for prospective screening of coronary occlusive heart disease. Conventional digital subtraction angiography (DSA) is widely known as a relatively noninvasive and useful technique is making a diagnosis of arterial occlusive disease, especially in making the diagnosis of ischemic heart disease. Conventional intravenous subtraction angiography by temporal subtraction, however, has several problems when applying to the moving objects. Digital subtraction method using high-speed switching above and below the K edge could be the ideal approach to this solution. We intend to make a synchrotron radiation digital K-edge subtraction angiography in the above policy, and to apply it to the human coronary ischemic disease on an outpatient basis. The principles and experimental systems have already been described in detail by our coworkers. Our prototype experimental system is situated at the AR (accumulation ring) for TRISTAN project of high energy physics. The available beam size is 70 mm by 120 mm. The electron energy of AR is 6.5 GeV and average beam current is approximately 10 mA. This paper will show the animal experiments of our K-edge subtraction system, and discuss some problems and technical difficulties. Three dogs, weighing approximately 15 kg, were examined to evaluate the ability of our prototype synchrotron radiation DSA unit, that we are now constructing. The dogs were anaesthetized with pentobarbital sodium, intravenously (30 mg/kg). Six french-sized (1.52 mm i.d.) pigtail catheter with multiple side holes were introduced via the right femoral vein into the right atrium by the cutdown technique under conventional x-ray fluoroscopic control. Respiration of the dogs was

  10. Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals.

    PubMed

    Guc, Maxim; Levcenko, Sergiu; Bodnar, Ivan V; Izquierdo-Roca, Victor; Fontane, Xavier; Volkova, Larisa V; Arushanov, Ernest; Pérez-Rodríguez, Alejandro

    2016-01-18

    A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone-center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm(-1) on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis.

  11. Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals

    NASA Astrophysics Data System (ADS)

    Guc, Maxim; Levcenko, Sergiu; Bodnar, Ivan V.; Izquierdo-Roca, Victor; Fontane, Xavier; Volkova, Larisa V.; Arushanov, Ernest; Pérez-Rodríguez, Alejandro

    2016-01-01

    A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone–center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm‑1 on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis.

  12. Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals

    PubMed Central

    Guc, Maxim; Levcenko, Sergiu; Bodnar, Ivan V.; Izquierdo-Roca, Victor; Fontane, Xavier; Volkova, Larisa V.; Arushanov, Ernest; Pérez-Rodríguez, Alejandro

    2016-01-01

    A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone–center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm−1 on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis. PMID:26776727

  13. Development of a graphite polarization analyzer for resonant inelastic x-ray scattering

    SciTech Connect

    Gao Xuan; Burns, Clement; Li Chengyang; Casa, Diego; Upton, Mary; Gog, Thomas; Kim, Jungho

    2011-11-15

    Resonant inelastic x-ray scattering (RIXS) is a powerful technique for studying electronic excitations in correlated electron systems. Current RIXS spectrometers measure the changes in energy and momentum of the photons scattered by the sample. A powerful extension of the RIXS technique is the measurement of the polarization state of the scattered photons which contains information about the symmetry of the excitations. This long-desired addition has been elusive because of significant technical challenges. This paper reports the development of a new diffraction-based polarization analyzer which discriminates between linear polarization components of the scattered photons. The double concave surface of the polarization analyzer was designed as a good compromise between energy resolution and throughput. Such a device was fabricated using highly oriented pyrolytic graphite for measurements at the Cu K-edge incident energy. Preliminary measurements on a CuGeO{sub 3} sample are presented.

  14. Charge-transfer and Mott-Hubbard Excitations in FeBo{sub 3} : Fe K-edge resonant Inelastic x-ray scattering study.

    SciTech Connect

    Kim, J.; Shvydko, Y.

    2011-06-06

    Momentum-resolved resonant inelastic x-ray scattering (RIXS) spectroscopy has been carried out successfully at the Fe K-edge for the first time. The RIXS spectra of a FeBO{sub 3} single crystal reveal a wealth of information on {approx} 1-10 eV electronic excitations. The IXS signal resonates when the incident photon energy approaches the pre-edge (1s{sup -}-3d) and the main-edge (1s{sup -}-4p) of the Fe K-edge absorption spectrum. The RIXS spectra measured at the pre-edge and the main-edge show quantitatively different dependences on the incident photon energy, momentum transfer, photon polarization, and temperature. We present a multielectron analysis of the Mott-Hubbard (MH) and charge transfer (CT) excitations, and calculate their energies. Electronic excitations observed in the pre-edge and main-edge RIXS spectra are interpreted as MH and CT excitations, respectively. We propose the electronic structure around the chemical potential in FeBO{sub 3} based on the experimental data.

  15. Ultra-Low Field SQUID-NMR using LN2 Cooled Cu Polarizing Field coil

    NASA Astrophysics Data System (ADS)

    Demachi, K.; Kawagoe, S.; Ariyoshi, S.; Tanaka, S.

    2017-07-01

    We are developing an Ultra-Low Field (ULF) Magnetic Resonance Imaging (MRI) system using a High-Temperature Superconductor superconducting quantum interference device (HTS rf-SQUID) for food inspection. The advantages of the ULF-NMR (Nuclear Magnetic Resonance) / MRI as compared with a conventional high field MRI are that they are compact and of low cost. In this study, we developed a ULF SQUID-NMR system using a polarizing coil to measure fat of which relaxation time T1 is shorter. The handmade polarizing coil was cooled by liquid nitrogen to reduce the resistance and accordingly increase the allowable current. The measured decay time of the polarizing field was 40 ms. The measurement system consisted of the liquid nitrogen cooled polarizing coil, a SQUID, a Cu wound flux transformer, a measurement field coil for the field of 47 μT, and an AC pulse coil for a 90°pulse field. The NMR measurements were performed in a magnetically shielded room to reduce the environmental magnetic field. The size of the sample was ϕ35 mm × L80 mm. After applying a polarizing field and a 90°pulse, an NMR signal was detected by the SQUID through the flux transformer. As a result, the NMR spectra of fat samples were obtained at 2.0 kHz corresponding to the measurement field Bm of 47 μT. The T1 relaxation time of the mineral oil measured in Bm was 45 ms. These results suggested that the ULF-NMR/MRI system has potential for food inspection.

  16. Observation of momentum-dependent charge excitations in hole-doped cuprates using resonant inelastic x-ray scattering at the oxygen K edge

    NASA Astrophysics Data System (ADS)

    Ishii, Kenji; Tohyama, Takami; Asano, Shun; Sato, Kentaro; Fujita, Masaki; Wakimoto, Shuichi; Tustsui, Kenji; Sota, Shigetoshi; Miyawaki, Jun; Niwa, Hideharu; Harada, Yoshihisa; Pelliciari, Jonathan; Huang, Yaobo; Schmitt, Thorsten; Yamamoto, Yoshiya; Mizuki, Jun'ichiro

    2017-09-01

    We investigate electronic excitations in La2 -x(Br,Sr ) xCuO4 using resonant inelastic x-ray scattering (RIXS) at the oxygen K edge. RIXS spectra of the hole-doped cuprates show clear momentum dependence below 1 eV. The broad spectral weight exhibits positive dispersion and shifts to higher energy with increasing hole concentration. Theoretical calculation of the dynamical charge structure factor on oxygen orbitals in a three-band Hubbard model is consistent with the experimental observation of the momentum and doping dependence, and therefore the momentum-dependent spectral weight is ascribed to intraband charge excitations which have been observed in electron-doped cuprates. Our results confirm that the momentum-dependent charge excitations exist on the order of the transfer energy (t ), and the broad spectral line shape indicates damped and incoherent character of the charge excitations at the energy range in the doped Mott insulators.

  17. B K-Edge XANES of Superstructural Units in Borate Glasses

    SciTech Connect

    Sipr, O.; Simunek, A.; Rocca, F.

    2007-02-02

    The potential of x-ray absorption near-edge structure (XANES) spectroscopy for studying medium range order in borate glasses is assessed by theoretical modelling of the spectra. B K edge XANES is calculated in case that B atoms are located in isolated BO3 and BO4 units and in case that B atom are located in superstructural units of 9-15 atoms. It is found that boroxol ring and diborate and ditriborate superstructural units give rise to spectra which differ from spectra obtained by a mere superposition of spectra of isolated BO3 and BO4 units. On the other hand, spectra of pentaborate and triborate units do not differ significantly from spectra of isolated BO3 and BO4.

  18. An energy dispersive bent Laue monochromator for K-edge subtraction imaging

    SciTech Connect

    Samadi, Nazanin; Martinson, Mercedes; Bassey, Bassey; Gomez, Ariel; Belev, George; Chapman, Dean

    2016-07-27

    K-Edge Subtraction (KES) is a powerful synchrotron imaging method that allows the quantifiable determination of a contrast element (e.g. iodine) and matrix material (usually represented as water) in both projection imaging and computed tomography. A bent Laue monochromator has been developed that has very good focal and energy dispersive properties for KES. Approximately 5% of the vertical beam profile is involved in “edge crossing” energies, thus no splitter is employed as has been done with previous implementations where approximately 33% of the beam size was blocked. The beam can be narrowed vertically allowing a smaller crossover angle than a splitter based system which minimizes artifacts. The combination of good spatial resolution, energy dispersive properties, flux and a unique approach to data analysis make this system nearly ideal for KES.

  19. Exotic sources of x-rays for iodine K-edge angiography

    SciTech Connect

    Carr, R.

    1993-08-01

    Digital Subtractive Angiography (DSA) has been performed to image human coronary arteries using wiggler radiation from electron storage rings. The significant medical promise of this procedure motivates the development of smaller and less costly x-ray sources. Several exotic sources are candidates for consideration, using effects such as Cherenkov, channeling, coherent bremsstrahlung, laser backscattering, microundulator, parametric, Smith-Purcell, and transition radiation. In this work we present an analysis of these effects as possible sources of intense x-rays at the iodine K-edge at 33.169 key. The criteria we use are energy, efficiency, flux, optical properties, and technical realizability. For each of the techniques, we find that they suffer either from low flux, a low energy cutoff, target materials heating, too high electron beam energy requirement, optical mismatch to angiography, or a combination of these. We conclude that the foreseeable state-of-the-art favors a compact storage ring design.

  20. NO binding kinetics in myoglobin investigated by picosecond Fe K-edge absorption spectroscopy

    PubMed Central

    Silatani, Mahsa; Lima, Frederico A.; Penfold, Thomas J.; Rittmann, Jochen; Reinhard, Marco E.; Rittmann-Frank, Hannelore M.; Borca, Camelia; Grolimund, Daniel; Milne, Christopher J.; Chergui, Majed

    2015-01-01

    Diatomic ligands in hemoproteins and the way they bind to the active center are central to the protein’s function. Using picosecond Fe K-edge X-ray absorption spectroscopy, we probe the NO-heme recombination kinetics with direct sensitivity to the Fe-NO binding after 532-nm photoexcitation of nitrosylmyoglobin (MbNO) in physiological solutions. The transients at 70 and 300 ps are identical, but they deviate from the difference between the static spectra of deoxymyoglobin and MbNO, showing the formation of an intermediate species. We propose the latter to be a six-coordinated domed species that is populated on a timescale of ∼200 ps by recombination with NO ligands. This work shows the feasibility of ultrafast pump–probe X-ray spectroscopic studies of proteins in physiological media, delivering insight into the electronic and geometric structure of the active center. PMID:26438842

  1. Beyond carbon K-edge harmonic emission using a spatial and temporal synthesized laser field.

    PubMed

    Pérez-Hernández, J A; Ciappina, M F; Lewenstein, M; Roso, L; Zaïr, A

    2013-02-01

    We present numerical simulations of high-order harmonic generation in helium using a temporally synthesized and spatially nonhomogeneous strong laser field. The combination of temporal and spatial laser field synthesis results in a dramatic cutoff extension far beyond the usual semiclassical limit. Our predictions are based on the convergence of three complementary approaches: resolution of the three dimensional time dependent Schrödinger equation, time-frequency analysis of the resulting dipole moment, and classical trajectory extraction. A laser field synthesized both spatially and temporally has been proven capable of generating coherent extreme ultraviolet photons beyond the carbon K edge, an energy region of high interest as it can be used to initiate inner-shell dynamics and study time-resolved intramolecular attosecond spectroscopy.

  2. Preliminary study of an angiographic and angio-tomographic technique based on K-edge filters

    SciTech Connect

    Golosio, Bruno; Brunetti, Antonio; Oliva, Piernicola; Carpinelli, Massimo; Luca Masala, Giovanni; Meloni, Francesco; Battista Meloni, Giovanni

    2013-08-14

    Digital Subtraction Angiography is commonly affected by artifacts due to the patient movements during the acquisition of the images without and with the contrast medium. This paper presents a preliminary study on an angiographic and angio-tomographic technique based on the quasi-simultaneous acquisition of two images, obtained using two different filters at the exit of an X-ray tube. One of the two filters (K-edge filter) contains the same chemical element used as a contrast agent (gadolinium in this study). This filter absorbs more radiation with energy just above the so called K-edge energy of gadolinium than the radiation with energy just below it. The other filter (an aluminium filter in this study) is simply used to suppress the low-energy contribution to the spectrum. Using proper calibration curves, the two images are combined to obtain an image of the contrast agent distribution. In the angio-tomographic application of the proposed technique two images, corresponding to the two filter types, are acquired for each viewing angle of the tomographic scan. From the two tomographic reconstructions, it is possible to obtain a three-dimensional map of the contrast agent distribution. The technique was tested on a sample consisting of a rat skull placed inside a container filled with water. Six small cylinders with 4.7 mm internal diameter containing the contrast medium at different concentrations were placed inside the skull. In the plain angiographic application of the technique, five out of six cylinders were visible, with gadolinium concentration down to 0.96%. In the angio-tomographic application, all six cylinders were visible, with gadolinium concentration down to 0.49%. This preliminary study shows that the proposed technique can provide images of the contrast medium at low concentration without most of the artifacts that are present in images produced by conventional techniques. The results encourage further investigation on the feasibility of a clinical

  3. The potential for neurovascular intravenous angiography using K-edge digital subtraction angiography

    NASA Astrophysics Data System (ADS)

    Schültke, E.; Fiedler, S.; Kelly, M.; Griebel, R.; Juurlink, B.; LeDuc, G.; Estève, F.; Le Bas, J.-F.; Renier, M.; Nemoz, C.; Meguro, K.

    2005-08-01

    Background: Catheterization of small-caliber blood vessels in the central nervous system can be extremely challenging. Alternatively, intravenous (i.v.) administration of contrast agent is minimally invasive and therefore carries a much lower risk for the patient. With conventional X-ray equipment, volumes of contrast agent that could be safely administered to the patient do not allow acquisition of high-quality images after i.v. injection, because the contrast bolus is extremely diluted by passage through the heart. However, synchrotron-based digital K-edge subtraction angiography does allow acquisition of high-quality images after i.v. administration of relatively small doses of contrast agent. Materials and methods: Eight adult male New Zealand rabbits were used for our experiments. Animals were submitted to both angiography with conventional X-ray equipment and synchrotron-based digital subtraction angiography. Results: With conventional X-ray equipment, no contrast was seen in either cerebral or spinal blood vessels after i.v. injection of iodinated contrast agent. However, using K-edge digital subtraction angiography, as little as 1 ml iodinated contrast agent, when administered as i.v. bolus, yielded images of small-caliber blood vessels in the central nervous system (both brain and spinal cord). Conclusions: If it would be possible to image blood vessels of the same diameter in the central nervous system of human patients, the synchrotron-based technique could yield high-quality images at a significantly lower risk for the patient than conventional X-ray imaging. Images could be acquired where catheterization of feeding blood vessels has proven impossible.

  4. Killing of Bacillus Megaterium Spores by X-Rays at the Phosphorus K-Edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10 photons/sec/mm . The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  5. Killing of Bacillus Megaterium Spores by X-rays at the Phosphorus K-edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10(exp 18) photons/sec/sq mm. The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140 eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  6. Preliminary study of an angiographic and angio-tomographic technique based on K-edge filters

    NASA Astrophysics Data System (ADS)

    Golosio, Bruno; Oliva, Piernicola; Brunetti, Antonio; Luca Masala, Giovanni; Carpinelli, Massimo; Meloni, Francesco; Battista Meloni, Giovanni

    2013-08-01

    Digital Subtraction Angiography is commonly affected by artifacts due to the patient movements during the acquisition of the images without and with the contrast medium. This paper presents a preliminary study on an angiographic and angio-tomographic technique based on the quasi-simultaneous acquisition of two images, obtained using two different filters at the exit of an X-ray tube. One of the two filters (K-edge filter) contains the same chemical element used as a contrast agent (gadolinium in this study). This filter absorbs more radiation with energy just above the so called K-edge energy of gadolinium than the radiation with energy just below it. The other filter (an aluminium filter in this study) is simply used to suppress the low-energy contribution to the spectrum. Using proper calibration curves, the two images are combined to obtain an image of the contrast agent distribution. In the angio-tomographic application of the proposed technique two images, corresponding to the two filter types, are acquired for each viewing angle of the tomographic scan. From the two tomographic reconstructions, it is possible to obtain a three-dimensional map of the contrast agent distribution. The technique was tested on a sample consisting of a rat skull placed inside a container filled with water. Six small cylinders with 4.7 mm internal diameter containing the contrast medium at different concentrations were placed inside the skull. In the plain angiographic application of the technique, five out of six cylinders were visible, with gadolinium concentration down to 0.96%. In the angio-tomographic application, all six cylinders were visible, with gadolinium concentration down to 0.49%. This preliminary study shows that the proposed technique can provide images of the contrast medium at low concentration without most of the artifacts that are present in images produced by conventional techniques. The results encourage further investigation on the feasibility of a clinical

  7. Killing of Bacillus Megaterium Spores by X-Rays at the Phosphorus K-Edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10 photons/sec/mm . The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  8. Killing of Bacillus Megaterium Spores by X-rays at the Phosphorus K-edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10(exp 18) photons/sec/sq mm. The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140 eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  9. A balanced filterless K-edge energy window multilayer detector for dual energy computed tomography

    NASA Astrophysics Data System (ADS)

    Allec, Nicholas; Karim, Karim S.

    2010-04-01

    Ross (or balanced) filter-based systems have been studied extensively in the past, however they have only recently been studied for medical applications such as computed tomography and contrast-enhanced mammography. Balanced filters are filters composed of different materials which have thicknesses designed to match the attenuation for all radiation energies except those within a certain energy window (between the K-edges of the filter materials). Images obtained using different filters to attenuate the incident x-rays can be subtracted to obtain an image which contains information solely within the energy window. The disadvantage of this image acquisition method is the requirement of a separate exposure for each filter. This can lead to motion artifacts in the resulting image for example due to cardiac, respiratory, or patient movement. In this paper we investigate a filterless, multilayer detector design using the general concept of balanced filters. In the proposed detector, energy discrimination is achieved using stacked layers of different conversion materials. Similar to how the thicknesses of balanced filters are chosen, the thicknesses of the conversion layers are designed to match the attenuation of x-rays except between the K-edges of the conversion materials. Motion artifacts are suppressed in the final image due to the simultaneous acquisition of images on all layers during a single exposure. The proposed multilayer design can be used for a number of applications depending on the energy range of interest. To study the proposed design, we consider dual energy computed tomography (CT) using a gadolinium-based contrast agent.

  10. Spin Polarization of Mg-23 in Mg-24 + Au, Cu and Al Collisions at 91 A MeV

    NASA Technical Reports Server (NTRS)

    Matsuta, K.; Fukuda, S.; Izumikawa, T.; Tanigaki, M.; Fukuda, M.; Nakazato, M.; Mihara, M.; Onishi, T.; Yamaguchi, T.; Miyake, T.

    1994-01-01

    Spin polarization of beta-emitting fragment Mg-23(I(sup pi) = 3/2(sup +), T(sub 1/2 = l1.3 s) produced through the projectile fragmentation process in Mg-24 + Au, Cu and Al collisions has been observed at 91 AMeV. General trend in the observed momentum dependence of polarization is reproduced well qualitatively by a simple fragmentation model based on the participant-spectator picture, for heavy and light targets. However the polarization behavior differs from this model in tern of zero crossing momentum, which become prominent in the case of Cu target, where the polarization is not monotone function of the fragment momentum.

  11. The growth of heteroepitaxial CuInSe{sub 2} on free-standing N-polar GaN

    SciTech Connect

    Shih, Cheng-Hung; Lo, Ikai You, Shuo-Ting; Tsai, Cheng-Da; Tseng, Bae-Heng; Chen, Yun-Feng; Chen, Chiao-Hsin; Lee, Chuo-Han; Lee, Wei-I; Hsu, Gary Z. L.

    2014-12-15

    We report that chalcopyrite CuInSe{sub 2} thin films were grown on free-standing N-polar GaN (0001{sup -}) by molecular beam epitaxy. X-ray diffraction showed that the CuInSe{sub 2} thin film was grown in (112) orientation, and its peak of rocking curve with full width at half maximum of about 897.8 arc-sec indicated the epitaxial growth of CuInSe{sub 2} (112) film on N-polar GaN. Microstructure analysis of the CuInSe{sub 2 } showed that the large lattice mismatch (28.5%) between CuInSe{sub 2 } and GaN is accommodated by domain matching, and no interface reaction occurs between CuInSe{sub 2} and GaN. Our experimental results show that GaN is stable for the epitaxial growth of CuInSe{sub 2} thin film, which exhibits a promising potential for optoelectronic applications.

  12. Partial-ion-yield studies of SOCl2 following x-ray absorption around the S and Cl K edges

    NASA Astrophysics Data System (ADS)

    Bowen, K. P.; Stolte, W. C.; Lago, A. F.; Dávalos, J. Z.; Piancastelli, M. N.; Lindle, D. W.

    2012-11-01

    We present a series of photoabsorption and partial-ion-yield experiments on thionyl chloride, SOCl2, at both the sulfur and chlorine K edges. The photoabsorption results exhibit better resolution than previously published data, leading to alternate spectral assignments for some of the features, particularly in the Rydberg-series region. Based on measured fragmentation patterns, we suggest the LUMO, of a' character, is delocalized over the entire molecular skeleton. Unusual behavior of the S2 + fragment hints at a relatively localized bond rupture (the S-O bond below the S K edge and the S-Cl bonds below the Cl K edge) following excitation to some of the higher lying intermediate states.

  13. Determining the Sulfur species in the dispersants Corexit 9500A and 9527A applying S K-edge XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Bovenkamp-Langlois, Lisa; Roy, Amitava

    2016-05-01

    The dispersants Corexit 9500A and 9527A were used extensively during the Deepwater Horizon oil spill in the Gulf of Mexico. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to investigate the dispersants for the sulfur based components. The main sulfur containing component should be dioctyl sodium sulfosuccinate (DOSS). S K-edge XANES analysis shows that indeed the major sulfur species in both kinds of Corexit (9500A and 9527A) is sulfonic acid which is a part of DOSS. In addition some fraction of sulfone was detected.

  14. Field flatteners fabricated with a rapid prototyper for K-edge subtraction imaging of small animals

    NASA Astrophysics Data System (ADS)

    Zhu, Ying; Zhang, Honglin; Bewer, Brian; Florin Gh. Popescu, Bogdan; Nichol, Helen; Chapman, Dean

    2008-04-01

    One of the difficulties in X-ray imaging is the need to record a wide dynamic range of intensities on the detector. For example, some rays may miss the object being imaged entirely while others may suffer many orders of magnitude attenuation in passing through. In K-edge subtraction (KES) [E. Rubenstein, et al., Trans. Am. Clin. Climatol. Assoc. 97 (1985) 27.] imaging subtle differences in transmission through an object about the absorption edge of an element are used to create an image of the projected density of that element. This is done by a logarithmic subtraction of images acquired with energies above and below the absorption edge. For KES, the detector must register this transmitted intensity range in a linear manner for the subtraction method to be successful. The range of intensities which may strike the detector has inspired the concept of a field flattener. A field flattener is a device placed in the beam path that attenuates the input monochromatic beam to equalize X-ray absorption due to differences in the density of soft and hard tissues of an object before it passes through the object and thus achieves a flattened image. This removes the need for a wide dynamic range linear detector and allows detectors with modest performance to be used successfully in KES applications. The field flattener improves the S/ N ratio since X-ray exposures can be increased up to detector saturation. However, a field flattener removes anatomical information from each raw image (above or below K-edge) that may provide useful landmarks. Using rapid prototyping technology, two sets of field flatteners were fabricated and used in a KES experiment. This paper describes the procedure to design and fabricate field flatteners based on animal images from X-ray computed tomography (CT). Analysis of experimental data and KES images of a rat head with and without the field flattener are also presented. The results show a promising improvement of S/ N ratio using a field flattener

  15. Observation of changes in the atomic and electronic structure of single-crystal YBa2Cu3O6.6 accompanying bromination

    NASA Astrophysics Data System (ADS)

    Dieng, L. M.; Ignatov, A. Yu.; Tyson, T. A.; Croft, M.; Dogan, F.; Kim, C.-Y.; Woicik, J. C.; Grow, J.

    2002-06-01

    To ascertain the role of bromination in the recovery of superconductivity in underdoped YBa2Cu3O6+y (YBCO), we have performed polarized multiple-edge x-ray-absorption fine structure (XAFS) measurements on normal (y~0.6) and brominated (Br/Cu~1/30, y~0.6) single crystals with superconducting transitions at 63 and 89 K, respectively. The brominated sample becomes strongly heterogeneous on an atomic length scale. Approximately one-third of YBCO is locally decomposed yet incorporated as a well-ordered ``host'' lattice as nanoscale regions. The decomposed phase consists of heavily distorted domains with an order not following that of the ``host'' lattice. Structurally, these domains are fragments of the YBCO lattice that are discontinued along the Cu(1)-O(1) containing planes. The local structure is consistent with the cluster expansions: Y-O(2,3)8-Cu(2)8-..., Ba-O8-Cu(2)4Cu(1)2-..., and Cu-O4-... about the Y, Ba, and Cu sites. Interatomic distances and Debye-Waller factors for the expansions were determined from fits to Y K-, Ba L3-, and Cu K-edge XAFS data at room temperature. Br K-edge data reveal that Br does not enter substitutionally or interstitially into the perfect YBCO lattice. However, Br does occupy the Cu(1) sites in a nanofragment of the YBCO lattice, forming Br-O(4)-Ba-Cu2(1)Cu(2)-... nanoclusters. From polarized measurements these nanoclusters were found to be almost randomly oriented with respect to the ``host'' crystal, and probably are the nucleus of the decomposed phase. This heterogeneity brings about the unusual structural and electronic properties of the normal state previously reported in the literature. Implications on for diffraction, transport, and magnetization measurements are discussed.

  16. Molecular anisotropy effects in carbon K-edge scattering: depolarized diffuse scattering and optical anisotropy

    SciTech Connect

    Stone, Kevin H.

    2014-07-14

    Some polymer properties, such as conductivity, are very sensitive to short- and intermediate-range orientational and positional ordering of anisotropic molecular functional groups, and yet means to characterize orientational order in disordered systems are very limited. We demonstrate that resonant scattering at the carbon K-edge is uniquely sensitive to short-range orientation correlations in polymers through depolarized scattering at high momentum transfers, using atactic polystyrene as a well-characterized test system. Depolarized scattering is found to coexist with unpolarized fluorescence, and to exhibit pronounced anisotropy. We also quantify the spatially averaged optical anisotropy from low-angle reflectivity measurements, finding anisotropy consistent with prior visible, x-ray absorption, and theoretical studies. The average anisotropy is much smaller than that in the depolarized scattering and the two have different character. Both measurements exhibit clear spectral signatures from the phenyl rings and the polyethylene-like backbone. Discussion focuses on analysis considerations and prospects for using this depolarized scattering for studies of disorder in soft condensed matter.

  17. Identification of Uranyl Minerals Using Oxygen K-Edge X Ray Absorption Spectroscopy

    SciTech Connect

    Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.; Smith, Steven C.; McNamara, Bruce K.; Buck, Edgar C.; Eiden, Gregory C.; Duffin, Andrew M.

    2016-03-01

    Uranium analysis is consistently needed throughout the fuel cycle, from mining to fuel fabrication to environmental monitoring. Although most of the world’s uranium is immobilized as pitchblende or uraninite, there exists a plethora of secondary uranium minerals, nearly all of which contain the uranyl cation. Analysis of uranyl compounds can provide clues as to a sample’s facility of origin and chemical history. X-ray absorption spectroscopy is one technique that could enhance our ability to identify uranium minerals. Although there is limited chemical information to be gained from the uranium X-ray absorption edges, recent studies have successfully used ligand NEXAFS to study the physical chemistry of various uranium compounds. This study extends the use of ligand NEXAFS to analyze a suite of uranium minerals. We find that major classes of uranyl compounds (carbonate, oxyhydroxide, silicate, and phosphate) exhibit characteristic lineshapes in the oxygen K-edge absorption spectra. As a result, this work establishes a library of reference spectra that can be used to classify unknown uranyl minerals.

  18. The blue of iron in mineral pigments: a Fe K-edge XANES study of vivianite

    NASA Astrophysics Data System (ADS)

    Figueiredo, M. O.; Silva, T. P.; Veiga, J. P.

    2010-05-01

    Iron is a powerful chromophore element whose pigmenting properties were the first to be recognized among transition metals. The interest in blue iron minerals as pigments for painting was enhanced with the use of vivianite—a natural hydrated ferrous phosphate, Fe3(PO4)2ṡ8H2O—which in medieval Europe became an alternative to the expensive lapis lazuli, (Na, Ca)4(AlSiO4)3(SO4, Cl, S), a member of the ultramarines whose appreciated blue tone is due to the presence of sulfur polyanions. Conversely, vivianite coloring is attributed to the intervalence charge transfer (IVCT) Fe2+-Fe3+ that in later decades was studied by optical techniques and Mössbauer spectroscopy. However, the aging of blue vivianite pigments in old paintings has become a serious concern for conservators, but the aging process still awaits a satisfactory explanation. As an input to this problem, an X-ray absorption near-edge structure (XANES) study at the Fe K-edge of vivianite with different colors and origins was undertaken at the European Synchrotron Radiation Facility using the instrumental facilities of beamline ID-21. The analysis of pre-edge features corroborates previous data on the origin of vivianite color and emphasizes the need for a precautious assessment of iron speciation on the exclusive basis of XANES data. Actual results are discussed and further work is outlined.

  19. Li K-Edge XANES Spectra of Lithium Niobate and Lithium Tantalite

    SciTech Connect

    Mizota, H.; Ito, Y.; Tochio, T.; Handa, K.; Takekawa, S.; Kitamura, K.

    2007-02-02

    The x-ray emission with the single crystal of lithium niobate (LiNbO3) or lithium tantalite (LiTaO3) by thermal changes in a vacuum system is closely concerned with the electronic state of each crystal. Therefore, lithium K-edge x-ray absorption near edge structures (XANES) spectra of these materials were measured in the region from 50 eV to 90 eV by means of total electron yield method (T.E.Y.), using the extremely soft x-ray. Samples were powder of lithium carbonate (Li2CO3) and single crystal of lithium fluoride (LiF), LiNbO3 and LiTaO3 in order to compare the shapes of these XANES spectra. Various peak structures appear in these spectra in the range from 55 eV to 80 eV and each spectrum has different shapes as a result of the difference of bond length and bond angles for the atoms which are in less than 60 nm from the absorbing atom. The relationship between these spectra and the electronic states was discussed by FEFF 8.

  20. K-edge digital subtraction imaging with dichromatic x-ray sources: SNR and dose studies

    NASA Astrophysics Data System (ADS)

    Sarnelli, A.; Elleaume, H.; Taibi, A.; Gambaccini, M.; Bravin, A.

    2006-09-01

    The aim of the present work is to analytically evaluate the signal to noise ratio (SNR) and the delivered dose in K-edge digital subtraction imaging (KES) using two types of x-ray sources: a monochromatic x-ray source (available at synchrotron radiation facilities and considered as gold standard) and a quasi-monochromatic compact source. The energy separation ΔE between the two monochromatic beams is 1 keV and 4 keV for the two sources, respectively. The evaluation has been performed for both radiography and computed tomography. Different geometries have been studied to mimic clinical situations. In mammography, a pathology perfused by a contrast agent has been modelled; in angiography, a vessel superimposed to a ventricle or a stand-alone artery stenosis has been studied. The SNR and the skin dose have been calculated as a function of the detail diameter, the contrast agent (iodine and gadolinium), and its concentration in the tissues. Results show that for ΔE = 4 keV a slightly higher delivered dose is required to obtain the same SNR with respect to ΔE < 1 keV. A similar study has been performed for KES-CT. Computer simulations of CT images performed with Snark software are shown to validate the analytical calculations.

  1. Using X-ray, K-edge densitometry in spent fuel characterization

    SciTech Connect

    Jensen, T.; Aljundi, T.; Gray, J.N.

    1998-06-01

    There are instances where records for spent nuclear fuel are incomplete, as well as cases where fuel assemblies have deteriorated during storage. To bring these materials into compliance for long term storage will require determination of parameters such as enrichment, total fissionable material, and burnup. To obtain accurate estimates of these parameters will require the combination of information from different inspection techniques. A method which can provide an accurate measure of the total uranium in the spent fuel is X-ray K-edge densitometry. To assess the potential for applying this method in spent fuel characterization, the authors have measured the amount of uranium in stacks of reactor fuel plates containing nuclear materials of different enrichments and alloys. They have obtained good agreement with expected uranium concentrations ranging from 60 mg/cm{sup 2} to 3,000 mg/cm{sup 2}, and have demonstrated that these measurements can be made in a high radiation field (> 200 mR/hr).

  2. Photoabsorption spectra of potassium and rubidium near the K-edge

    SciTech Connect

    Azuma, Y.; Berry, H.G.; Cowan, P.L.

    1995-08-01

    We have used a high-temperature circulating heat-pipe absorption cell together with monochromatized X-ray beams at the X24A and X23A2 beam lines at the NSLS to obtain photoabsorption spectra of potassium and rubidium at their K- and KM-edges. The photon-energy ranges lay near 3600 eV and 15200 eV, respectively. We have also obtained first measurements of the LII and LIII edges in cesium. Although the K-edge photoabsorptions of the rare gases have been studied, there is little previous work on other atomic vapors. Most of the edges and resonance peaks that we observed have now been identified using Dirac Hartree-Fock calculations. As a check, we have compared these results with those obtained previously in closed-shell rare-gas absorption spectra. The absolute energies were obtained through a calibration of the X24A systems using measurements of several metal L-edges in the 3200-5000 eV energy range. We found that the 4p resonance in potassium is significantly enhanced compared with the corresponding situation in argon. Likewise, the 5p resonance in krypton is unresolved from the background ionization cross section, whereas it is well resolved in rubidium. As suggested by Amusia, these enhancements may be due to the enhanced potential seen in the excited state of the alkali systems as a result of the presence of an s-electron which reduces the nuclear shielding.

  3. Molecular anisotropy effects in carbon K-edge scattering: Depolarized diffuse scattering and optical anisotropy

    NASA Astrophysics Data System (ADS)

    Stone, Kevin H.; Kortright, Jeffrey B.

    2014-09-01

    Some polymer properties, such as conductivity, are very sensitive to short- and intermediate-range orientational and positional ordering of anisotropic molecular functional groups, and yet means to characterize orientational order in disordered systems are very limited. We demonstrate that resonant scattering at the carbon K edge is uniquely sensitive to short-range orientation correlations in polymers through depolarized scattering at high momentum transfers, using atactic polystyrene as a well-characterized test system. Depolarized scattering is found to coexist with unpolarized fluorescence and to exhibit pronounced anisotropy. We also quantify the spatially averaged optical anisotropy from low-angle reflectivity measurements, finding anisotropy consistent with prior visible, x-ray absorption, and theoretical studies. The average anisotropy is much smaller than that in the depolarized scattering and the two have different character. Both measurements exhibit clear spectral signatures from the phenyl rings and the polyethylenelike backbone. Discussion focuses on analysis considerations and prospects for using this depolarized scattering for studies of disorder in soft condensed matter.

  4. Demonstration of enhanced K-edge angiography using a cerium target x-ray generator

    SciTech Connect

    Sato, Eiichi; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Ichimaru, Toshio; Sato, Shigehiro; Takayama, Kazuyoshi; Ido, Hideaki

    2004-11-01

    The cerium target x-ray generator is useful in order to perform enhanced K-edge angiography using a cone beam because K-series characteristic x rays from the cerium target are absorbed effectively by iodine-based contrast mediums. The x-ray generator consists of a main controller, a unit with a Cockcroft-Walton circuit and a fixed anode x-ray tube, and a personal computer. The tube is a glass-enclosed diode with a cerium target and a 0.5-mm-thick beryllium window. The maximum tube voltage and current were 65 kV and 0.4 mA, respectively, and the focal-spot sizes were 1.0x1.3 mm. Cerium K{alpha} lines were left using a barium sulfate filter, and the x-ray intensity was 0.48 {mu}C/kg at 1.0 m from the source with a tube voltage of 60 kV, a current of 0.40 mA, and an exposure time of 1.0 s. Angiography was performed with a computed radiography system using iodine-based microspheres. In coronary angiography of nonliving animals, we observed fine blood vessels of approximately 100 {mu}m with high contrasts.

  5. Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory

    SciTech Connect

    George, S.DeBeer; Petrenko, T.; Neese, F.

    2009-05-14

    Iron K-edge X-ray absorption pre-edge features have been calculated using a time-dependent density functional approach. The influence of functional, solvation, and relativistic effects on the calculated energies and intensities has been examined by correlation of the calculated parameters to experimental data on a series of 10 iron model complexes, which span a range of high-spin and low-spin ferrous and ferric complexes in O{sub h} to T{sub d} geometries. Both quadrupole and dipole contributions to the spectra have been calculated. We find that good agreement between theory and experiment is obtained by using the BP86 functional with the CP(PPP) basis set on the Fe and TZVP one of the remaining atoms. Inclusion of solvation yields a small improvement in the calculated energies. However, the inclusion of scalar relativistic effects did not yield any improved correlation with experiment. The use of these methods to uniquely assign individual spectral transitions and to examine experimental contributions to backbonding is discussed.

  6. Time-Dependent Density Functional Calculations of Ligand K-Edge X-Ray Absorption Spectra

    SciTech Connect

    DeBeer George, S.; Petrenko, T.; Neese, F.

    2007-07-10

    X-ray absorption spectra (XAS) at the Cl and S K edge and Mo L edge have been calculated at the TDDFT level for a series of dioxomolybdenum complexes LMoO{sub 2}X (L = hydrotris(3,5-dimethyl-1-pyrazolyl)borate, X = Cl, SCH{sub 2}Ph, OPh), which play an important role in modeling the catalytic cycle of the sulfite oxidase enzyme. Also, the XAS spectra of model molecules of the Mo complexes have been simulated and interpreted in terms of the Mo 4d orbital splitting, in order to find possible correlations with the spectral pattern of the complexes. Comparison with the available experimental data allows us to assess the performances of the present computational scheme to describe the core excitations in large bioinorganic systems. The theoretical interpretation of the spectral features of both the metal and ligand core excitations in terms of the oscillator strength distribution provides important insight into the covalency of the metal-ligand bond.

  7. Theoretical simulations of oxygen K -edge resonant inelastic x-ray scattering of kaolinite

    NASA Astrophysics Data System (ADS)

    Ertan, Emelie; Kimberg, Victor; Gel'mukhanov, Faris; Hennies, Franz; Rubensson, Jan-Erik; Schmitt, Thorsten; Strocov, Vladimir N.; Zhou, Kejin; Iannuzzi, Marcella; Föhlisch, Alexander; Odelius, Michael; Pietzsch, Annette

    2017-04-01

    Near-edge x-ray absorption fine structure (NEXAFS) and resonant inelastic x-ray scattering (RIXS) measurements at the oxygen K edge were combined with theoretical spectrum simulations, based on periodic density functional theory and nuclear quantum dynamics, to investigate the electronic structure and chemical bonding in kaolinite Al2Si2O5 (OH) 4. We simulated NEXAFS spectra of all crystallographically inequivalent oxygen atoms in the crystal and RIXS spectra of the hydroxyl groups. Detailed insight into the ground-state potential energy surface of the electronic states involved in the RIXS process were accessed by analyzing the vibrational excitations, induced by the core excitation, in quasielastic scattering back to the electronic ground state. In particular, we find that the NEXAFS pre-edge is dominated by features related to OH groups within the silica and alumina sheets, and that the vibrational progression in RIXS can be used to selectively probe vibrational modes of this subclass of OH groups. The signal is dominated by the OH stretching mode, but also other lower vibrational degrees of freedom, mainly hindered rotational modes, contribute to the RIXS signal.

  8. Sulfur K-edge XANES for methylene blue in photocatalytic reaction over WO3 nanomaterials

    NASA Astrophysics Data System (ADS)

    Komori, K.; Yoshida, T.; Nomoto, T.; Yamamoto, M.; Tsukada, C.; Yagi, S.; Yajima, M.; Kajita, S.; Ohno, N.

    2015-12-01

    We investigated the photocatalysis of dendritic nanostructured WO3/W composite materials fabricated by He plasma irradiation to tungsten plates, followed by the surface oxidation. The samples promoted the decolorization reaction of methylene blue (MB) aqueous solution under near infrared (NIR) light irradiation. To verify the MB molecule is actually decomposed by the photocatalysis of the samples, reaction products were analyzed by S K-edge XANES measurements for the MB solution kept with the samples under the light irradiation or in the dark. By the light irradiation, the σ*(S-C) peak in the XANES spectra reduced and a new peak originated from SO42- species was clearly observed, suggesting that S-C bonds in a MB molecule are broken by the NIR light irradiation and finally the sulfur species exists in the solution in the state of SO42- ion. After the adsorption reaction in the dark, the XANES spectra of the sample surfaces showed a sharp π*(S-C) peaks, indicating that MB molecules are adsorbed on the sample surfaces and stacked each other by the π-π interaction. These results demonstrate that the photocatalytic decomposition of MB molecules really proceeds over WO3/W composite materials even under NIR light irradiation.

  9. K-edge imaging with the XPAD3 hybrid pixel detector, direct comparison of CdTe and Si sensors.

    PubMed

    Cassol, F; Portal, L; Graber-Bolis, J; Perez-Ponce, H; Dupont, M; Kronland, C; Boursier, Y; Blanc, N; Bompard, F; Boudet, N; Buton, C; Clémens, J C; Dawiec, A; Debarbieux, F; Delpierre, P; Hustache, S; Vigeolas, E; Morel, C

    2015-07-21

    We investigate the improvement from the use of high-Z CdTe sensors for pre-clinical K-edge imaging with the hybrid pixel detectors XPAD3. We compare XPAD3 chips bump bonded to Si or CdTe sensors in identical experimental conditions. Image performance for narrow energy bin acquisitions and contrast-to-noise ratios of K-edge images are presented and compared. CdTe sensors achieve signal-to-noise ratios at least three times higher than Si sensors within narrow energy bins, thanks to their much higher detection efficiency. Nevertheless Si sensors provide better contrast-to-noise ratios in K-edge imaging when working at equivalent counting statistics, due to their better estimation of the attenuation coefficient of the contrast agent. Results are compared to simulated data in the case of the XPAD3/Si detector. Good agreement is observed when including charge sharing between pixels, which have a strong impact on contrast-to-noise ratios in K-edge images.

  10. Photoabsorption study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

    NASA Technical Reports Server (NTRS)

    Frigo, Sean P.; McNulty,Ian; Richmond, Robert C.; Ehret, Charles F.

    2003-01-01

    We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include red phosphorus, hydrated sodium phosphate (Na3PO4 12 H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position, where each is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B.meguterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition, the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

  11. Photoabsorption Study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

    NASA Technical Reports Server (NTRS)

    Frigo, Sean P.; McNulty, Ian; Richmond, Robert C.; Ehret, Charles F.

    2002-01-01

    We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include elemental red phosphorus, hydrated sodium phosphate (Na3PO4.12H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Elemental red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position. Each spectrum for these substances is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for elemental red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B. megaterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition,the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

  12. Photoabsorption Study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

    NASA Technical Reports Server (NTRS)

    Frigo, Sean P.; McNulty, Ian; Richmond, Robert C.; Ehret, Charles F.

    2002-01-01

    We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include elemental red phosphorus, hydrated sodium phosphate (Na3PO4.12H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Elemental red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position. Each spectrum for these substances is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for elemental red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B. megaterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition,the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

  13. Double-core ionization and excitation above the sulphur K-edge in ?, ? and ?

    NASA Astrophysics Data System (ADS)

    Reynaud, Cécile; Gaveau, Marc-André; Bisson, Kristel; Millié, Philippe; Nenner, Irène; Bodeur, Suzanne; Archirel, Pierre; Lévy, Bernard

    1996-11-01

    Experimental and theoretical results are reported on double-core excitation and ionization processes in some sulphur containing molecules. X-ray absorption spectra have been recorded at the sulphur K-edge using synchrotron radiation delivered by the DCI ring at LURE (Orsay, France). Absolute x-ray absorption cross sections have been determined for gas phase 0953-4075/29/22/017/img12, 0953-4075/29/22/017/img13 and 0953-4075/29/22/017/img14 molecules in the 2400 - 2800 eV region. Several narrow features are observed far from the edge and assigned to 0953-4075/29/22/017/img15 double-core excited states. Two series of states are present corresponding to the triplet and singlet configurations, due to the core 1s - 2p exchange term. The energy, width and intensity of the features are strongly molecule dependent. In the case of 0953-4075/29/22/017/img12, a theoretical determination of all the single- and double-core vacancy ionization potentials has been performed using a new theoretical approach which makes it possible to solve the convergence problem inherent in a simple SCF calculation. Results compare favourably with available experimental values. In particular, the singlet - triplet separation is correctly predicted for all the double-core ionized states. The relation between the double-core relaxation energies and the associated single-core relaxation values is discussed. Finally, the double-core excited state energies are determined within a Z + 2 core equivalent model, allowing a full assignment of the 0953-4075/29/22/017/img15 experimental spectra of 0953-4075/29/22/017/img12.

  14. Extended X- ray absorption fine structure study at the K-edge of copper in mixed ligand complexes having benzimidazole as one of the ligands

    NASA Astrophysics Data System (ADS)

    Hinge, V. K.; Joshi, S. K.; Nitin Nair, N.; Singh Verma, Vikram; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

    2014-09-01

    Extended X-ray absorption fine structure (EXAFS) spectra have been studied at the K-edge of copper in some of its biologically important complexes, viz., [Cu(BzImH)4X2] and [Cu(BzIm)2], where X= Cl, Br, 1/2SO4, ClO4, NO3, and BzIm = Benzimidazolato anion. The spectra have been recorded using a bent crystal 0.4 m Cauchois-type transmission spectrograph. The positions of EXAFS maxima and minima have been used to determine the bond lengths in the complexes with the help of three different methods, namely, Levy's, Lytle's and Lytle, Sayers and Stern's (L.S.S.) methods. The phase uncorrected bond lengths have also been determined from Fourier transforms of the experimental spectra. The results obtained from these methods have been discussed and it has been found that the results obtained by L.S.S. method are comparable with the results obtained by Fourier transformation method and that these two methods give phase uncorrected bond lengths.

  15. Local Structure of CuIn3Se5

    SciTech Connect

    Chang, C. H.; Wei, S. H.; Leyarovska, N.; Johnson, J. W.; Zhang, S. B.; Stanbery, B. J.; Anderson, T. J.

    2000-01-01

    The results of a detailed EXAFS study of the Cu-K, In-K, and Se-K edges CuIn3Se5 are reported. The Cu and In first nearest neighbor local structures were found to be almost identical to those in CuInSe2.

  16. Neuronal activity during a cued strategy task: Comparison of dorsolateral, orbital and polar prefrontal cortex

    PubMed Central

    Tsujimoto, Satoshi; Genovesio, Aldo; Wise, Steven P.

    2012-01-01

    We compared neuronal activity in the dorsolateral (PFdl), orbital (PFo) and polar (PFp) prefrontal cortex as monkeys performed three tasks. In two tasks, a cue instructed one of two strategies: stay with the previous response or shift to the alternative. Visual stimuli served as cues in one of these tasks; in the other, fluid rewards did so. In the third task, visuospatial cues instructed each response. A delay period followed each cue. As reported previously, PFdl encoded strategies (stay or shift) and responses (left or right) during the cue and delay periods, while PFo encoded strategies and PFp encoded neither strategies nor responses; during the feedback period, all three areas encoded responses, not strategies. Four novel findings emerged from the present analysis. (1) The strategy encoded by PFdl and PFo cells during the cue and delay periods was modality specific. (2) The response encoded by PFdl cells was task- and modality specific during the cue period, but during the delay and feedback periods it became task- and modality general. (3) Although some PFdl and PFo cells responded to or anticipated rewards, we could rule out reward effects for most strategy-and response-related activity. (4) Immediately before feedback, only PFp signaled responses that were correct according to the cued strategy; after feedback, only PFo signaled the response that had been made, whether correct or incorrect. These signals support a role in generating responses by PFdl, assigning outcomes to choices by PFo, and assigning outcomes to cognitive processes by PFp. PMID:22875935

  17. Space charge polarization modulated instability of low frequency permittivity in CaCu3Ti4O12 ceramics

    NASA Astrophysics Data System (ADS)

    Wu, Kangning; Huang, Yuwei; Li, Jianying; Li, Shengtao

    2017-07-01

    A low frequency dielectric relaxation process of CaCu3Ti4O12 ceramics, which is generally overlapped by dc conduction in traditional dielectric spectra, is detected and clarified based on an improved analytical methodology in this letter. This relaxation process remarkably contributes to instability of low frequency permittivity and it clearly demonstrates the correlation between charge migration and space charge polarization. It is revealed that conduction will be achieved if carriers migrate and combine in the electrodes, while space charge polarization will be achieved if carriers migrate to the electrodes without combination.

  18. Studies on effective atomic numbers, electron densities from mass attenuation coefficients near the K edge in some samarium compounds.

    PubMed

    Akman, F; Durak, R; Turhan, M F; Kaçal, M R

    2015-07-01

    The effective atomic numbers and electron densities of some samarium compounds were determined using the experimental total mass attenuation coefficient values near the K edge in the X-ray energy range from 36.847 up to 57.142 keV. The measurements, in the region from 36.847 to 57.142 keV, were done in a transmission geometry utilizing the Kα2, Kα1, Kβ1 and Kβ2 X-rays from different secondary source targets excited by the 59.54 keV gamma-photons from an Am-241 annular source. This paper presents the first measurement of the effective atomic numbers and electron densities for some samarium compounds near the K edge. The results of the study showed that the measured values were in good agreement with the theoretically calculated ones. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Nitrogen K-edge x-ray absorption near edge structure of pyrimidine-containing nucleotides in aqueous solution

    SciTech Connect

    Shimada, Hiroyuki Minami, Hirotake; Okuizumi, Naoto; Sakuma, Ichiro; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    2015-05-07

    X-ray absorption near edge structure (XANES) was measured at energies around the N K-edge of the pyrimidine-containing nucleotides, cytidine 5′-monophosphate (CMP), 2′-deoxythymidine 5′-monophosphate (dTMP), and uridine 5′-monophosphate (UMP), in aqueous solutions and in dried films under various pH conditions. The features of resonant excitations below the N K-edge in the XANES spectra for CMP, dTMP, and UMP changed depending on the pH of the solutions. The spectral change thus observed is systematically explained by the chemical shift of the core-levels of N atoms in the nucleobase moieties caused by structural changes due to protonation or deprotonation at different proton concentrations. This interpretation is supported by the results of theoretical calculations using density functional theory for the corresponding nucleobases in the neutral and protonated or deprotonated forms.

  20. Nitrogen K-edge x-ray absorption near edge structure of pyrimidine-containing nucleotides in aqueous solution.

    PubMed

    Shimada, Hiroyuki; Minami, Hirotake; Okuizumi, Naoto; Sakuma, Ichiro; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    2015-05-07

    X-ray absorption near edge structure (XANES) was measured at energies around the N K-edge of the pyrimidine-containing nucleotides, cytidine 5'-monophosphate (CMP), 2'-deoxythymidine 5'-monophosphate (dTMP), and uridine 5'-monophosphate (UMP), in aqueous solutions and in dried films under various pH conditions. The features of resonant excitations below the N K-edge in the XANES spectra for CMP, dTMP, and UMP changed depending on the pH of the solutions. The spectral change thus observed is systematically explained by the chemical shift of the core-levels of N atoms in the nucleobase moieties caused by structural changes due to protonation or deprotonation at different proton concentrations. This interpretation is supported by the results of theoretical calculations using density functional theory for the corresponding nucleobases in the neutral and protonated or deprotonated forms.

  1. Probing single magnon excitations in Sr₂IrO₄ using O K-edge resonant inelastic x-ray scattering

    DOE PAGES

    Liu, X.; Dean, M. P. M.; Liu, J.; ...

    2015-04-28

    Resonant inelastic X-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr₂IrO₄, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edgemore » RIXS energy resolutions in the hard X-ray region is usually poor.« less

  2. EPR studies of 5-bromouracil crystal after irradiation with X rays in the bromine K-edge region.

    PubMed

    Yokoya, Akinari; Takakura, Kaoru; Watanabe, Ritsuko; Akamatsu, Ken; Ito, Takashi

    2004-10-01

    Radicals induced in a single crystal of 5-bromouracil (BrUra) by synchrotron soft X rays in the bromine K-edge region (13.461-13.482 keV) were investigated using the X-band EPR method. The crystal was irradiated at three peak energies of the absorption spectrum at room temperature or at 80 K. A hydrogen abstraction radical derived from N1 of the pyrimidine ring was commonly observed for all of the energies used, though with some variation in quantity. Similar characteristics were also observed in the EPR signal for the off-K-edge low-energy (13.42 keV) and (60)Co gamma rays used for comparison. When irradiated at 80 K, a much larger exposure (roughly 10 times) of soft X rays was needed to obtain the same signal intensity as that observed at room temperature. EPR signals were not detectable with gamma irradiation at liquid nitrogen temperature.

  3. Probing single magnon excitations in Sr₂IrO₄ using O K-edge resonant inelastic x-ray scattering

    SciTech Connect

    Liu, X.; Dean, M. P. M.; Liu, J.; Chiuzbaian, S. G.; Jaouen, N.; Nicolaou, A.; Yin, W. G.; Rayan Serrao, C.; Ramesh, R.; Ding, H.; Hill, J. P.

    2015-04-28

    Resonant inelastic X-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr₂IrO₄, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolutions in the hard X-ray region is usually poor.

  4. Sulfur K-edge X-ray absorption spectroscopy as an experimental probe for S-nitroso proteins

    SciTech Connect

    Szilagyi, Robert K. . E-mail: Szilagyi@Montana.EDU; Schwab, David E.

    2005-04-29

    X-ray absorption spectroscopy at the sulfur K-edge (2.4-2.6 keV) provides a sensitive and specific technique to identify S-nitroso compounds, which have significance in nitric oxide-based cell signaling. Unique spectral features clearly distinguish the S-nitroso-form of a cysteine residue from the sulfhydryl-form or from a methionine thioether. Comparison of the sulfur K-edge spectra of thiolate, thiol, thioether, and S-nitroso thiolate compounds indicates high sensitivity of energy positions and intensities of XAS pre-edge features as determined by the electronic environment of the sulfur absorber. A new experimental setup is being developed for reaching the in vivo concentration range of S-nitroso thiol levels in biological samples.

  5. Intermolecular bonding of hemin in solution and in solid state probed by N K-edge X-ray spectroscopies.

    PubMed

    Golnak, Ronny; Xiao, Jie; Atak, Kaan; Stevens, Joanna S; Gainar, Adrian; Schroeder, Sven L M; Aziz, Emad F

    2015-11-21

    X-ray absorption/emission spectroscopy (XAS/XES) at the N K-edge of iron protoporphyrin IX chloride (FePPIX-Cl, or hemin) has been carried out for dissolved monomers in DMSO, dimers in water and for the solid state. This sequence of samples permits identification of characteristic spectral features associated with the hemin intermolecular bonding. These characteristic features are further analyzed and understood at the molecular orbital (MO) level based on the DFT calculations.

  6. Comparison of quantitative k-edge empirical estimators using an energy-resolved photon-counting detector

    NASA Astrophysics Data System (ADS)

    Zimmerman, Kevin C.; Gilat Schmidt, Taly

    2016-03-01

    Using an energy-resolving photon counting detector, the amount of k-edge material in the x-ray path can be estimated using a process known as material decomposition. However, non-ideal effects within the detector make it difficult to accurately perform this decomposition. This work evaluated the k-edge material decomposition accuracy of two empirical estimators. A neural network estimator and a linearized maximum likelihood estimator with error look-up tables (A-table method) were evaluated through simulations and experiments. Each estimator was trained on system-specific calibration data rather than specific modeling of non-ideal detector effects or the x-ray source spectrum. Projections through a step-wedge calibration phantom consisting of different path lengths through PMMA, aluminum, and a k-edge material was used to train the estimators. The estimators were tested by decomposing data acquired through different path lengths of the basis materials. The estimators had similar performance in the chest phantom simulations with gadolinium. They estimated four of the five densities of gadolinium with less than 2mg/mL bias. The neural networks estimates demonstrated lower bias but higher variance than the A-table estimates in the iodine contrast agent simulations. The neural networks had an experimental variance lower than the CRLB indicating it is a biased estimator. In the experimental study, the k-edge material contribution was estimated with less than 14% bias for the neural network estimator and less than 41% bias for the A-table method.

  7. K-edge XANES investigation of octakis(DMSO)lanthanoid(III) complexes in DMSO solution and solid iodides.

    PubMed

    D'Angelo, Paola; Migliorati, Valentina; Spezia, Riccardo; De Panfilis, Simone; Persson, Ingmar; Zitolo, Andrea

    2013-06-14

    The potential of high energy XANES (X-ray absorption near edge structure) as a tool for the structural analysis of lanthanoid-containing systems has been explored. The K-edge XANES spectra of La(3+), Gd(3+), and Lu(3+) ions both in DMSO solution and solid octakis(DMSO)lanthanoid(III) iodides have been analysed. Although the K-edges of lanthanoids cover the energy range of 38 (La) to 65 (Lu) keV, the large widths of the core hole states do not appreciably reduce the potential structural information of the XANES data. We show that, for lanthanoid compounds, accurate structural parameters are obtained from the analysis of K-edge XANES signals if a deconvolution procedure is carried out. We found that in solid octakis(DMSO)lanthanoid(III) iodides the Ln(3+) ions are coordinated by eight DMSO ligands arranged in a quite symmetric fashion. In DMSO solution the Ln(3+) ions retain a regular eight-coordination structure and the coordination number does not change along the series. In contrast to when in water the second coordination shell has been found to provide a negligible contribution to the XANES spectra of Ln(3+) ions in DMSO solution.

  8. Characterization of extracellular polymeric substances in the biofilms of typical bacteria by the sulfur K-edge XANES spectroscopy.

    PubMed

    Lin, Huirong; Ye, Chengsong; Lv, Lu; Zheng, Clark Renjun; Zhang, Shenghua; Zheng, Lei; Zhao, Yidong; Yu, Xin

    2014-08-01

    A combined approach of physicochemical extraction and sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy was applied to characterize the extracellular polymeric substances (EPS) of typical bacterial biofilms in this study. Physicochemical analysis showed variation of the contents of DNA, polysaccharide and protein in different fractions of EPS in different mediums. The sulfur K-edge XANES analysis yielded a variety of spectra. Spectral fitting of the XANES spectra utilizing a large set of model compounds showed that there was more reduced sulfur in both LB-EPS (loosely bound EPS) and TB-EPS (tightly bound EPS) of all the biofilms in LB medium than in R2A medium. More oxidized sulfur was identified in LB-EPS than that in TB-EPS, suggesting different niches and physiological heterogeneity in the biofilms. Our results suggested that the sulfur K-edge XANES can be a useful tool to analyze the sulfur speciation in EPS of biofilms.

  9. Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer.

    PubMed

    Van Kuiken, Benjamin E; Ross, Matthew R; Strader, Matthew L; Cordones, Amy A; Cho, Hana; Lee, Jae Hyuk; Schoenlein, Robert W; Khalil, Munira

    2017-07-01

    Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400 nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps) and decays within 6 ns. The second transient species forms on a timescale of ∼400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowest-lying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.

  10. K-edge XANES investigation of octakis(DMSO)lanthanoid(III) complexes in DMSO solution and solid iodides

    PubMed Central

    D’Angelo, Paola; Migliorati, Valentina; Spezia, Riccardo; De Panfilis, Simone; Persson, Ingmar; Zitolo, Andrea

    2014-01-01

    The potentiality of high energy XANES (X-ray absorption near edge structure) as a structural tool for lanthanoid-containing systems has been explored. The K-edge XANES spectra of La3+, Gd3+, and Lu3+ ions both in DMSO solution and solid octakis(DMSO) lanthanoid(III) iodides have been analysed. Although the K-edges of lanthanoids cover the energy range 38 (La) to 65 (Lu) keV, the large widths of the core hole states do not appreciably reduce the potential structural information of XANES data. We show that, for lanthanoid compounds, accurate structural parameters are obtained from the analysis of K-edge XANES signal if a deconvolution procedure is carried out. We found that in solid octakis(DMSO) lanthanoid(III) iodides the Ln3+ ions are coordinated by eight DMSO ligands arranged in a quite symmetric fashion. In DMSO solution the Ln3+ ions retain a regular eight-coordination structure and the coordination number does not change along the series. At variance with water the second coordination shell has been found to provide a negligible contribution to the XANES spectra of Ln3+ ions in DMSO solution. PMID:23657739

  11. Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

    PubMed Central

    Van Kuiken, Benjamin E.; Ross, Matthew R.; Strader, Matthew L.; Cordones, Amy A.; Cho, Hana; Lee, Jae Hyuk; Schoenlein, Robert W.; Khalil, Munira

    2017-01-01

    Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400 nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps) and decays within 6 ns. The second transient species forms on a timescale of ∼400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowest-lying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems. PMID:28529962

  12. Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

    DOE PAGES

    Van Kuiken, Benjamin E.; Ross, Matthew R.; Strader, Matthew L.; ...

    2017-05-08

    Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (~2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps)more » and decays within 6 ns. The second transient species forms on a timescale of ~400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowestlying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.« less

  13. Three-dimensional labeling of newly formed bone using synchrotron radiation barium K-edge subtraction imaging

    NASA Astrophysics Data System (ADS)

    Panahifar, Arash; Swanston, Treena M.; Pushie, M. Jake; Belev, George; Chapman, Dean; Weber, Lynn; Cooper, David M. L.

    2016-07-01

    Bone is a dynamic tissue which exhibits complex patterns of growth as well as continuous internal turnover (i.e. remodeling). Tracking such changes can be challenging and thus a high resolution imaging-based tracer would provide a powerful new perspective on bone tissue dynamics. This is, particularly so if such a tracer can be detected in 3D. Previously, strontium has been demonstrated to be an effective tracer which can be detected by synchrotron-based dual energy K-edge subtraction (KES) imaging in either 2D or 3D. The use of strontium is, however, limited to very small sample thicknesses due to its low K-edge energy (16.105 keV) and thus is not suitable for in vivo application. Here we establish proof-of-principle for the use of barium as an alternative tracer with a higher K-edge energy (37.441 keV), albeit for ex vivo imaging at the moment, which enables application in larger specimens and has the potential to be developed for in vivo imaging of preclinical animal models. New bone formation within growing rats in 2D and 3D was demonstrated at the Biomedical Imaging and Therapy bending magnet (BMIT-BM) beamline of the Canadian Light Source synchrotron. Comparative x-ray fluorescence imaging confirmed those patterns of uptake detected by KES. This initial work provides a platform for the further development of this tracer and its exploration of applications for in vivo development.

  14. Cu,Zn-Superoxide Dismutase-Mediated Redox Regulation of Jumonji Domain Containing 3 Modulates Macrophage Polarization and Pulmonary Fibrosis.

    PubMed

    He, Chao; Larson-Casey, Jennifer L; Gu, Linlin; Ryan, Alan J; Murthy, Shubha; Carter, A Brent

    2016-07-01

    M2 macrophages are implicated in the development of pulmonary fibrosis as they generate profibrotic signals. The polarization process, at least in part, is regulated by epigenetic modulation. Because Cu,Zn-superoxide dismutase-induced H2O2 can polarize macrophages to a profibrotic M2 phenotype, we hypothesized that modulation of the redox state of the cell is involved in the epigenetic modulation of the macrophage phenotype. In this study, we show that signal transducer and activator of transcription 6 (STAT6) regulates Jumonji domain containing (Jmjd) 3, a histone H3 lysine 27 demethylase, and mutation of a redox-sensitive cysteine in STAT6 attenuates jmjd3 expression. Moreover, Jmjd3 deficiency abrogates profibrotic M2 gene expression. Treatment with leflunomide, which reduces mitochondrial reactive oxygen species production and tyrosine phosphorylation, inhibits jmjd3 expression and M2 polarization, as well as development of a fibrotic phenotype. Taken together, these observations provide evidence that the redox regulation of Jmjd3 is a unique regulatory mechanism for Cu,Zn-superoxide dismutase-mediated profibrotic M2 polarization. Furthermore, leflunomide, which reduces reactive oxygen species production and tyrosine phosphorylation, may prove to be therapeutic in the treatment of asbestos-induced pulmonary fibrosis.

  15. Spin polarization in photoemission from the cuprate superconductor Bi2Sr2CaCu2O8 +δ

    NASA Astrophysics Data System (ADS)

    Fanciulli, Mauro; Muff, Stefan; Weber, Andrew P.; Dil, J. Hugo

    2017-06-01

    Photoelectrons produced from the excitation of spin-degenerate states in solids can have a sizable spin polarization, which is related to the phase of interfering channels in the photoemission matrix elements. Such spin polarization can be measured by spin-resolved photoemission spectroscopy to gain information about the transitions and the Wigner time delay of the process. Incorporating strongly correlated electron systems into this paradigm could yield a novel means of extracting phase information crucial to understanding the mechanism of their emergent behavior. In this work, we present, as a case study, experimental measurements of the cuprate superconductor Bi2Sr2CaCu2O8 +δ by spin-resolved photoemission while maintaining full angular and energy resolution. A spin polarization of at least 10 % is observed, which is related to the phase of the photoelectron wave function.

  16. Ti K-edge EXAFS and XANES study on tektites from different strewnfields

    NASA Astrophysics Data System (ADS)

    Wang, L.; Furuta, T.; Okube, M.; Yoshiasa, A.

    2011-12-01

    The concentration and local structure of each element may have various kinds of information about the asteroid impact and mass extinction. Farges and Brown have discussed about the Ti local structure by XANES, and concluded that Ti in tektite occupies 4-coordinated site. EXAFS can be analyzed to give precise information about the distance from Ti to near neighbors. The XAFS measurement of Ti local structure was preformed at the beamline 9C of the Photon Factory in KEK, Tsukuba, Japan. The specimens of tektites are from different strewnfields, they are: indochinite, bediasite, hainanite, philippinite, australite and moldavite. Sample for comparison are Libya desert glass and suevite. The k3χ(k) function was transformed into the radial structure function (RSF) for Ti K-edge of six tektites. The RSF for the Ti atom in indochinite and bediasite are similar; hainanite, australite and philippinite are similar; and moldavite is discriminated from others. It indicates that they have the same local atomic environmental around the Ti atoms and extended structure respectively. Coordination numbers and radial structure function are determined by EXAFS analyses (Table 1). We classified the tektites in three types: in indochinite and bediasite, Ti occupies 4-coordinated tetrahedral site and Ti-O distances are 1.84-1.81 Å; in hainanite, australite and philippinite, Ti occupies 5-coordinated trigonal bi-pyramidal or tetragonal pyramidal site and Ti-O distances are 1.92-1.87 Å; in moldavite, Ti occupies the 6-coordinated octahedral site and Ti-O distance is 2.00-1.96 Å. Formation of tektites is related to the impact process. It is generally recognized that tektites were formed under higher temperature and high pressure. But through this study, local structures of Ti are differing in three strewnfields and even different locations of the same strewnfield. What caused the various local structures will be another topic of tektite studies. Local structure of Ti may be changed in

  17. Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

    NASA Astrophysics Data System (ADS)

    Furnare, Luca J.; Vailionis, Arturas; Strawn, Daniel G.

    2005-11-01

    Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength ( I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.

  18. Spin polarized low energy electron microscopy of quantum well resonances in Fe films on the Cu-covered W(110) surface.

    PubMed

    Wu, Qiang; Altman, M S

    2013-07-01

    Spin polarized low energy electron microscopy has been used to investigate the quantum size effect (QSE) in electron reflectivity from Fe films grown on a pseudomorphic Cu layer on a W(110) surface. Intensity oscillations caused by the QSE as functions of Fe film thickness and incident electron energy identify quantum well resonance conditions in the film. Evaluation of these intensity oscillations using the phase accumulation model provides information on the unoccupied spin polarized band structure in the Fe film above the vacuum level. We also find evidence that the presence of the non-magnetic Cu layer shifts spin polarized quantum well resonances in the Fe layer uniformly downward in energy by 1.1eV compared to Fe/W(110) films without an interface Cu layer, suggesting that the Cu layer gives a small degree of control over the quantum well resonances.

  19. Removing arsenic from synthetic groundwater with iron electrocoagulation: an Fe and As K-edge EXAFS study.

    PubMed

    van Genuchten, Case M; Addy, Susan E A; Peña, Jasquelin; Gadgil, Ashok J

    2012-01-17

    Electrocoagulation (EC) using iron electrodes is a promising arsenic removal strategy for Bangladesh groundwater drinking supplies. EC is based on the rapid in situ dissolution of a sacrificial Fe(0) anode to generate iron precipitates with a high arsenic sorption affinity. We used X-ray absorption spectroscopy (XAS) to investigate the local coordination environment (<4.0 Å) of Fe and As in EC precipitates generated in synthetic Bangladesh groundwater (SBGW). Fe and As K-edge EXAFS spectra were found to be similar between samples regardless of the large range of current density (0.02, 1.1, 5.0, 100 mA/cm(2)) used to generate samples. Shell-by-shell fits of the Fe K-edge EXAFS spectra indicated that EC precipitates consist of primarily edge-sharing FeO(6) octahedra. The absence of corner-sharing FeO(6) octahedra implies that EC precipitates resemble nanoscale clusters (polymers) of edge-sharing octahedra that efficiently bind arsenic. Shell-by-shell fits of As K-edge EXAFS spectra show that arsenic, initially present as a mixture of As(III) and As(V), forms primarily binuclear, corner-sharing As(V) surface complexes on EC precipitates. This specific coordination geometry prevents the formation of FeO(6) corner-sharing linkages. Phosphate and silicate, abundant in SBGW, likely influence the structure of EC precipitates in a similar way by preventing FeO(6) corner-sharing linkages. This study provides a better understanding of the structure, reactivity, and colloidal stability of EC precipitates and the behavior of arsenic during EC. The results also offer useful constraints for predicting arsenic remobilization during the long-term disposal of EC sludge.

  20. Absorption and scattering by interstellar dust in the silicon K-edge of GX 5-1

    NASA Astrophysics Data System (ADS)

    Zeegers, S. T.; Costantini, E.; de Vries, C. P.; Tielens, A. G. G. M.; Chihara, H.; de Groot, F.; Mutschke, H.; Waters, L. B. F. M.; Zeidler, S.

    2017-03-01

    Context. We study the absorption and scattering of X-ray radiation by interstellar dust particles, which allows us to access the physical and chemical properties of dust. The interstellar dust composition is not well understood, especially on the densest sight lines of the Galactic plane. X-rays provide a powerful tool in this study. Aims: We present newly acquired laboratory measurements of silicate compounds taken at the Soleil synchrotron facility in Paris using the Lucia beamline. The dust absorption profiles resulting from this campaign were used in this pilot study to model the absorption by interstellar dust along the line of sight of the low-mass X-ray binary GX 5-1. Methods: The measured laboratory cross-sections were adapted for astrophysical data analysis and the resulting extinction profiles of the Si K-edge were implemented in the SPEX spectral fitting program. We derive the properties of the interstellar dust along the line of sight by fitting the Si K-edge seen in absorption in the spectrum of GX 5-1. Results: We measured the hydrogen column density towards GX 5-1 to be 3.40 ± 0.1 × 1022 cm-2. The best fit of the silicon edge in the spectrum of GX 5-1 is obtained by a mixture of olivine and pyroxene. In this study, our modeling is limited to Si absorption by silicates with different Mg:Fe ratios. We obtained an abundance of silicon in dust of 4.0 ± 0.3 × 10-5 per H atom and a lower limit for total abundance, considering both gas and dust of >4.4 × 10-5 per H atom, which leads to a gas to dust ratio of >0.22. Furthermore, an enhanced scattering feature in the Si K-edge may suggest the presence of large particles along the line of sight.

  1. K-edge subtraction angiography with synchrotron x-rays: Final technical report, (February 1, 1984 to January 31, 1987)

    SciTech Connect

    Hofstadter, R

    1987-09-01

    The aim was the development of an angiographic method and appropriate equipment for imaging with x-rays the coronary arteries in a non-invasive manner. Successive steps involved studies with phantoms, live animals and finally with human subjects. Clinical evaluation of human coronary arteries remains a goal of this and a continuing project, and steps along the way to such an achievement are in process. Transvenous injection of a dye using the method of iodine dichromography near 33.2 keV, the K-edge of iodine, forms the basis of the method. 11 refs.

  2. K-edge Subtraction Angiography with Synchrotron X-Rays: Final Technical Report, (February 1, 1984 to January 31, 1987)

    DOE R&D Accomplishments Database

    Hofstadter, R.

    1987-09-01

    The aim was the development of an angiographic method and appropriate equipment for imaging with x-rays the coronary arteries in a non-invasive manner. Successive steps involved studies with phantoms, live animals and finally with human subjects. Clinical evaluation of human coronary arteries remains a goal of this and a continuing project, and steps along the way to such an achievement are in process. Transvenous injection of a dye using the method of iodine dichromography near 33.2 keV, the K-edge of iodine, forms the basis of the method

  3. Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge

    NASA Astrophysics Data System (ADS)

    Schreck, Simon; Wernet, Philippe

    2016-09-01

    The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

  4. Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

    PubMed

    Schreck, Simon; Wernet, Philippe

    2016-09-14

    The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

  5. Polar Kerr Effect Measurements of YBa_2Cu_3O_6+x: Evidence for Broken Symmetry Near the Pseudogap Temperature

    SciTech Connect

    Xia, Jing

    2011-08-24

    Polar Kerr effect in the high-Tc superconductor YBa{sub 2}Cu{sub 3}O{sub 6+x} was measured at zero magnetic field with high precision using a cyogenic Sagnac fiber interferometer. We observed non-zero Kerr rotations of order {approx} 1 {micro}rad appearing near the pseudogap temperature T*, and marking what appears to be a true phase transition. Anomalous magnetic behavior in magnetic-field training of the effect suggests that time reversal symmetry is already broken above room temperature.

  6. In situ Polarized Neutron Reflectometry: Epitaxial Thin-Film Growth of Fe on Cu(001) by dc Magnetron Sputtering

    NASA Astrophysics Data System (ADS)

    Kreuzpaintner, Wolfgang; Wiedemann, Birgit; Stahn, Jochen; Moulin, Jean-François; Mayr, Sina; Mairoser, Thomas; Schmehl, Andreas; Herrnberger, Alexander; Korelis, Panagiotis; Haese, Martin; Ye, Jingfan; Pomm, Matthias; Böni, Peter; Mannhart, Jochen

    2017-05-01

    The stepwise growth of epitaxial Fe on Cu (001 )/Si (001 ) , investigated by in situ polarized neutron reflectometry is presented. A sputter deposition system was integrated into the neutron reflectometer AMOR at the Swiss neutron spallation source SINQ, which enables the analysis of the microstructure and magnetic moments during all deposition steps of the Fe layer. We report on the progressive evolution of the accessible parameters describing the microstructure and the magnetic properties of the Fe film, which reproduce known features and extend our knowledge on the behavior of ultrathin iron films.

  7. Ni K-Edge XAS Suggests that Coordination of Ni II to the Unstructured Amyloidogenice Region of the Human Prion Protein Produces a Ni2 bis-u-hydroxo Dimer

    SciTech Connect

    Shearer,J.; Soh, P.

    2007-01-01

    Prion diseases are thought to be caused by the misfolding of the ubiquitous neuronal membrane prion protein (PrP) through an unknown mechanism that may involve Cu{sup II} coordination to the PrP. Previous work has utilized Ni{sup II} as a diamagnetic probe for Cu{sup II} coordination [C.E. Jones, M. Klewpatinond, S.R. Abdelraheim, D.R. Brown, J.H. Viles, J. Mol. Biol. 346 (2005) 1393-1407]. Herein we investigate Ni{sup II} coordination to the PrP fragment PrP(93-114) (AcN-GGTHSQWNKPSKPKTNMKHMAG) at pH = 10.0 by Ni K-edge X-ray absorption spectroscopy (XAS). We find that two equivalents of Ni{sup II} will coordinate to PrP(93-114) by UV/Vis titrations and mass spectrometry. Ni K-edge XAS data is consistent with Ni{sup II} ligated by five N/O based ligands (three N/O ligands at 2.01(2) {angstrom} and two at 1.855(2) {angstrom}). We were also able to locate a Ni-Ni vector at 3.1(1) {angstrom}, which suggests the two Ni{sup II} centers are contained in a bis-{mu}-hydroxo dimer. We therefore suggest that Ni{sup II} may not be a suitable diamagnetic mimic for Cu{sup II} coordination within the PrP since differential coordination modes for the two metals exist.

  8. Structure of Alkali Borate Glasses at High Pressure: B and Li K-Edge Inelastic X-Ray Scattering Study

    SciTech Connect

    Lee, Sung Keun; Eng, Peter J.; Mao, Ho-kwang; Meng, Yue; Shu, Jinfu

    2008-06-16

    We report the first in situ boron K-edge inelastic x-ray scattering (IXS) spectra for alkali borate glasses (Li{sub 2}B{sub 4}O{sub 7}) at high pressure up to 30 GPa where pressure-induced coordination transformation from three-coordinated to four-coordinated boron was directly probed. Coordination transformation (reversible upon decompression) begins around 5 GPa and the fraction of four-coordinated boron increases with pressure from about 50% (at 1 atm) to more than 95% (at 30 GPa) with multiple densification mechanisms, evidenced by three distinct pressure ranges for (d{sup [4]}B/dP){sub T}. The lithium K-edge IXS spectrum for Li-borate glasses at 5 GPa shows IXS features similar to that at 1 atm, suggesting that the Li environment does not change much with pressure up to 5 GPa. These results provide improved understanding of the structure of low-z glass at high pressure.

  9. Near-coincident K-line and K-edge energies as ionization diagnostics for some high atomic number plasmas

    SciTech Connect

    Pereira, N. R.; Weber, B. V.; Phipps, D. G.; Schumer, J. W.; Seely, J. F.; Carroll, J. J.; Vanhoy, J. R.; Slabkowska, K.; Polasik, M.

    2012-10-15

    For some high atomic number atoms, the energy of the K-edge is tens of eVs higher than the K-line energy of another atom, so that a few eV increase in the line's energy results in a decreasing transmission of the x-ray through a filter of the matching material. The transmission of cold iridium's Asymptotically-Equal-To 63.287 keV K{alpha}{sub 2} line through a lutetium filter is 7% lower when emitted by ionized iridium, consistent with an energy increase of {Delta}{epsilon} Asymptotically-Equal-To 10{+-}1 eV associated with the ionization. Likewise, the transmission of the K{beta}{sub 1} line of ytterbium through a near-coincident K-edge filter changes depending on plasma parameters that should affect the ionization. Systematic exploration of filter-line pairs like these could become a unique tool for diagnostics of suitable high energy density plasmas.

  10. Experimental feasibility of multi-energy photon-counting K-edge imaging in pre-clinical computed tomography

    NASA Astrophysics Data System (ADS)

    Schlomka, J. P.; Roessl, E.; Dorscheid, R.; Dill, S.; Martens, G.; Istel, T.; Bäumer, C.; Herrmann, C.; Steadman, R.; Zeitler, G.; Livne, A.; Proksa, R.

    2008-08-01

    Theoretical considerations predicted the feasibility of K-edge x-ray computed tomography (CT) imaging using energy discriminating detectors with more than two energy bins. This technique enables material-specific imaging in CT, which in combination with high-Z element based contrast agents, opens up possibilities for new medical applications. In this paper, we present a CT system with energy detection capabilities, which was used to demonstrate the feasibility of quantitative K-edge CT imaging experimentally. A phantom was imaged containing PMMA, calcium-hydroxyapatite, water and two contrast agents based on iodine and gadolinium, respectively. Separate images of the attenuation by photoelectric absorption and Compton scattering were reconstructed from energy-resolved projection data using maximum-likelihood basis-component decomposition. The data analysis further enabled the display of images of the individual contrast agents and their concentrations, separated from the anatomical background. Measured concentrations of iodine and gadolinium were in good agreement with the actual concentrations. Prior to the tomographic measurements, the detector response functions for monochromatic illumination using synchrotron radiation were determined in the energy range 25 keV-60 keV. These data were used to calibrate the detector and derive a phenomenological model for the detector response and the energy bin sensitivities.

  11. Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

    DOE PAGES

    Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.; ...

    2017-06-22

    Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

  12. Ab initio x-ray absorption near-edge structure study of Ti K-edge in rutile.

    PubMed

    Chaboy, J; Nakajima, N; Tezuka, Y

    2007-07-04

    This work reports a theoretical x-ray absorption near-edge structure (XANES) spectroscopy study at the Ti K-edge in TiO(2) rutile. We present detailed ab initio computations of the Ti K-edge XANES spectrum performed within the multiple-scattering framework. An extensive discussion is presented concerning the size of the cluster needed to reproduce the experimental spectrum, especially regarding the split main absorption line. In addition, the role of the exchange and correlation potential (ECP) in reproducing all the experimental XANES features is discussed. The best agreement between experimental data and computations is obtained by using real ECP potentials, i.e. the energy-dependent Dirac-Hara exchange potential, or by using only the real part of the energy-dependent Hedin-Lundqvist complex potential, together with an additional imaginary constant to account for the core-hole lifetime and the experimental resolution. The addition of the imaginary part of the HL potential worsens the agreement between the experimental and calculated spectra, indicating the failure of the complex part of the Hedin-Lundqvist ECP in accounting for the electron damping in these systems.

  13. Observation of yttrium oxide nanoparticles in cabbage (Brassica oleracea) through dual energy K-edge subtraction imaging

    SciTech Connect

    Chen, Yunyun; Sanchez, Carlos; Yue, Yuan; de Almeida, Mauricio; González, Jorge M.; Parkinson, Dilworth Y.; Liang, Hong

    2016-03-25

    Background: The potential transfer of engineered nanoparticles (ENPs) from plants into the food chain has raised widespread concerns. In order to investigate the effects of ENPs on plants, young cabbage plants (Brassica oleracea) were exposed to a hydroponic system containing yttrium oxide (yttria) ENPs. The objective of this study was to reveal the impacts of NPs on plants by using K-edge subtraction imaging technique. Results: Using synchrotron dual-e nergy X-ray micro-tomography with K-edge subtraction technique, we studied the uptake, accumulation, distribution and concentration mapping of yttria ENPs in cabbage plants. It was found that yttria ENPs were uptaken by the cabbage roots but did not effectively transferred and mobilized through the cabbage stem and leaves. This could be due to the accumulation of yttria ENPs blocked at primary-lateral-root junction. Instead, non-yttria minerals were found in the xylem vessels of roots and stem. Conclusions: Synchrotron dual-energy X-ray micro-tomography is an effective method to observe yttria NPs inside the cabbage plants in both whole body and microscale level. Furthermore, the blockage of a plant's roots by nanoparticles is likely the first and potentially fatal environmental effect of such type of nanoparticles.

  14. Long-range chemical sensitivity in the sulfur K-edge X-ray absorption spectra of substituted thiophenes.

    PubMed

    George, Graham N; Hackett, Mark J; Sansone, Michael; Gorbaty, Martin L; Kelemen, Simon R; Prince, Roger C; Harris, Hugh H; Pickering, Ingrid J

    2014-09-11

    Thiophenes are the simplest aromatic sulfur-containing compounds and are stable and widespread in fossil fuels. Regulation of sulfur levels in fuels and emissions has become and continues to be ever more stringent as part of governments' efforts to address negative environmental impacts of sulfur dioxide. In turn, more effective removal methods are continually being sought. In a chemical sense, thiophenes are somewhat obdurate and hence their removal from fossil fuels poses problems for the industrial chemist. Sulfur K-edge X-ray absorption spectroscopy provides key information on thiophenic components in fuels. Here we present a systematic study of the spectroscopic sensitivity to chemical modifications of the thiophene system. We conclude that while the utility of sulfur K-edge X-ray absorption spectra in understanding the chemical composition of sulfur-containing fossil fuels has already been demonstrated, care must be exercised in interpreting these spectra because the assumption of an invariant spectrum for thiophenic forms may not always be valid.

  15. Observation of yttrium oxide nanoparticles in cabbage (Brassica oleracea) through dual energy K-edge subtraction imaging.

    PubMed

    Chen, Yunyun; Sanchez, Carlos; Yue, Yuan; de Almeida, Mauricio; González, Jorge M; Parkinson, Dilworth Y; Liang, Hong

    2016-03-25

    The potential transfer of engineered nanoparticles (ENPs) from plants into the food chain has raised widespread concerns. In order to investigate the effects of ENPs on plants, young cabbage plants (Brassica oleracea) were exposed to a hydroponic system containing yttrium oxide (yttria) ENPs. The objective of this study was to reveal the impacts of NPs on plants by using K-edge subtraction imaging technique. Using synchrotron dual-energy X-ray micro-tomography with K-edge subtraction technique, we studied the uptake, accumulation, distribution and concentration mapping of yttria ENPs in cabbage plants. It was found that yttria ENPs were uptaken by the cabbage roots but did not effectively transferred and mobilized through the cabbage stem and leaves. This could be due to the accumulation of yttria ENPs blocked at primary-lateral-root junction. Instead, non-yttria minerals were found in the xylem vessels of roots and stem. Synchrotron dual-energy X-ray micro-tomography is an effective method to observe yttria NPs inside the cabbage plants in both whole body and microscale level. Furthermore, the blockage of a plant's roots by nanoparticles is likely the first and potentially fatal environmental effect of such type of nanoparticles.

  16. Observation of yttrium oxide nanoparticles in cabbage (Brassica oleracea) through dual energy K-edge subtraction imaging

    DOE PAGES

    Chen, Yunyun; Sanchez, Carlos; Yue, Yuan; ...

    2016-03-25

    Background: The potential transfer of engineered nanoparticles (ENPs) from plants into the food chain has raised widespread concerns. In order to investigate the effects of ENPs on plants, young cabbage plants (Brassica oleracea) were exposed to a hydroponic system containing yttrium oxide (yttria) ENPs. The objective of this study was to reveal the impacts of NPs on plants by using K-edge subtraction imaging technique. Results: Using synchrotron dual-e nergy X-ray micro-tomography with K-edge subtraction technique, we studied the uptake, accumulation, distribution and concentration mapping of yttria ENPs in cabbage plants. It was found that yttria ENPs were uptaken by themore » cabbage roots but did not effectively transferred and mobilized through the cabbage stem and leaves. This could be due to the accumulation of yttria ENPs blocked at primary-lateral-root junction. Instead, non-yttria minerals were found in the xylem vessels of roots and stem. Conclusions: Synchrotron dual-energy X-ray micro-tomography is an effective method to observe yttria NPs inside the cabbage plants in both whole body and microscale level. Furthermore, the blockage of a plant's roots by nanoparticles is likely the first and potentially fatal environmental effect of such type of nanoparticles.« less

  17. Long-Range Chemical Sensitivity in the Sulfur K-Edge X-ray Absorption Spectra of Substituted Thiophenes

    PubMed Central

    2015-01-01

    Thiophenes are the simplest aromatic sulfur-containing compounds and are stable and widespread in fossil fuels. Regulation of sulfur levels in fuels and emissions has become and continues to be ever more stringent as part of governments’ efforts to address negative environmental impacts of sulfur dioxide. In turn, more effective removal methods are continually being sought. In a chemical sense, thiophenes are somewhat obdurate and hence their removal from fossil fuels poses problems for the industrial chemist. Sulfur K-edge X-ray absorption spectroscopy provides key information on thiophenic components in fuels. Here we present a systematic study of the spectroscopic sensitivity to chemical modifications of the thiophene system. We conclude that while the utility of sulfur K-edge X-ray absorption spectra in understanding the chemical composition of sulfur-containing fossil fuels has already been demonstrated, care must be exercised in interpreting these spectra because the assumption of an invariant spectrum for thiophenic forms may not always be valid. PMID:25116792

  18. Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption.

    PubMed

    Wolf, T J A; Myhre, R H; Cryan, J P; Coriani, S; Squibb, R J; Battistoni, A; Berrah, N; Bostedt, C; Bucksbaum, P; Coslovich, G; Feifel, R; Gaffney, K J; Grilj, J; Martinez, T J; Miyabe, S; Moeller, S P; Mucke, M; Natan, A; Obaid, R; Osipov, T; Plekan, O; Wang, S; Koch, H; Gühr, M

    2017-06-22

    Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. High-level-coupled cluster calculations confirm the method's impressive electronic structure sensitivity for excited-state investigations.Many photo-induced processes such as photosynthesis occur in organic molecules, but their femtosecond excited-state dynamics are difficult to track. Here, the authors exploit the element and site selectivity of soft X-ray absorption to sensitively follow the ultrafast ππ*/nπ* electronic relaxation of hetero-organic molecules.

  19. High-sensitivity determination of Zn(II) and Cu(II) in vitro by fluorescence polarization

    NASA Astrophysics Data System (ADS)

    Thompson, Richard B.; Maliwal, Badri P.; Feliccia, Vincent; Fierke, Carol A.

    1998-04-01

    Recent work has suggested that free Cu(II) may play a role in syndromes such as Crohn's and Wilson's diseases, as well as being a pollutant toxic at low levels to shellfish and sheep. Similarly, Zn(II) has been implicated in some neural damage in the brain resulting from epilepsy and ischemia. Several high sensitivity methods exist for determining these ions in solution, including GFAAS, ICP-MS, ICP-ES, and electrochemical techniques. However, these techniques are generally slow and costly, require pretreatment of the sample, require complex instruments and skilled personnel, and are incapable of imaging at the cellular and subcellular level. To address these shortcomings we developed fluorescence polarization (anisotropy) biosensing methods for these ions which are very sensitivity, highly selective, require simple instrumentation and little pretreatment, and are inexpensive. Thus free Cu(II) or Zn(II) can be determined at picomolar levels by changes in fluorescence polarization, lifetime, or wavelength ratio using these methods; these techniques may be adapted to microscopy.

  20. Reducing radiation dose by application of optimized low-energy x-ray filters to K-edge imaging with a photon counting detector.

    PubMed

    Choi, Yu-Na; Lee, Seungwan; Kim, Hee-Joung

    2016-01-21

    K-edge imaging with photon counting x-ray detectors (PCXDs) can improve image quality compared with conventional energy integrating detectors. However, low-energy x-ray photons below the K-edge absorption energy of a target material do not contribute to image formation in the K-edge imaging and are likely to be completely absorbed by an object. In this study, we applied x-ray filters to the K-edge imaging with a PCXD based on cadmium zinc telluride for reducing radiation dose induced by low-energy x-ray photons. We used aluminum (Al) filters with different thicknesses as the low-energy x-ray filters and implemented the iodine K-edge imaging with an energy bin of 34-48 keV at the tube voltages of 50, 70 and 90 kVp. The effects of the low-energy x-ray filters on the K-edge imaging were investigated with respect to signal-difference-to-noise ratio (SDNR), entrance surface air kerma (ESAK) and figure of merit (FOM). The highest value of SDNR was observed in the K-edge imaging with a 2 mm Al filter, and the SDNR decreased as a function of the filter thicknesses. Compared to the K-edge imaging with a 2 mm Al filter, the ESAK was reduced by 66%, 48% and 39% in the K-edge imaging with a 12 mm Al filter for 50 kVp, 70 kVp and 90 kVp, respectively. The FOM values, which took into account the ESAK and SDNR, were maximized for 8, 6 to 8 and 4 mm Al filters at 50 kVp, 70 kVp and 90 kVp, respectively. We concluded that the use of an optimal low-energy filter thickness, which was determined by maximizing the FOM, could significantly reduce radiation dose while maintaining image quality in the K-edge imaging with the PCXD.

  1. Polarized-thermoreflectance study of the band-edge transitions in Cu(Al 0.5 In 0.5)S2 solar-energy related crystal.

    PubMed

    Ho, Ching-Hwa; Huang, Guan-Tzu

    2010-02-15

    Polarization dependence of band-edge excitonic transitions in Cu(Al(0.5)In(0.5))S(2) [denoted as Cu(AlIn)S(2)] has been characterized using polarized-thermoreflectance (PTR) measurements with E || <111 > and E perpendicular <111 > polarizations in the temperature range between 30 and 320 K. The measurements were done on as-grown {112} surface of the chalcopyrite crystal. The polarization dependence of the band-edge transitions of Cu(AlIn)S(2) clearly showed that the E(A) exciton is present prominently with E || <111 > polarization while the E(B) exciton appears significantly only in the E perpendicular <111 > polarized spectra. For the unpolarized spectra, both E(A) and E(B) features were combined. The E(A) feature is closely related to the E(0) transition, while the E(B) feature is that of E(0) + Delta(0) transition in the chalcopyrite. The crystal-field splitting energy of Delta(0) of Cu(AlIn)S(2) at the valence-band top is determined accurately by PTR experiments. Temperature dependences of transition energies of E(A) and E(B) transitions were analyzed. The band-edge excitons reveal an anomalous temperature-energy shift with increasing the temperatures from 30 to 320 K due to the variation of Cu d electrons' contribution to valence band that affected by the native defects inside Cu(AlIn)S(2). The PTR technique is more effective in studying the band-edge structure of the chalcopyrite crystal.

  2. Trace metal analysis by laser ablation-inductively coupled plasmamass spectrometry and x-ray K-edge densitometry of forensic samples

    SciTech Connect

    Berry, Jonna Elizabeth

    2016-10-25

    This dissertation describes a variety of studies on the determination of trace elements in samples with forensic importance. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine the trace element composition of numerous lipstick samples. Lipstick samples were determined to be homogeneous. Most lipstick samples of similar colors were readily distinguishable at a 95% confidence interval based on trace element composition. Numerous strands of a multi-strand speaker cable were analyzed by LA-ICP-MS. The strands in this study are spatially heterogeneous in trace element composition. In actual forensic applications, the possibility of spatial heterogeneity must be considered, especially in cases where only small samples (e.g., copper wire fragments after an explosion) are available. The effects of many unpredictable variables, such as weather, temperature, and human activity, on the retention of gunshot residue (GSR) around projectile wounds were assessed with LAICP- MS. Skin samples around gunshot and stab wounds and larvae feeding in and around the wounds on decomposing pig carcasses were analyzed for elements consistent with GSR (Sb, Pb, Ba, and Cu). These elements were detected at higher levels in skin and larvae samples around the gunshot wounds compared to the stab wounds for an extended period of time throughout decomposition in both a winter and summer study. After decomposition, radiographic images of the pig bones containing possible damage from bullets revealed metallic particles embedded within a number of bones. Metallic particles within the bones were analyzed with x-ray, K-edge densitometry and determined to contain lead, indicating that bullet residue can be retained throughout decomposition and detected within bones containing projectile trauma.

  3. Carbon K-Edge Scanning Transmission X-ray Spectromicroscopy (STXM) of Uranium Binding to Bacterial Cells

    NASA Astrophysics Data System (ADS)

    Gillow, J.; Wirick, S.; Feser, M.; Jacobsen, C.; Francis, A.

    2002-12-01

    The sorption of uranium by bacteria was studied by interrogation of the C K-absorption edge using scanning transmission x-ray spectromicroscopy (STXM). The unique imaging and spectroscopy capability of STXM was used to elucidate the chemical environment of C in the bacterial cell. Washed whole cells and cell wall preparations of bacteria commonly found in soil environments including Pseudomonas fluorescens, Bacillus subtilis, the facultative anaerobe Shewanella putrefaciens and the strict anaerobe Clostridium sp. were exposed to uranyl nitrate at pH 5. After washing to remove potential surface precipitates and non-bonded uranium the cells and walls were dried onto TEM gridx. Standards (uranyl salts and organic complexes), bacterial cells unexposed, and U-exposed cells were analyzed by STXM at 280-310 eV with the C K-edge x-ray absorption near-edge spectroscopy (XANES) examined for evidence of U in the C coordination environment. Principle spectral features of the bacteria included the 285 eV C=C and 288 eV C=O 1s-π * resonances due to the major C function groups that comprise the bacterial cell wall. There was no change in peak position of 1s-π * spectral features for whole cells or cell walls when U was present. This indicates that U does not exert an influence on the electron resonance of C when bonded as carboxylate species at the bacterial cell surface. This finding is supported by the analysis of uranyl citrate and uranyl alanine standards. The extended x-ray absorption fine structure spectroscopy region of the C K-edge of bacterial cells exposed to U shows slight changes in spectral features at >290 eV. Other absorption edges accessible by soft x-ray spectroscopy were examined; U was detected at it's NV (736.2 eV) and NIV (778.3 eV) edges however there was poor resolution of U associated with the bacteria. Analysis at the O K-edge (529 eV) provided evidence for metal-ligand interaction and forms the basis for further study to gain a molecular

  4. Ca and S K-edge XANES studies of calcite-acid mine water interactions

    SciTech Connect

    Myneni, S.C.B.; Perera, R.C.C.

    1997-04-01

    Heavy metal-rich acidic waters (SO{sub 4}{sup 2{minus}}, AsO{sub 4}{sup 3{minus}}, SeO{sub 4}{sup 2{minus}}, Fe{sup 2+}, Fe{sup 3+}, Al{sup 3+}, Cu{sup 2+}, Zn{sup 2+}, Cd{sup 2+}) and related ochreous coatings are common around abandoned sulfide and coal mine sites. This is mainly caused by the natural weathering of pyrite (FeS{sub 2}), arsenopyrite (FeAsS), and other metal sulfide containing shales. Acid generation in the case of pyrite can be explained by a general reaction: FeS{sub 2} + 3.5 O{sub 2} + H{sub 2}O {leftrightarrow} Fe{sup 2+} + SO{sub 4}{sup 2{minus}} + 2H{sup +}. Also, these low pH waters interact with the soils, and mobilize their soluble elements. One of the common remediation strategies is to allow these acid waters to react with limestone (CaCO{sub 3}-rich rock) and neutralize the pH and precipitate out soluble metals. Yet, the associated problem is the precipitation of Fe and Al oxides and hydroxy sulfate coatings on limestone surfaces, which block calcite reactive sites, and make them ineffective a few hours after initiation of treatment. The main objectives of this research are to examine: (1) the chemistry of limestone surface coatings, and (2) their toxic metal uptake and the conditions that inhibit their formation. Previous molecular studies using X-ray diffraction, and vibrational spectroscopy on limestone surface coatings (sampled from Athens, OH) indicate that the surface-most layer (the layer in contact with water) is composed of schwertmannite (Fe(III)-hydroxy sulfate) like phases. However, white, X-ray amorphous; Al-, sulfate- and carbonate-rich; and Ca-poor phases appeared at the interface between the limestone and the iron oxide coatings. The structure, morphology, and coordination chemistry of component major and trace elements of these white precipitate phases have not previously been examined.

  5. Possible superconductivity in hetero-polar interfaces of CuCl/Si superlattices: (001) and (111)

    NASA Astrophysics Data System (ADS)

    Rhim, S. H.; Saniz, R.; Freeman, A. J.; Yu, J. J.

    2006-03-01

    To investigate possible interfacial superconductivity in CuCl/Si superlattices, we carried out first-principles calculations using the highly precise FLAPW method. Two possible growth directions, (001) and (111), are compared through their band structures, density of states (DOS), charge densities and Fermi surfaces. While the (111) superlattice is always metallic, the (001) superlattice is metallic or insulating depending on the number of Si and CuCl layers. Both directions exhibit two dimensional (2D) character at the interfaces which is a result of charge transfer between CuCl and Si layers. For metallic superlattices, the 2D conduction bands at the interfaces, resemble the 2D Cu-O dpσ bands of cuprate superconductors. To obtain TC based on conventional electron-phonon (e-p) interactions, we calculated the e-p coupling constant, λ, within the rigid muffin-tin approximation. The results indicate that while e-p coupling is present in both directions, it gives TC=0.41˜1.69 K, i.e. one order of magnitude lower than the previously reported high transition temperature^2- which, if confirmed, would indicate a possible role for excitonic effects. Mattes and Foiles, Physica 135B, 139 (1985) Wimmer, Krakauer, Weinert, and Freeman, Phys.Rev.B, 24, 864 (1981) Gaspari and Gyoffry, Phys. Rev. Lett. 28, 801, (1972)

  6. Vulcanization reaction of squalene and S8 powder studied by Sulfur K-edge NEXAFS under liquid phase

    NASA Astrophysics Data System (ADS)

    Yagi, S.; Menjo, Y.; Tsukada, C.; Ogawa, S.; Kutluk, G.; Namatame, H.; Taniguchi, M.

    2015-03-01

    Vulcanized rubber materials are useful in our surroundings. However, detail structure and reaction are not revealed even in present. Since squalene molecule possesses some same properties compared with natural rubber, we have prepared the samples of vulcanized squalene at 140 °C for several hours. To understand the vulcanization reaction,sulfur K-edge NEXAFS measurements have been carried out for the vulcanized squalene under liquid phase with He-path system and fluorescence detection mode. Moreover, we have tried curve fitting analysis of NEXAFS spectra. The results indicate that the squalene has been vulcanized by the S8 molecule at 140 °C and the S8 molecule length is shortened from 8 to 5-6 after the vulcanization reaction.

  7. Automated Chemical Analysis of Internally Mixed Aerosol Particles Using X-ray Spectromicroscopy at the Carbon K-Edge

    SciTech Connect

    Gilles, Mary K; Moffet, R.C.; Henn, T.; Laskin, A.

    2011-01-20

    We have developed an automated data analysis method for atmospheric particles using scanning transmission X-ray microscopy coupled with near edge X-ray fine structure spectroscopy (STXM/NEXAFS). This method is applied to complex internally mixed submicrometer particles containing organic and inorganic material. Several algorithms were developed to exploit NEXAFS spectral features in the energy range from 278 to 320 eV for quantitative mapping of the spatial distribution of elemental carbon, organic carbon, potassium, and noncarbonaceous elements in particles of mixed composition. This energy range encompasses the carbon K-edge and potassium L2 and L3 edges. STXM/NEXAFS maps of different chemical components were complemented with a subsequent analysis using elemental maps obtained by scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM/EDX). We demonstrate the application of the automated mapping algorithms for data analysis and the statistical classification of particles.

  8. Investigation of the mica x-ray absorption near-edge structure spectral features at the Al K-edge

    NASA Astrophysics Data System (ADS)

    Wu, Ziyu; Marcelli, A.; Cibin, G.; Mottana, A.; Della Ventura, G.

    2003-10-01

    Near-edge features of Al x-ray absorption near-edge structure (XANES) spectra in aluminosilicate compounds with mixed coordination number are usually assigned to a fourfold coordinated site contribution followed by a sixfold coordinated site contribution that is displaced towards higher energy because of the increasing ligand nucleus potentials, neglecting possible contributions due to bond distance variations and local geometrical distortion. Here we present and discuss the Al K-edge XANES spectra of synthetic micas with either fourfold coordinated Al (phlogopite), or with sixfold coordinated Al (polylithionite), as well as with mixed coordination (preiswerkite). Multiple scattering simulations of XANES spectra demonstrate that octahedral contributions may overlap the tetrahedral ones so that the lower energy structures in mixed coordination compounds may be associated with the octahedral sites. This unexpected behaviour can be described as due to the effect of a significant reduction of the ligand field strength (i.e. large local distortion and Al-O bond distances).

  9. Bethe-Salpeter equation calculations of resonant inelastic x-ray scattering at the nitrogen K edge

    NASA Astrophysics Data System (ADS)

    Vinson, John; Jach, Terrence; Elam, Tim; Denlinger, Jonathon

    2013-03-01

    We present theoretical calculations of resonant inelastic x-ray scattering (RIXS) at the nitrogen K edge of several materials along with direct comparison to experimental results. Our approach is based on a Bethe-Salpeter equation formalism, and our calculations are carried out using an extension of the OCEAN package,[1] including both intermediate and final-state excitonic effects. By building upon a DFT basis we include ground-state effects without system-dependent fitting parameters. We are able to account for the general trends and features seen in experiment. A more ad hoc account of other contributions to the measured spectra, primarily phonon coupling, is attempted, but this highlights some current shortcomings limiting fully ab initio calculations of the near-edge x-ray spectra of extended systems.

  10. Iron K-edge X-ray absorption spectroscopy of the iron-molybdenum cofactor of nitrogenase from Klebsiella pneumoniae.

    PubMed Central

    Arber, J M; Flood, A C; Garner, C D; Gormal, C A; Hasnain, S S; Smith, B E

    1988-01-01

    Iron K-edge X-ray absorption data for the iron-molybdenum cofactor ('FeMoco') from Klebsiella pneumoniae reported here provide the first evidence for long-range structural order in the cofactor [Fe...Fe(Mo) = 0.368 nm in addition to Fe...S = 0.22 nm and Fe...Fe(Mo) = 0.27 nm] and, in contrast with previously published data [Antonio, Teo, Orme-Johnson, Nelson, Groh, Lindahl, Kauzlarich & Averill (1982) J. Am. Chem. Soc. 104, 4703-4705], indicate that most of the iron centres are not co-ordinated to light (oxygen, nitrogen) atoms. This demonstrates that presently available chemical models for FeMoco are inadequate. PMID:3046607

  11. Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge

    SciTech Connect

    Zubarev, Dmitry Yu.; Austin, Brian M.; Lester, William A. Jr.

    2012-04-14

    Fixed-node diffusion Monte Carlo (FNDMC) is used to simulate the x-ray absorption spectrum of a gas-phase pyrrole molecule at the nitrogen K-edge. Trial wave functions for core-excited states are constructed from ground-state Kohn-Sham determinants substituted with singly occupied natural orbitals from configuration interaction with single excitations calculations of the five lowest valence-excited triplet states. The FNDMC ionization potential (IP) is found to lie within 0.3 eV of the experimental value of 406.1 {+-} 0.1 eV. The transition energies to anti-bonding virtual orbitals match the experimental spectrum after alignment of IP values and agree with the existing assignments.

  12. Phosphine and phosphine oxide groups in metal-organic frameworks detected by P K-edge XAS.

    PubMed

    Morel, F L; Pin, S; Huthwelker, T; Ranocchiari, M; van Bokhoven, J A

    2015-02-07

    Phosphine metal-organic frameworks (P-MOFs) are crystalline porous coordination polymers that contain phosphorus functional groups within their pores. We present the use of X-ray absorption spectroscopy (XAS) at the P K-edge to determine the phosphine to phosphine oxide ratio in two P-MOFs with MIL-101 topology. The phosphorus oxidation state is of particular interest as it strongly influences the coordination affinity of these materials for transition metals. This method can determine the oxidation state of phosphorus even when the material contains paramagnetic nuclei, differently from NMR spectroscopy. We observed that phosphine in LSK-15 accounts for 72 ± 4% of the total phosphorus groups and that LSK-12 contains only phosphine oxide.

  13. Oxygen K-edge fine structures of water by x-ray Raman scattering spectroscopy under pressure conditions

    SciTech Connect

    Fukui, Hiroshi; Huotari, Simo; Andrault, Denis; Kawamoto, Tatsuhiko

    2007-10-07

    Fine structure of the oxygen K edge was investigated for water at ambient pressure, 0.16, 0.21, 0.27, 0.47, and 0.60 GPa using x-ray Raman scattering spectroscopy (XRS). Similarity in near-edge structures at 0.16 and 0.60 GPa suggests little difference in the electronic state of oxygen in the low-pressure and high-pressure forms of water. Yet, we observed significant variation of preedge structure of the XRS spectra with compression. The intensity of the preedge peak at 535.7 eV has a minimal value at around 0.3 GPa, indicating that the number of hydrogen bonding increases first and then decreases as a function of pressure.

  14. Electrostatic polarization is crucial in reproducing Cu(I) interaction energies and hydration.

    PubMed

    Ponomarev, Sergei Y; Click, Timothy H; Kaminski, George A

    2011-08-25

    We have explored the suitability of fixed-charges and polarizable force fields for modeling interactions of the monovalent Cu(I) ion. Parameters for this ion have been tested and refitted within the fixed-charges OPLS-AA and polarizable force field (PFF) frameworks. While this ion plays an important role in many protein interactions, the attention to it in developing empirical force fields is limited. Our PFF parameters for the copper ion worked very well for the Cu(I) interactions with water, while both the original OPLS2005 and our refitted OPLS versions moderately underestimated the copper-water interaction energy. However, the greatest problem in using the nonpolarizable fixed-charges OPLS force field was observed while calculating interaction energies and distances for Cu(I)-benzene complexes. The OPLS2005 model underestimates the interaction energy by a factor of 4. Refitting the OPLS parameters reduced this underestimation to a factor of 2.2-2.4, but only at a cost of distorting the complex geometry. At the same time, the polarizable calculations had an error of about 4%. Moreover, we then used the PFF and nonpolarizable refitted OPLS models for finding free energy of hydration for copper ion via molecular dynamics simulations. While the OPLS calculations lead to a 22% error in the solvation energy, the PFF result was off by only 1.8%. This was achieved with no refitting of the parameters but simply by employing the model developed for the Cu(I) interaction with a single water molecule. We believe that the presented results not only lead to a conclusion about a qualitatively greater suitability of polarizable force fields for simulating molecular interactions with ions but also attest to the excellent level of transferability of PFF parameters.

  15. Electrostatic polarization is crucial in reproducing Cu(I) interaction energies and hydration

    PubMed Central

    Ponomarev, Sergei Y.; Click, Timothy H.; Kaminski, George A.

    2011-01-01

    We have explored suitability of fixed-charges and polarizable force fields for modeling interactions of the monovalent Cu(I) ion. Parameters for this ion have been tested and refitted within the fixed-charges OPLS-AA and polarizable force field (PFF) frameworks. While this ion plays an important role in many protein interactions, the attention to it in developing empirical force fields is limited. Our PFF parameters for the copper ion worked very well for the Cu(I) interactions with water, while both the original OPLS2005 and our refitted OPLS versions moderately underestimated the copper-water interaction energy. However, the greatest problem in using the non-polarizable fixed-charges OPLS force field was observed while calculating interaction energies and distances for Cu(I) – benzene complexes. The OPLS2005 model underestimates the interaction energy by a factor of four. Refitting the OPLS parameters reduced this underestimation to a factor of 2.2 to 2.4, but only at a cost of distorting the complex geometry. At the same time, the polarizable calculations had an error of about 4%. Moreover, we then used the PFF and non-polarizable refitted OPLS models for finding free energy of hydration for copper ion via molecular dynamics simulations. While the OPLS calculations lead to a 22% error in the solvation energy, the PFF result was off by only 1.8%. This was achieved with no refitting of the parameters but simply by employing the model developed for the Cu(I) interaction with a single water molecule. We believe that the presented results not only lead to a conclusion about a qualitatively greater suitability of polarizable force fields for simulating molecular interactions with ions but also attest to the excellent level of transferability of PFF parameters. PMID:21761909

  16. Surface morphology of CuFeS2: The stability of the polar (112 ) /(112 ¯) surface pair

    NASA Astrophysics Data System (ADS)

    Chen, Vincent H.-Y.; Mallia, Giuseppe; Martínez-Casado, Ruth; Harrison, Nicholas M.

    2015-10-01

    The reconstruction and energetics for a range of chalcopyrite (CuFeS2) surfaces have been investigated using hybrid-exchange density functional theory. The stable nonpolar surfaces in increasing order of surface energy are (110), (102), and (114). In addition, the polar (112 ) /(112 ¯) surface pair was found to be remarkably stable with a surface formation energy that is only slightly higher than that of the (110) surface. The stability of (112 ) /(112 ¯) can be attributed to a combination of geometric and electronic mechanisms that result in the suppression of the electrostatic dipole perpendicular to the surface. Defect formation is a third mechanism that can further stabilize the (112 ) /(112 ¯) surface pair to an extent that it is thermodynamically preferred over the (110) surface. The stability of (112 ) /(112 ¯) means that regardless of the growth conditions, (112) and (112 ¯) facets are expected to have a significant presence in the surface morphology of CuFeS2.

  17. Theory and X-ray Absorption Spectroscopy for Aluminum Coordination Complexes – Al K-Edge Studies of Charge and Bonding in (BDI)Al, (BDI)AlR2, and (BDI)AlX2 Complexes.

    PubMed

    Altman, Alison B; Pemmaraju, C D; Camp, Clément; Arnold, John; Minasian, Stefan G; Prendergast, David; Shuh, David K; Tyliszczak, Tolek

    2015-08-19

    Polarized aluminum K-edge X-ray absorption near edge structure (XANES) spectroscopy and first-principles calculations were used to probe electronic structure in a series of (BDI)Al, (BDI)AlX2, and (BDI)AlR2 coordination compounds (X = F, Cl, I; R = H, Me; BDI = 2,6-diisopropylphenyl-β-diketiminate). Spectral interpretations were guided by examination of the calculated transition energies and polarization-dependent oscillator strengths, which agreed well with the XANES spectroscopy measurements. Pre-edge features were assigned to transitions associated with the Al 3p orbitals involved in metal-ligand bonding. Qualitative trends in Al 1s core energy and valence orbital occupation were established through a systematic comparison of excited states derived from Al 3p orbitals with similar symmetries in a molecular orbital framework. These trends suggested that the higher transition energies observed for (BDI)AlX2 systems with more electronegative X(1-) ligands could be ascribed to a decrease in electron density around the aluminum atom, which causes an increase in the attractive potential of the Al nucleus and concomitant increase in the binding energy of the Al 1s core orbitals. For (BDI)Al and (BDI)AlH2 the experimental Al K-edge XANES spectra and spectra calculated using the eXcited electron and Core-Hole (XCH) approach had nearly identical energies for transitions to final state orbitals of similar composition and symmetry. These results implied that the charge distributions about the aluminum atoms in (BDI)Al and (BDI)AlH2 are similar relative to the (BDI)AlX2 and (BDI)AlMe2 compounds, despite having different formal oxidation states of +1 and +3, respectively. However, (BDI)Al was unique in that it exhibited a low-energy feature that was attributed to transitions into a low-lying p-orbital of b1 symmetry that is localized on Al and orthogonal to the (BDI)Al plane. The presence of this low-energy unoccupied molecular orbital on electron-rich (BDI)Al distinguishes

  18. A set of f-polarization functions for pseudo-potential basis sets of the transition metals ScCu, YAg and LaAu

    NASA Astrophysics Data System (ADS)

    Ehlers, A. W.; Böhme, M.; Dapprich, S.; Gobbi, A.; Höllwarth, A.; Jonas, V.; Köhler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G.

    1993-06-01

    A Set of seven-component f-type polarization functions has been optimized for use with the pseudo-potentials of Hay and Wadt at the CISD level of theory for the transition metals ScCu, YAg, LaAu in the energetically lowest-lying s 1 d n electronic state.

  19. Asymptotically-Equal-To 10 eV ionization shift in Ir K{alpha}{sub 2} from a near-coincident Lu K-edge

    SciTech Connect

    Pereira, N. R.; Weber, B. V.; Phipps, D.; Schumer, J. W.; Seely, J. F.; Carroll, J. J.; VanHoy, J. R.; Slabkowska, K.; Polasik, M.

    2012-10-15

    Close to an x-ray filter's K-edge the transmission depends strongly on the photon energy. For a few atom pairs, the K-edge of one is only a few tens of eV higher than a K-line energy of another, so that a small change in the line's energy becomes a measurable change in intensity behind such a matching filter. Lutetium's K-edge is Asymptotically-Equal-To 27 eV above iridium's K{alpha}{sub 2} line, Asymptotically-Equal-To 63.287 keV for cold Ir. A Lu filter reduces this line's intensity by Asymptotically-Equal-To 10 % when it is emitted by a plasma, indicating an ionization shift {Delta}E Asymptotically-Equal-To 10{+-}1 eV.

  20. Absolute determination of charge-coupled device quantum detection efficiency using Si K-edge x-ray absorption fine structure

    SciTech Connect

    Dunn, J; Steel, A B

    2012-05-06

    We report a method to determine the quantum detection efficiency and the absorbing layers on a front-illuminated charge-coupled device (CCD). The CCD under study, as part of a crystal spectrometer, measures intense continuum x-ray emission from a picosecond laser-produced plasma and spectrally resolves the Si K-edge x-ray absorption fine structure features due to the electrode gate structure of the device. The CCD response across the Si K-edge shows a large discontinuity as well as a number of oscillations that are identified individually and uniquely from Si, SiO{sub 2}, and Si{sub 3}N{sub 4} layers. From the spectral analysis of the structure and K-edge discontinuity, the active layer thickness and the different absorbing layers thickness can be determined precisely. A precise CCD detection model from 0.2-10 keV can be deduced from this highly sensitive technique.

  1. Photoconductivity measurements of x-ray absorption fine structures in liquids in the soft x-ray region: Si and Cl K-edge

    SciTech Connect

    Sham, T.K.; Xiong, J.Z.; Feng, X.H.; Holroyd, R.A.; Yang, B.X.

    1992-12-31

    Photoconductivity measurements of X-ray absorption fine structures (XAFS) at the Si and Cl K-edge have been carried out in a liquid cell for (CH{sub 3}){sub 4},Si [(CH{sub 3}){sub 3}Si]{sub 4}Si and eitheras a pure liquid or 2,2,4-trimethylpentane solution. It is found that for the pure liquids and their concentrated hydrocarbon solutions, all K-edge XAFS spectra are inverted as expected under the condition of total absorption. A sharp conductivity dip is also observed in CCl{sub 4} at the Cl K-edge. The concentration dependence of the XAFS spectrum of CCl{sub 4} is reported. These results are discussed in terms of soft X-ray induced ion yields of the solute and solvent molecules in liquids.

  2. Photoconductivity measurements of x-ray absorption fine structures in liquids in the soft x-ray region: Si and Cl K-edge

    SciTech Connect

    Sham, T.K.; Xiong, J.Z.; Feng, X.H. . Dept. of Chemistry); Holroyd, R.A. ); Yang, B.X. )

    1992-01-01

    Photoconductivity measurements of X-ray absorption fine structures (XAFS) at the Si and Cl K-edge have been carried out in a liquid cell for (CH[sub 3])[sub 4],Si [(CH[sub 3])[sub 3]Si][sub 4]Si and eitheras a pure liquid or 2,2,4-trimethylpentane solution. It is found that for the pure liquids and their concentrated hydrocarbon solutions, all K-edge XAFS spectra are inverted as expected under the condition of total absorption. A sharp conductivity dip is also observed in CCl[sub 4] at the Cl K-edge. The concentration dependence of the XAFS spectrum of CCl[sub 4] is reported. These results are discussed in terms of soft X-ray induced ion yields of the solute and solvent molecules in liquids.

  3. Local structure of ball-milled LaNi{sub 5} hydrogen storage material by Ni K-edge EXAFS

    SciTech Connect

    Joseph, B.; Iadecola, A.; Schiavo, B.; Cognigni, A.; Olivi, L.; D'Ali Staiti, G.; Saini, N.L.

    2010-07-15

    Local structure of the nanostructured LaNi{sub 5} hydrogen storage alloys, prepared by ball-milling, has been studied using Ni K-edge extended X-ray absorption fine structure spectroscopy. Results indicate that the ball-milling up to 100 h results in the production of nanoparticles characterized by large atomic disorder and slightly reduced unit-cell volume, compared to the bulk LaNi{sub 5}. High temperature annealing appears to help in partial recovery of atomic order in the ball-milled samples; however, long-time ball-milled samples retain large disorder even after the high temperature annealing. The results suggest that the large disorder and the reduced unit-cell volume might be causing a higher energy-barrier for the hydride-phase formation in the long time ball-milled LaNi{sub 5} powders. - Graphical Abstract: X-ray diffraction (XRD) pattern (left panel) and Fourier transforms of the Ni K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy (right panel) of bulk LaNi{sub 5} hydrogen storage material (structure model is given in the middle) together with the same after 100 h ball-milling. Milled samples show a remarkable reduction intensity and broadening of the XRD peaks. Substantial damping of the amplitude and a slight shrinkage of the profile are observed in the EXAFS spectrum. These results indicate that the ball-milling up to 100 h results in the production of nanoparticles characterized by slightly reduced unit-cell volume and substantial atomic disorder compared to the bulk LaNi5. High temperature annealing appears to help in partial recovery of atomic order in the ball-milled samples; however, long-time ball-milled samples retain the disorder even after the high temperature annealing. The results suggest that the large disorder and the reduced unit-cell volume might be causing a higher energy-barrier for the hydride-phase formation in the long-time ball-milled LaNi{sub 5} powders.

  4. Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition

    SciTech Connect

    Kortright, Jeffrey Barrett; Sun, Jing; Spencer, Ryan K.; Jiang, Xi; Zuckermann, Ronald N.

    2016-12-14

    The evolution of molecular morphology in bulk samples of comb diblock copolymer pNdc12-b-pNte21 across the lamellar order-disorder transition (ODT) is studied using resonant x-ray scattering at the oxygen K edge, with the goal of determining whether the molecules remain extended or collapse above the ODT. The distinct spectral resonances of carbonyl oxygen on the backbone and ether oxygen in the pNte side chains combine with their different site symmetry within the molecule to yield strong differences in bulk structural sensitivity at all temperatures. Comparison with simple models for the disordered phase clearly reveals that disordering at the ODT corresponds to loss of positional order of molecules with extended backbones that retain orientational order, rather than backbone collapse into a locally isotropic disordered phase. This conclusion is facilitated directly by the distinct structural sensitivity at the two resonances. Lastly, we discuss the roles of depolarized scattering in enhancing this sensitivity, and background fluorescence in limiting dynamic range, in oxygen resonant scattering.

  5. High-speed K-edge angiography achieved with tantalum K-series characteristic x rays (Honorable Mention Poster Award)

    NASA Astrophysics Data System (ADS)

    Sato, Eiichi; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Inoue, Takashi; Ogawa, Akira; Sato, Shigehiro; Takayama, Kazuyoshi; Ido, Hideaki

    2005-04-01

    The tantalum plasma flash x-ray generator is useful in order to perform high-speed K-edge angiography using cone beams because Kα rays from the tantalum target are absorbed effectively by gadolinium-based contrast media. In the flash x-ray generator, a 150 nF condenser is charged up to 80 kV by a power supply, and flash x rays are produced by the discharging. The x-ray tube is a demountable diode, and the turbomolecular pump evacuates air from the tube with a pressure of approximately 1 mPa. Since the electric circuit of the high-voltage pulse generator employs a cable transmission line, the high-voltage pulse generator produces twice the potential of the condenser charging voltage. When the charging voltage was increased, the K-series characteristic x-ray intensities of tantalum increased. The K lines were clean and intense, and hardly any bremsstrahlung rays were detected. The x-ray pulse widths were approximately 100 ns, and the time-integrated x-ray intensity had a value of approximately 300 μGy at 1.0 m from the x-ray source with a charging voltage of 80 kV. Angiography was performed using a film-less computed radiography (CR) system and gadolinium-based contrast media. In angiography of non-living animals, we observed fine blood vessels of approximately 100 μm with high contrasts.

  6. Resonant soft x-ray reflectivity of Me/B4C multilayers near the boron K edge

    SciTech Connect

    Ksenzov, Dmitriy; Schlemper, Christoph; Pietsch, Ullrich

    2010-09-01

    Energy dependence of the optical constants of boron carbide in the short period Ru/B4C and Mo/B4C multilayers (MLs) are evaluated from complete reflectivity scans across the boron K edge using the energy-resolved photon-in-photon-out method. Differences between the refractive indices of the B4Cmaterial inside and close to the surface are obtained from the peak profile of the first order ML Bragg peak and the reflection profile near the critical angle of total external reflection close to the surface. Where a Mo/B4C ML with narrow barrier layers appears as a homogeneous ML at all energies, a Ru/B4C ML exhibits another chemical nature of boron at the surface compared to the bulk. From evaluation of the critical angle of total external reflection in the energy range between 184 and 186 eV, we found an enriched concentration of metallic boron inside the Ru-rich layer at the surface, which is not visible in other energy ranges.

  7. Photoionization of Ne Atoms and Ne+ Ions Near the K Edge: Precision Spectroscopy and Absolute Cross-sections

    NASA Astrophysics Data System (ADS)

    Müller, Alfred; Bernhardt, Dietrich; Borovik, Alexander, Jr.; Buhr, Ticia; Hellhund, Jonas; Holste, Kristof; Kilcoyne, A. L. David; Klumpp, Stephan; Martins, Michael; Ricz, Sandor; Seltmann, Jörn; Viefhaus, Jens; Schippers, Stefan

    2017-02-01

    Single, double, and triple photoionization of Ne+ ions by single photons have been investigated at the synchrotron radiation source PETRA III in Hamburg, Germany. Absolute cross-sections were measured by employing the photon-ion merged-beams technique. Photon energies were between about 840 and 930 eV, covering the range from the lowest-energy resonances associated with the excitation of one single K-shell electron up to double excitations involving one K- and one L-shell electron, well beyond the K-shell ionization threshold. Also, photoionization of neutral Ne was investigated just below the K edge. The chosen photon energy bandwidths were between 32 and 500 meV, facilitating the determination of natural line widths. The uncertainty of the energy scale is estimated to be 0.2 eV. For comparison with existing theoretical calculations, astrophysically relevant photoabsorption cross-sections were inferred by summing the measured partial ionization channels. Discussion of the observed resonances in the different final ionization channels reveals the presence of complex Auger-decay mechanisms. The ejection of three electrons from the lowest K-shell-excited Ne+(1s2{s}22{p}6{}2{{{S}}}1/2) level, for example, requires cooperative interaction of at least four electrons.

  8. Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition

    DOE PAGES

    Kortright, Jeffrey Barrett; Sun, Jing; Spencer, Ryan K.; ...

    2016-12-14

    The evolution of molecular morphology in bulk samples of comb diblock copolymer pNdc12-b-pNte21 across the lamellar order-disorder transition (ODT) is studied using resonant x-ray scattering at the oxygen K edge, with the goal of determining whether the molecules remain extended or collapse above the ODT. The distinct spectral resonances of carbonyl oxygen on the backbone and ether oxygen in the pNte side chains combine with their different site symmetry within the molecule to yield strong differences in bulk structural sensitivity at all temperatures. Comparison with simple models for the disordered phase clearly reveals that disordering at the ODT corresponds tomore » loss of positional order of molecules with extended backbones that retain orientational order, rather than backbone collapse into a locally isotropic disordered phase. This conclusion is facilitated directly by the distinct structural sensitivity at the two resonances. Lastly, we discuss the roles of depolarized scattering in enhancing this sensitivity, and background fluorescence in limiting dynamic range, in oxygen resonant scattering.« less

  9. Iron K-edge X-ray absorption near-edge structure spectroscopy of aerodynamically levitated silicate melts and glasses

    DOE PAGES

    Alderman, O. L. G.; Wilding, M. C.; Tamalonis, A.; ...

    2017-01-26

    Here, the local structure about Fe(II) and Fe(III) in silicate melts was investigated in-situ using iron K-edge X-ray absorption near-edge structure (XANES) spectroscopy. An aerodynamic levitation and laser heating system was used to allow access to high temperatures without contamination, and was combined with a chamber and gas mixing system to allow the iron oxidation state, Fe3+/ΣFe, to be varied by systematic control of the atmospheric oxygen fugacity. Eleven alkali-free, mostly iron-rich and depolymerized base compositions were chosen for the experiments, including pure oxide FeO, olivines (Fe,Mg)2SiO4, pyroxenes (Fe,Mg)SiO3, calcic FeO-CaSiO3, and a calcium aluminosilicate composition, where total iron contentmore » is denoted by FeO for convenience. Melt temperatures varied between 1410 and 2160 K and oxygen fugacities between FMQ – 2.3(3) to FMQ + 9.1(3) log units (uncertainties in parentheses) relative to the fayalite-magnetite-β-quartz (FMQ) buffer.« less

  10. Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite.

    PubMed

    Zougrou, I M; Katsikini, M; Brzhezinskaya, M; Pinakidou, F; Papadopoulou, L; Tsoukala, E; Paloura, E C

    2016-08-01

    Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

  11. Investigation of S H bonds in biologically important compounds by sulfur K-edge X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Prange, A.; Dahl, C.; Trüper, H. G.; Behnke, M.; Hahn, J.; Modrow, H.; Hormes, J.

    2002-09-01

    X-ray Absorption Near Edge Structure (XANES) spectroscopy, often provides a direct correlation between observed resonances in the spectrum and molecular bonds in the sample. This can be used as a fingerprint for the presence of a given molecular environment of the absorber atom in a sample. As the white line is found at similar energy positions for S C and S H bonds, this approach is impossible when both types of bond are present simultaneously, as often in biological systems. To develop a criterium for the presence of S H bonds in such samples, reduced glutathione, reduced coenzyme A, cysteine and their corresponding oxidized forms were investigated using sulfur K-edge XANES, revealing a unique feature at 2 475.8 eV in the respective difference spectra. To correlate this structure to S H bonds, H2S and H2S2 were measured, whose difference spectrum also shows a structure at this energy position, whereas it is not present throughout a variety of C S C/C S S C environments. Theoretical investigations suggest its correlation to a Rydberg transition occurring in the case of a S H bond. Using this criterium, the presence of S H bonds is in the purple sulfur bacterium Allochromatium vinosum during oxidation of intracellular accumulated sulfur, is proved, as expected from biological considerations.

  12. Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite

    NASA Astrophysics Data System (ADS)

    Zougrou, I. M.; Katsikini, M.; Brzhezinskaya, M.; Pinakidou, F.; Papadopoulou, L.; Tsoukala, E.; Paloura, E. C.

    2016-08-01

    Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

  13. Photoionization of Ne Atoms and Ne + Ions Near the K Edge: PrecisionSpectroscopy and Absolute Cross-sections

    DOE PAGES

    Müller, Alfred; Bernhardt, Dietrich; Borovik, Alexander; ...

    2017-02-17

    Single, double, and triple photoionization of Ne + ions by single photons have been investigated at the synchrotron radiation source PETRA III in Hamburg, Germany. Absolute cross-sections were measured by employing the photon-ion merged-beams technique. Photon energies were between about 840 and 930 eV, covering the range from the lowest-energy resonances associated with the excitation of one single K-shell electron up to double excitations involving one K- and one L-shell electron, well beyond the K-shell ionization threshold. Also, photoionization of neutral Ne was investigated just below the K edge. The chosen photon energy bandwidths were between 32 and 500 meV,more » facilitating the determination of natural line widths. The uncertainty of the energy scale is estimated to be 0.2 eV. For comparison with existing theoretical calculations, astrophysically relevant photoabsorption cross-sections were inferred by summing the measured partial ionization channels. Discussion of the observed resonances in the different final ionization channels reveals the presence of complex Auger-decay mechanisms. The ejection of three electrons from the lowest K-shell-excited Ne + (1s2s2p6 2S1/2) level, for example, requires cooperative interaction of at least four electrons.« less

  14. High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory.

    PubMed

    Lima, Frederico A; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena

    2013-12-28

    X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core-hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas-Kroll-Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.

  15. First Principles Fe L2,3-Edge and O K-Edge XANES and XMCD Spectra for Iron Oxides.

    PubMed

    Sassi, Michel; Pearce, Carolyn I; Bagus, Paul S; Arenholz, Elke; Rosso, Kevin M

    2017-09-21

    X-ray absorption near edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) spectroscopies are tools in widespread use for providing detailed local atomic structure, oxidation state, and magnetic structure information for materials and organometallic complexes. Analysis of these spectra for transition metal L-edges is routinely performed on the basis of ligand-field multiplet theory because one- and two-particle mean field ab initio methods typically cannot describe the multiplet structure. Here we show that multireference configuration interaction (MRCI) calculations can satisfactorily reproduce measured XANES spectra for a range of complex iron oxide materials including hematite and magnetite. MRCI Fe L2,3-edge XANES and XMCD spectra of Fe(II)O6, Fe(III)O6 and Fe(III)O4 in magnetite are found to be in very good qualitative agreement with experiment and multiplet calculations. Point charge embedding and small distortions of the first shell oxygen ligands have only small effects. Oxygen K-edge XANES/XMCD spectra for magnetite investigated by a real-space Green's function approach completes the very good qualitative agreement with experiment. Material-specific differences in local coordination and site symmetry are well reproduced, making the approach useful for assigning spectral features to specific oxidation states and coordination environments.

  16. Local electronic structure of aqueous zinc acetate: oxygen K-edge X-ray absorption and emission spectroscopy on micro-jets.

    PubMed

    Golnak, Ronny; Atak, Kaan; Suljoti, Edlira; Hodeck, Kai F; Lange, Kathrin M; Soldatov, Mikhail A; Engel, Nicholas; Aziz, Emad F

    2013-06-07

    Oxygen K-edge X-ray absorption, emission, and resonant inelastic X-ray scattering spectra were measured to site selectively gain insights into the electronic structure of aqueous zinc acetate solution. The character of the acetate ion and the influence of zinc and water on its local electronic structure are discussed.

  17. Correction: Ligand K-edge XAS, DFT, and TDDFT analysis of pincer linker variations in Rh(i) PNP complexes: reactivity insights from electronic structure.

    PubMed

    Lee, Kyounghoon; Wei, Haochuan; Blake, Anastasia V; Donahue, Courtney M; Kwon, Hyuk Yong; Keith, Jason M; Daly, Scott R

    2016-07-21

    Correction for 'Ligand K-edge XAS, DFT, and TDDFT analysis of pincer linker variations in Rh(i) PNP complexes: reactivity insights from electronic structure' by Jason M. Keith, Scott R. Daly, et al., Dalton Trans., 2016, 45, 9774-9785.

  18. Electronic structure and hybridization of CaS by means of X-ray absorption spectroscopy at Ca and S K-edges.

    PubMed

    Xu, Wei; Liu, Lijuan; Cui, Mingqi; Zheng, Lei; Hu, Yongfeng; Marcelli, Augusto; Wu, Ziyu

    2013-01-01

    The cubic calcium sulfide (CaS) is a well known system and an attractive building block material for many luminescence technological applications. However, it is essential to achieve an accurate understanding of its electronic structure in order to engineer its band structure for optimized applications. Here a study of the electronic structure of CaS by means of X-ray absorption spectroscopy performed at both Ca and S K-edges, and calculations performed in the framework of the multiple-scattering theory and of the finite difference method are presented. At the Ca K-edge the presence of an anomalous d states feature is discussed while in the S K-edge spectrum the presence of a pre-edge shoulder owing to the hybridization among Ca d states and S p states is pointed out. Although the l-projected density of states of CaS is in good agreement with previous first-principles calculations, the standard muffin-tin potential is inadequate to reproduce near-edge structures at both Ca and S K-edges in this system. Indeed, with its highly symmetric and less compact structure, CaS is characterized by a large set of collinear atomic configurations that pose severe constraints on the construction of the atomic potential. On the contrary, the finite-difference method with no muffin-tin approximation is more suitable for X-ray absorption calculations in this system.

  19. SU-C-207-06: In Vivo Quantification of Gold Nanoparticles Using K-Edge Imaging Via Spectrum Shaping by Gold Filter

    SciTech Connect

    Chen, H; Cormack, R; Bhagwat, M; Berbeco, R

    2015-06-15

    Purpose: Gold nanoparticles (AuNP) are multifunctional platforms ideal for drug delivery, targeted imaging and radiosensitization. We have investigated quantitative imaging of AuNPs using on board imager (OBI) cone beam computed tomography (CBCT). To this end, we also present, for the first time, a novel method for k-edge imaging of AuNP by filter-based spectral shaping. Methods: We used a digital 25 cm diameter water phantom, embedded with 3 cm spheres filled with AuNPs of different concentrations (0 mg/ml – 16 mg/ml). A poly-energetic X-ray spectrum of 140 kVp from a conventional X-ray tube is shaped by balanced K-edge filters to create an excess of photons right above the K-edge of gold at 80.7 keV. The filters consist of gold, tin, copper and aluminum foils. The phantom with appropriately assigned attenuation coefficients is forward projected onto a detector for each energy bin and then integrated. FKD reconstruction is performed on the integrated projections. Scatter, detector efficiency and noise are included. Results: We found that subtracting the results of two filter sets (Filter A:127 µm gold foil with 254 µm tin, 330 µm copper and 1 mm aluminum, and Filter B: 635 µm tin with 264 µm copper and 1 mm aluminum), provides substantial image contrast. The resulting filtered spectra match well below 80.7 keV, while maintaining sufficient X-ray quanta just above that. Voxel intensities of AuNP containing spheres increase linearly with AuNP concentration. K-edge imaging provides 18% more sensitivity than the tin filter alone, and 38% more sensitivity than the gold filter alone. Conclusion: We have shown that it is feasible to quantitatively detect AuNP distributions in a patient-sized phantom using clinical CBCT and K-edge spectral shaping.

  20. Correlation between spin helicity and an electric polarization vector in quantum-spin chain magnet LiCu2O2.

    PubMed

    Seki, S; Yamasaki, Y; Soda, M; Matsuura, M; Hirota, K; Tokura, Y

    2008-03-28

    Measurements of polarized neutron scattering were performed on a S=1/2 chain multiferroic LiCu2O2. In the ferroelectric ground state with the spontaneous polarization along the c axis, the existence of transverse spiral spin component in the bc plane was confirmed. When the direction of electric polarization is reversed, the vector spin chirality as defined by C_(ij)=S_(i)xS_(j) (i and j being the neighboring spin sites) is observed to be reversed, indicating that the spin-current model or the inverse Dzyaloshinskii-Moriya mechanism is applicable even to this e_(g)-electron quantum-spin system. Differential scattering intensity of polarized neutrons shows a large discrepancy from that expected for the classical-spin bc-cycloidal structure, implying the effect of large quantum fluctuation.

  1. Characterization of process-induced damage in Cu/low-k interconnect structure by microscopic infrared spectroscopy with polarized infrared light

    SciTech Connect

    Seki, Hirofumi Hashimoto, Hideki; Ozaki, Yukihiro

    2016-09-07

    Microscopic Fourier-transform infrared (FT-IR) spectra are measured for a Cu/low-k interconnect structure using polarized IR light for different widths of low-k spaces and Cu lines, and for different heights of Cu lines, on Si substrates. Although the widths of the Cu line and the low-k space are 70 nm each, considerably smaller than the wavelength of the IR light, the FT-IR spectra of the low-k film were obtained for the Cu/low-k interconnect structure. A suitable method was established for measuring the process-induced damage in a low-k film that was not detected by the TEM-EELS (Transmission Electron Microscope-Electron Energy-Loss Spectroscopy) using microscopic IR polarized light. Based on the IR results, it was presumed that the FT-IR spectra mainly reflect the structural changes in the sidewalls of the low-k films for Cu/low-k interconnect structures, and the mechanism of generating process-induced damage involves the generation of Si-OH groups in the low-k film when the Si-CH{sub 3} bonds break during the fabrication processes. The Si-OH groups attract moisture and the OH peak intensity increases. It was concluded that the increase in the OH groups in the low-k film is a sensitive indicator of low-k damage. We achieved the characterization of the process-induced damage that was not detected by the TEM-EELS and speculated that the proposed method is applicable to interconnects with line and space widths of 70 nm/70 nm and on shorter scales of leading edge devices. The location of process-induced damage and its mechanism for the Cu/low-k interconnect structure were revealed via the measurement method.

  2. Characterization of process-induced damage in Cu/low-k interconnect structure by microscopic infrared spectroscopy with polarized infrared light

    NASA Astrophysics Data System (ADS)

    Seki, Hirofumi; Hashimoto, Hideki; Ozaki, Yukihiro

    2016-09-01

    Microscopic Fourier-transform infrared (FT-IR) spectra are measured for a Cu/low-k interconnect structure using polarized IR light for different widths of low-k spaces and Cu lines, and for different heights of Cu lines, on Si substrates. Although the widths of the Cu line and the low-k space are 70 nm each, considerably smaller than the wavelength of the IR light, the FT-IR spectra of the low-k film were obtained for the Cu/low-k interconnect structure. A suitable method was established for measuring the process-induced damage in a low-k film that was not detected by the TEM-EELS (Transmission Electron Microscope-Electron Energy-Loss Spectroscopy) using microscopic IR polarized light. Based on the IR results, it was presumed that the FT-IR spectra mainly reflect the structural changes in the sidewalls of the low-k films for Cu/low-k interconnect structures, and the mechanism of generating process-induced damage involves the generation of Si-OH groups in the low-k film when the Si-CH3 bonds break during the fabrication processes. The Si-OH groups attract moisture and the OH peak intensity increases. It was concluded that the increase in the OH groups in the low-k film is a sensitive indicator of low-k damage. We achieved the characterization of the process-induced damage that was not detected by the TEM-EELS and speculated that the proposed method is applicable to interconnects with line and space widths of 70 nm/70 nm and on shorter scales of leading edge devices. The location of process-induced damage and its mechanism for the Cu/low-k interconnect structure were revealed via the measurement method.

  3. Cu-Ni core-shell nanoparticles: structure, stability, electronic, and magnetic properties: a spin-polarized density functional study

    NASA Astrophysics Data System (ADS)

    Wang, Qiang; Wang, Xinyan; Liu, Jianlan; Yang, Yanhui

    2017-02-01

    Bimetallic core-shell nanoparticles (CSNPs) have attracted great interest not only because of their superior stability, selectivity, and catalytic activity but also due to their tunable properties achieved by changing the morphology, sequence, and sizes of both core and shell. In this study, the structure, stability, charge transfer, electronic, and magnetic properties of 13-atom and 55-atom Cu and Cu-Ni CSNPs were investigated using the density functional theory (DFT) calculations. The results show that Ni@Cu CSNPs with a Cu surface shell are more energetically favorable than Cu@Ni CSNPs with a Ni surface shell. Interestingly, three-shell Ni@Cu12@Ni42 is more stable than two-shell Cu13@Ni42, while two-shell Ni13@Cu42 is more stable than three-shell Cu@Ni12@Cu42. Analysis of Bader charge illustrates that the charge transfer increases from Cu core to Ni shell in Cu@Ni NPs, while it decreases from Ni core to Cu shell in Ni@Cu NPs. Furthermore, the charge transfer results that d-band states have larger shift toward the Fermi level for the Ni@Cu CSNPs with Cu surface shell, while the Cu@Ni CSNPs with Ni surface shell have similar d-band state curves and d-band centers with the monometallic Ni NPs. In addition, the Cu-Ni CSNPs possess higher magnetic moment when the Ni atoms aggregated at core region of CSNPs, while having lower magnetic moment when the Ni atoms segregate on surface region. The change of the Cu atom location in CSNPs has a weak effect on the total magnetic moment. Our findings provide useful insights for the design of bimetallic core-shell catalysts.

  4. Enhanced k-edge angiography utilizing a superfluorescent x-ray generator with a gadolinium-target tube

    NASA Astrophysics Data System (ADS)

    Sato, Eiichi; Germer, Rudolf; Obara, Haruo; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Inoue, Takashi; Ogawa, Akira; Sato, Shigehiro; Takayama, Kazuyoshi

    2007-01-01

    The gadolinium plasma flash x-ray generator is useful for performing high-speed enhanced K-edge angiography using cone beams because K-series characteristic x-rays from the gadolinium target are absorbed effectively by iodine-based contrast media. In the flash x-ray generator, a 150 nF condenser is charged up to 80 kV by a power supply, and flash x-rays are produced by the discharging. The x-ray tube is a demountable cold-cathode diode, and the turbomolecular pump evacuates air from the tube with a pressure of approximately 1 mPa. Since the electric circuit of the high-voltage pulse generator employs a cable transmission line, the high-voltage pulse generator produces twice the potential of the condenser charging voltage. At a charging voltage of 80 kV, the estimated maximum tube voltage and current are approximately 160 kV and 40 kA, respectively. When the charging voltage was increased, the K-series characteristic x-ray intensities of gadolinium increased. Bremsstrahlung x-ray intensity rate decreased with increasing the charging voltage, and clean K lines were produced with a charging voltage of 80 kV. The x-ray pulse widths were approximately 100 ns, and the time-integrated x-ray intensity had a value of approximately 500 μGy at 1.0 m from the x-ray source with a charging voltage of 80 kV. Angiography was performed using a filmless computed radiography (CR) system and iodine-based contrast media. In the angiography of nonliving animals, we observed fine blood vessels of approximately 100 μm with high contrasts.

  5. Ab initio and experimental pre-edge investigations of the Mn K -edge XANES in oxide-type materials

    NASA Astrophysics Data System (ADS)

    Farges, François

    2005-04-01

    Mn K edge ab initio FEFF8.2 calculations of the pre-edge features of the x-ray-absorption near-edge structure (XANES) region were undertaken for a series of Mn-bearing oxide-type compounds. The aim of the study is to provide a reliable method for determining quantitative and accurate redox and symmetry information for manganese. In agreement with multiplet calculations by Glatzel and co-workers, FEFF8.2 predicts a doublet and a triplet for Mn(II) and Mn(III) in octahedral symmetry, respectively, in agreement with high-resolution XANES experiments. Site distortion increases notably the contribution from dipolar transitions and, consequently, the pre-edge feature integrated area. An even more intense pre-edge feature is calculated and measured for the Td symmetry (singletlike). For Mn(IV), a triplet is predicted and measured for the Oh symmetry. However, additional transitions are found in Mn(IV)-rich compounds, that are related to metal-metal transitions. These transitions overlap strongly with the “true pre-edge,” making extraction of redox and symmetry information for Mn(IV) more challenging. However, a model of the pre-edge with pseudo-Voigt functions of fixed calculated width (based on core-hole lifetime and experimental resolution) helps to separate the contributions related to first-neighbor symmetry from those of the metal-metal pairs. Application to multivalent defective manganese oxide materials suggests that the pre-edge information varies linearly as a function of Mn redox state or symmetry but varies nonlinearly as a function of both parameters. Finally, the polymerization of the manganese networks can be estimated from the metal-metal transitions found in the pre-edge region.

  6. K-edge angiography utilizing a tungsten plasma X-ray generator in conjunction with gadolinium-based contrast media

    NASA Astrophysics Data System (ADS)

    Sato, Eiichi; Hayasi, Yasuomi; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Inoue, Takashi; Ogawa, Akira; Sato, Shigehiro; Takayama, Kazuyoshi; Onagawa, Jun; Ido, Hideaki

    2006-11-01

    The tungsten plasma flash X-ray generator is useful in order to perform high-speed enhanced K-edge angiography using cone beams because K-series characteristic X-rays from the tungsten target are absorbed effectively by gadolinium-based contrast media. In the flash X-ray generator, a 150 nF condenser is charged up to 80 kV by a power supply, and flash X-rays are produced by the discharging. The X-ray tube is a demountable diode, and the turbomolecular pump evacuates air from the tube with a pressure of approximately 1 mPa. Since the electric circuit of the high-voltage pulse generator employs a cable transmission line, the high-voltage pulse generator produces twice the potential of the condenser charging voltage. At a charging voltage of 80 kV, the estimated maximum tube voltage and current were approximately 160 kV and 40 kA, respectively. When the charging voltage was increased, the characteristic X-ray intensities of tungsten K α lines increased. The K α lines were clean, and hardly any bremsstrahlung rays were detected. The X-ray pulse widths were approximately 110 ns, and the time-integrated X-ray intensity had a value of approximately 0.35 mGy at 1.0 m from the X-ray source with a charging voltage of 80 kV. Angiography was performed using a film-less computed radiography (CR) system and gadolinium-based contrast media. In angiography of non-living animals, we observed fine blood vessels of approximately 100 μm with high contrasts.

  7. Sulphur Speciation and Turnover in Soils: Evidence from Sulphur K-Edge XANES Spectroscopy and Isotope Dilution Studies

    SciTech Connect

    Zhao,F.; Lehmann, J.; Solomon, D.; Fox, M.; McGrath, S.

    2005-01-01

    Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to quantify S species in humic substance extracts from ten soils from the UK, China and New Zealand, which differ in land use and agricultural management. XANES spectroscopy showed the presence of most reduced (sulphides, disulphides, thiols and thiophenes), intermediate (sulphoxides and sulphonates) and highly oxidised S (ester sulphates) forms, with the three groups representing 14-32%, 33-50% and 22-53% of the organic S in the humic substance extracts, respectively. Land use had a profound influence on the relative proportions of S species. Well-drained arable soils generally had a higher proportion of organic S present in the most oxidised form than the grassland soils collected nearby, whereas paddy soils showed a more reduced profile due to episodic flooding. In the Broadbalk Classical Experiment at Rothamsted, reversion of an arable system to grassland or woodland in the 1880s resulted in an increase of the most reduced and intermediate S species at the expense of the most oxidised S species. Long-term applications of farmyard manure to an arable plot also shifted S species from the most oxidised to the intermediate and the most reduced species. Sulphur immobilization and gross mineralization were determined in seven soils using the {sup 35}S isotope dilution method. Gross mineralization during a 53-day incubation correlated more closely with the amounts of the most reduced and intermediate S species than with the most oxidised S species, suggesting that the former (C-bonded S) were the main source of organic S for mineralization in the short-term.

  8. Sulphur Speciation and Turnover in Soils: Evidence from Sulfur K-Edge XANES Spectroscopy and Isotope Dilution Studies

    SciTech Connect

    Zhao,F.; Lehmann, J.; Solomon, D.; Fox, M.; McGrath, S.

    2006-01-01

    Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to quantify S species in humic substance extracts from ten soils from the UK, China and New Zealand, which differ in land use and agricultural management. XANES spectroscopy showed the presence of most reduced (sulphides, disulphides, thiols and thiophenes), intermediate (sulphoxides and sulphonates) and highly oxidised S (ester sulphates) forms, with the three groups representing 14-32%, 33-50% and 22-53% of the organic S in the humic substance extracts, respectively. Land use had a profound influence on the relative proportions of S species. Well-drained arable soils generally had a higher proportion of organic S present in the most oxidised form than the grassland soils collected nearby, whereas paddy soils showed a more reduced profile due to episodic flooding. In the Broadbalk Classical Experiment at Rothamsted, reversion of an arable system to grassland or woodland in the 1880s resulted in an increase of the most reduced and intermediate S species at the expense of the most oxidised S species. Long-term applications of farmyard manure to an arable plot also shifted S species from the most oxidised to the intermediate and the most reduced species. Sulphur immobilisation and gross mineralisation were determined in seven soils using the {sup 35}S isotope dilution method. Gross mineralisation during a 53-day incubation correlated more closely with the amounts of the most reduced and intermediate S species than with the most oxidised S species, suggesting that the former (C-bonded S) were the main source of organic S for mineralisation in the short-term.

  9. Evaluation of spectral photon counting computed tomography K-edge imaging for determination of gold nanoparticle biodistribution in vivo.

    PubMed

    Si-Mohamed, Salim; Cormode, David P; Bar-Ness, Daniel; Sigovan, Monica; Naha, Pratap C; Langlois, Jean-Baptiste; Chalabreysse, Lara; Coulon, Philippe; Blevis, Ira; Roessl, Ewald; Erhard, Klaus; Boussel, Loic; Douek, Philippe

    2017-07-20

    Spectral photon counting computed tomography (SPCCT) is an emerging medical imaging technology. SPCCT scanners record the energy of incident photons, which allows specific detection of contrast agents due to measurement of their characteristic X-ray attenuation profiles. This approach is known as K-edge imaging. Nanoparticles formed from elements such as gold, bismuth or ytterbium have been reported as potential contrast agents for SPCCT imaging. Furthermore, gold nanoparticles have many applications in medicine, such as adjuvants for radiotherapy and photothermal ablation. In particular, longitudinal imaging of the biodistribution of nanoparticles would be highly attractive for their clinical translation. We therefore studied the capabilities of a novel SPCCT scanner to quantify the biodistribution of gold nanoparticles in vivo. PEGylated gold nanoparticles were used. Phantom imaging showed that concentrations measured on gold images correlated well with known concentrations (slope = 0.94, intercept = 0.18, RMSE = 0.18, R(2) = 0.99). The SPCCT system allowed repetitive and quick acquisitions in vivo, and follow-up of changes in the AuNP biodistribution over time. Measurements performed on gold images correlated with the inductively coupled plasma-optical emission spectrometry (ICP-OES) measurements in the organs of interest (slope = 0.77, intercept = 0.47, RMSE = 0.72, R(2) = 0.93). TEM results were in agreement with the imaging and ICP-OES in that much higher concentrations of AuNPs were observed in the liver, spleen, bone marrow and lymph nodes (mainly in macrophages). In conclusion, we found that SPCCT can be used for repetitive and non-invasive determination of the biodistribution of gold nanoparticles in vivo.

  10. Ab initio and experimental pre-edge investigations of the Mn K-edge XANES in oxide-type materials

    SciTech Connect

    Farges, Francois

    2005-04-15

    Mn K edge ab initio FEFF8.2 calculations of the pre-edge features of the x-ray-absorption near-edge structure (XANES) region were undertaken for a series of Mn-bearing oxide-type compounds. The aim of the study is to provide a reliable method for determining quantitative and accurate redox and symmetry information for manganese. In agreement with multiplet calculations by Glatzel and co-workers, FEFF8.2 predicts a doublet and a triplet for Mn(II) and Mn(III) in octahedral symmetry, respectively, in agreement with high-resolution XANES experiments. Site distortion increases notably the contribution from dipolar transitions and, consequently, the pre-edge feature integrated area. An even more intense pre-edge feature is calculated and measured for the T{sub d} symmetry (singletlike). For Mn(IV), a triplet is predicted and measured for the O{sub h} symmetry. However, additional transitions are found in Mn(IV)-rich compounds, that are related to metal-metal transitions. These transitions overlap strongly with the 'true pre-edge', making extraction of redox and symmetry information for Mn(IV) more challenging. However, a model of the pre-edge with pseudo-Voigt functions of fixed calculated width (based on core-hole lifetime and experimental resolution) helps to separate the contributions related to first-neighbor symmetry from those of the metal-metal pairs. Application to multivalent defective manganese oxide materials suggests that the pre-edge information varies linearly as a function of Mn redox state or symmetry but varies nonlinearly as a function of both parameters. Finally, the polymerization of the manganese networks can be estimated from the metal-metal transitions found in the pre-edge region.

  11. Relativistic spin - polarized theory of magnetoelastic coupling and magnetic anisotropy strain dependence: application to Co/Cu(001).

    NASA Astrophysics Data System (ADS)

    Shick, A. B.; Novikov, D. L.; Freeman, A. J.

    1997-08-01

    A self-consistent relativistic spin-polarized version of the total energy full potential linearized augmented plane wave (FLAPW) method (E. Wimmer, H. Krakauer, M. Weinert and A.J. Freeman, Phys. Rev. B 24), 864 (1981). is applied to determine the magnetoelastic coupling, orbital magnetic moment anisotropy and magnetic anisotropy energy (MAE) of a Co overlayer on Cu(001). The total energy as a function of perpendicular overlayer/substrate strain is well fitted by a parabola and the MAE (-0.36 meV) at the equilibrium is in good agreement with experiment. As discovered earlier by Wu and Freeman (R.Q. Wu and A.J. Freeman, J.Appl.Phys. 79), 6209 (1996). , we find a linear dependence of the MAE on the overlayer/substrate distance. The calculated positive effective magnetoelastic coupling coefficient (1.13 meV) is caused by a positive surface magnetoelastic anisotropy (0.23 meV). The relativistic total energy based model for ultrathin film magnetostriction yields a magnetostriction coefficient λ_001= -5.20×10-5 and an isotropic magnetostriction coefficient λ_s=-5.65×10-5 that is in very good agreement with previous studies based on a perturbative SOC treatment. The negative sign of the magnetostriction coefficient is caused by a positive surface magnetoelastic anisotropy.

  12. Nuclear spins, magnetic moments, and quadrupole moments of Cu isotopes from N=28 to N=46: Probes for core polarization effects

    SciTech Connect

    Vingerhoets, P.; Avgoulea, M.; Bissell, M. L.; De Rydt, M.; Neyens, G.; Flanagan, K. T.; Billowes, J.; Cheal, B.; Mane, E.; Blaum, K.; Schug, M.; Brown, B. A.; Forest, D. H.; Tungate, G.; Geppert, Ch.; Noertershaeuser, W.; Honma, M.; Kowalska, M.; Kraemer, J.; Krieger, A.

    2010-12-15

    Measurements of the ground-state nuclear spins and magnetic and quadrupole moments of the copper isotopes from {sup 61}Cu up to {sup 75}Cu are reported. The experiments were performed at the CERN online isotope mass separator (ISOLDE) facility, using the technique of collinear laser spectroscopy. The trend in the magnetic moments between the N=28 and N=50 shell closures is reasonably reproduced by large-scale shell-model calculations starting from a {sup 56}Ni core. The quadrupole moments reveal a strong polarization of the underlying Ni core when the neutron shell is opened, which is, however, strongly reduced at N=40 due to the parity change between the pf and g orbits. No enhanced core polarization is seen beyond N=40. Deviations between measured and calculated moments are attributed to the softness of the {sup 56}Ni core and weakening of the Z=28 and N=28 shell gaps.

  13. Formation and stability of Pb-, Zn- & Cu-PO₄ phases at low temperatures: implications for heavy metal fixation in polar environments.

    PubMed

    White, Duanne A; Hafsteinsdóttir, Erla G; Gore, Damian B; Thorogood, Gordon; Stark, Scott C

    2012-02-01

    Low temperatures and frequent soil freeze-thaw in polar environments present challenges for the immobilisation of metals. To address these challenges we investigated the chemical forms of Pb, Zn and Cu in an Antarctic landfill, examined in vitro reaction kinetics of these metals and orthophosphate at 2 and 22 °C for up to 185 days, and subjected the products to freeze-thaw. Reaction products at both temperatures were similar, but the rate of production varied, with Cu-PO(4) phases forming faster, and the Zn- and Pb-PO(4) phases slower at 2 °C. All metal-orthophosphate phases produced were stable during a 2.5 h freeze-thaw cycle to -30 °C. Metal immobilisation using orthophosphate can be successful in polar regions, but treatments will need to consider differing mineral stabilities and reaction rates at low temperatures. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Optical phonons in the wurtzstannite Cu2ZnGeS4 semiconductor: Polarized Raman spectroscopy and first-principle calculations

    NASA Astrophysics Data System (ADS)

    Guc, M.; Litvinchuk, A. P.; Levcenko, S.; Izquierdo-Roca, V.; Fontané, X.; Valakh, M. Ya.; Arushanov, E.; Pérez-Rodríguez, A.

    2014-05-01

    The vibrational properties of the wurtzstannite Cu2ZnGeS4 are studied experimentally by polarized Raman scattering in off-resonant and resonant conditions and theoretically by ab initio lattice dynamics calculations. Twenty-nine modes from 45 Raman active theoretically predicted have been experimentally detected and identified, including polar A1(TO),A1(LO), and B1(TO+LO)/B2(TO+LO) and nonpolar A2 symmetry phonon modes from measurements on (2 1 0) and (0 0 1) crystallographic planes of Cu2ZnGeS4 single crystals. The lattice dynamics calculations provide a full picture of the zone center phonon spectrum and allow the assignment of experimentally observed lines to first- and second-order lattice vibrations. Using resonance Raman conditions, a strong enhancement of the A1(LO) modes with the highest longitudinal-transversal spiting is observed.

  15. High resolution short focal distance Bent Crystal Laue Analyzer for copper K edge x-ray absorption spectroscopy

    SciTech Connect

    Kujala, N. G.; Barrea, R. A.; Karanfil, C.

    2011-06-15

    We have developed a compact short focal distance Bent Crystal Laue Analyzer (BCLA) for Cu speciation studies of biological systems with specific applications to cancer biology. The system provides high energy resolution and high background rejection. The system is composed of an aluminum block serving as a log spiral bender for a 15 micron thick Silicon 111 crystal and a set of soller slits. The energy resolution of the BCLA--about 14 eV at the Cu K{alpha} line-- allows resolution of the Cu K{alpha}{sub 1} and CuK{alpha}{sub 2} lines. The system is easily aligned by using a set of motorized XYZ linear stages. Two operation modes are available: incident energy scans (IES) and emission energy scans (EES). IES allows scanning of the incident energy while the BCLA system is maintained at a preselected fixed position - typically CuK{alpha}{sub 1} line. EES is used when the incident energy is fixed and the analyzer is scanned to provide the peak profile of the emission lines of Cu.

  16. Si K-edge XANES study of SiO{sub x}C{sub y}H{sub z} amorphous polymeric materials

    SciTech Connect

    Chaboy, J.; Barranco, A.; Yanguas-Gil, A.; Yubero, F.; Gonzalez-Elipe, A. R.

    2007-02-15

    This work reports on x-ray absorption spectroscopy study at the Si K edge of several amorphous SiO{sub x}C{sub y}H{sub z} polymers prepared by plasma-enhanced chemical-vapor deposition with different C/O ratios. SiO{sub 2} and SiC have been used as reference materials. The comparison of the experimental Si K-edge x-ray absorption near-edge structure spectra with theoretical computations based on multiple scattering theory has allowed us to monitor the modification of the local coordination around Si as a function of the overall C/O ratio in this kind of materials.

  17. Simulating Cl K-edge X-ray absorption spectroscopy in MCl62- (M= U, Np, Pu) complexes and UOCl5- using time-dependent density functional theory

    SciTech Connect

    Govind, Niranjan; De Jong, Wibe A.

    2014-02-21

    We report simulations of the X-ray absorption near edge structure (XANES) at the Cl K-edge of actinide hexahalides MCl62- (M = U, Np, Pu) and the UOCl5- complex using linear-response time-dependent density functional theory (LR-TDDFT) extended for core excitations. To the best of our knowledge, these are the first calculations of the Cl K-edge spectra of NpCl62- and PuCl62-. In addition, the spectra are simulated with and without the environmental effects of the host crystal as well as ab initio molecular dynamics (AIMD) to capture the dynamical effects due to atomic motion. The calculated spectra are compared with experimental results, where available and the observed trends are discussed.

  18. Interaction of Nanostructured Calcium Silicate Hydrate with Ibuprofen Drug Molecules: X-ray Absorption Near Edge Structure (XANES) Study at the Ca, Si and O K-edge

    NASA Astrophysics Data System (ADS)

    Guo, X. X.; Sham, T. K.; Zhu, Y. J.; Hu, Y. F.

    2013-04-01

    Mesoporous calcium silicate hydrate (CSH) nanostructure has been proven to be bioactive and biocompatible, and has a bright future in the application of bone treatment among other applications. X-ray absorption near edge structure (XANES) is a powerful tool for the study of the interactions of calcium silicate hydrates with drug molecules because it is element specific and it probes the unoccupied electronic states. Herein, we report the use of the calcium, silicon and oxygen K-edge XANES spectroscopy to identify how drug molecules interact with different groups in calcium silicate hydrate mesoporous nano-carriers with different morphologies. Significant changes are observed in XANES spectra after drug loading into the calcium silicate hydrate system, especially at the Si and O K-edge. The implications of these findings are discussed.

  19. Measurement of X-ray mass attenuation coefficient of nickel around the K-edge using synchrotron radiation based X-ray absorption study

    NASA Astrophysics Data System (ADS)

    Roy, Bunty Rani; Rajput, Parasmani; Jha, S. N.; Nageswara Rao, A. S.

    2015-09-01

    The work presents the X-ray absorption fine structure (XAFS) technique for measuring the X-ray mass attenuation coefficient of nickel metal foil in the X-ray energy range of 8271.2-8849.4 eV using scanning XAFS beam line (BL-09) at Indus-2 synchrotron radiation source facility, Raja Ramanna Centre for Advanced Technology (RRCAT) at Indore, India. The result represents the X-ray mass attenuation coefficient data for 0.02 mm thick Ni metal foil in the XAFS region of Ni K-edge. However, the results are compared to theoretical values using X-COM. There is a maximum deviation which is found exactly near the K-edge jump and decreases as we move away from the absorption edge. Oscillatory structure appears just above the observed absorption edge i.e., 8348.7 eV and is confined to around 250 eV above the edge.

  20. Nitrogen K-edge X-ray absorption near edge structure (XANES) spectra of purine-containing nucleotides in aqueous solution.

    PubMed

    Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    2014-08-07

    The N K-edge X-ray absorption near edge structure (XANES) spectra of the purine-containing nucleotide, guanosine 5'-monophosphate (GMP), in aqueous solution are measured under various pH conditions. The spectra show characteristic peaks, which originate from resonant excitations of N 1s electrons to π* orbitals inside the guanine moiety of GMP. The relative intensities of these peaks depend on the pH values of the solution. The pH dependence is explained by the core-level shift of N atoms at specific sites caused by protonation and deprotonation. The experimental spectra are compared with theoretical spectra calculated by using density functional theory for GMP and the other purine-containing nucleotides, adenosine 5'-monophosphate, and adenosine 5'-triphosphate. The N K-edge XANES spectra for all of these nucleotides are classified by the numbers of N atoms with particular chemical bonding characteristics in the purine moiety.

  1. Probing single magnon excitations in Sr2IrO4 using O K-edge resonant inelastic x-ray scattering

    NASA Astrophysics Data System (ADS)

    Liu, X.; Dean, M. P. M.; Liu, J.; Chiuzbăian, S. G.; Jaouen, N.; Nicolaou, A.; Yin, W. G.; Rayan Serrao, C.; Ramesh, R.; Ding, H.; Hill, J. P.

    2015-05-01

    Resonant inelastic x-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr2IrO4, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolution in the hard x-ray region is usually poor.

  2. Optical properties of boron carbide near the boron K edge evaluated by soft-x-ray reflectometry from a Ru/B4C multilayer

    SciTech Connect

    Ksenzov, Dmitriy; Panzner, Tobias; Schlemper, Christoph; Morawe, Christian; Pietsch, Ullrich

    2009-12-10

    Soft-x-ray Bragg reflection from two Ru/B4C multilayers with 10 and 63 periods was used for independent determination of both real and imaginary parts of the refractive index n = 1 -{delta} + i{beta} close to the boron K edge ({approx}188 eV). Prior to soft x-ray measurements, the structural parameters of the multilayers were determined by x-ray reflectometry using hard x rays. For the 63-period sample, the optical properties based on the predictions made for elemental boron major deviations were found close to the K edge of boron for the 10-period sample explained by chemical bonding of boron to B4C and various boron oxides.

  3. Performance of computed tomography for contrast agent concentration measurements with monochromatic x-ray beams: comparison of K-edge versus temporal subtraction

    NASA Astrophysics Data System (ADS)

    Elleaume, H.; Charvet, A. M.; Corde, S.; Estève, F.; LeBas, J. F.

    2002-09-01

    We investigated the performance of monochromatic computed tomography for the quantification of contrast agent concentrations. Two subtraction methods (K-edge subtraction and temporal subtraction) were evaluated and compared theoretically and experimentally in terms of detection limit, precision and accuracy. Measurements were performed using synchrotron x-rays with Lucite phantoms (10 cm and 17.5 cm in diameter) containing iodine or gadolinium solutions ranging from 50 μg ml-1 to 5 mg ml-1. The experiments were carried out using monochromators developed at the European Synchrotron Radiation Facility (ESRF) medical beamline. The phantoms were imaged either above and below the contrast agent K-edge, or before and after the addition of the contrast agent. Both methods gave comparable performance for phantoms less than 10 cm in diameter. For large phantoms, equivalent to a human head, the temporal subtraction is more suitable for detecting elements such as iodine, keeping a reasonable x-ray dose delivered to the phantom. A good agreement was obtained between analytical calculations, simulations and measurements. The beam harmonic content was taken into account in the simulations. It explains the performance degradation with high contrast agent concentrations. The temporal subtraction technique has the advantage of energy tunability and is well suited for imaging elements, such as iodine or gadolinium, in highly absorbing samples. For technical reasons, the K-edge method is preferable when the imaged organ is moving since the two measurements can be performed simultaneously, which is mandatory for obtaining a good subtraction.

  4. Vibrationally resolved NEXAFS at C and N K-edges of pyridine, 2-fluoropyridine and 2,6-difluoropyridine: A combined experimental and theoretical assessment

    SciTech Connect

    Baiardi, Alberto; Mendolicchio, Marco; Barone, Vincenzo; Fronzoni, Giovanna; Cardenas Jimenez, Gustavo Adolfo; Stener, Mauro; Grazioli, Cesare; Simone, Monica de; Coreno, Marcello

    2015-11-28

    In the present work, the near edge X-ray absorption spectroscopy (NEXAFS) spectra at both C and N K-edges of pyridine, 2-fluoropyridine, and 2,6-difluoropyridine have been studied both experimentally and theoretically. From an electronic point of view, both transition potential density functional theory and time-dependent density functional theory approaches lead to reliable results provided that suitable basis sets and density functionals are employed. In this connection, the global hybrid B3LYP functional in conjunction with the EPR-III basis set appears particularly suitable after constant scaling of the band positions. For the N K-edge, vertical energies obtained at these levels and broadened by symmetric Gaussian distributions provide spectra in reasonable agreement with the experiment. Vibronic contributions further modulate the band-shapes leading to a better agreement with the experimental results, but are not strictly necessary for semi-quantitative investigations. On the other hand, vibronic contributions are responsible for strong intensity redistribution in the NEXAFS C K-edge spectra, and their inclusion is thus mandatory for a proper description of experiments. In this connection, the simple vertical gradient model is particularly appealing in view of its sufficient reliability and low computational cost. For more quantitative results, the more refined vertical Hessian approach can be employed, and its effectiveness has been improved thanks to a new least-squares fitting approach.

  5. Sulfur K-edge x-ray absorption spectroscopy: A spectroscopic tool to examine the redox state of S-containing metabolites in vivo

    PubMed Central

    Rompel, Annette; Cinco, Roehl M.; Latimer, Matthew J.; McDermott, Ann E.; Guiles, R. D.; Quintanilha, Alexandre; Krauss, Ronald M.; Sauer, Kenneth; Yachandra, Vittal K.; Klein, Melvin P.

    1998-01-01

    The sulfur K-edge x-ray absorption spectra for the amino acids cysteine and methionine and their corresponding oxidized forms cystine and methionine sulfoxide are presented. Distinct differences in the shape of the edge and the inflection point energy for cysteine and cystine are observed. For methionine sulfoxide the inflection point energy is 2.8 eV higher compared with methionine. Glutathione, the most abundant thiol in animal cells, also has been investigated. The x-ray absorption near-edge structure spectrum of reduced glutathione resembles that of cysteine, whereas the spectrum of oxidized glutathione resembles that of cystine. The characteristic differences between the thiol and disulfide spectra enable one to determine the redox status (thiol to disulfide ratio) in intact biological systems, such as unbroken cells, where glutathione and cyst(e)ine are the two major sulfur-containing components. The sulfur K-edge spectra for whole human blood, plasma, and erythrocytes are shown. The erythrocyte sulfur K-edge spectrum is similar to that of fully reduced glutathione. Simulation of the plasma spectrum indicated 32% thiol and 68% disulfide sulfur. The whole blood spectrum can be simulated by a combination of 46% disulfide and 54% thiol sulfur. PMID:9600928

  6. In situ removal of carbon contamination from a chromium-coated mirror: ideal optics to suppress higher-order harmonics in the carbon K-edge region.

    PubMed

    Toyoshima, Akio; Kikuchi, Takashi; Tanaka, Hirokazu; Mase, Kazuhiko; Amemiya, Kenta

    2015-11-01

    Carbon-free chromium-coated optics are ideal in the carbon K-edge region (280-330 eV) because the reflectivity of first-order light is larger than that of gold-coated optics while the second-order harmonics (560-660 eV) are significantly suppressed by chromium L-edge and oxygen K-edge absorption. Here, chromium-, gold- and nickel-coated mirrors have been adopted in the vacuum ultraviolet and soft X-ray branch beamline BL-13B at the Photon Factory in Tsukuba, Japan. Carbon contamination on the chromium-coated mirror was almost completely removed by exposure to oxygen at a pressure of 8 × 10(-2) Pa for 1 h under irradiation of non-monochromated synchrotron radiation. The pressure in the chamber recovered to the order of 10(-7) Pa within a few hours. The reflectivity of the chromium-coated mirror of the second-order harmonics in the carbon K-edge region (560-660 eV) was found to be a factor of 0.1-0.48 smaller than that of the gold-coated mirror.

  7. In situ Fe K-edge X-ray absorption fine structure of a pyrite electrode in a Li/polyethylene oxide (LiClO{sub 4})/FeS{sub 2} battery environment

    SciTech Connect

    Totir, D.; Bae, I.T.; Hu, Y.; Scherson, D.A.; Antonio, M.R.

    1996-12-31

    Electronic and structural properties of materials generated by the reduction and subsequent oxidation of pyrite in a lithium-based solid polymer electrolyte have been examined by in situ fluorescence Fe K-edge X-ray absorption fine structure (XAFS) in a FeS{sub 2}/Li battery environment. The XAFS results obtained are consistent with the formation of metallic iron as one of the products of the full (4-electron) discharge, in agreement with information reported in other laboratories. Extended X-ray absorption fine structure (EXAFS) data reveal that a subsequent 2-electron or 4-electron recharge generates a species with a Fe-S bond distance identical to that of pyrite, d(Fe-S) = 2.259 {angstrom}, with no other clearly detectable interactions due to more distant atoms. Based on the similarities between the metrical parameters and other features in the X-ray absorption near edge structure (XANES), the ferrous sites in these species appear to be tetrahedrally coordinated, as in chalcopyrite (CuFeS{sub 2}), for which d(Fe-S) is 2.257 {angstrom}, and, thus, different than in Li{sub 2} FeS{sub 2}, a material that exhibits longer Fe-S distances.

  8. Magnetic state of Nb(l-7nm)/Cu30Ni70 (6nm) superlattices revealed by Polarized Neutron Reflectometry and SQUID magnetometry

    NASA Astrophysics Data System (ADS)

    Khaydukov, Yu.; Morari, R.; Lenk, D.; Zdravkov, V.; Merkel, D. G.; Seidlhofer, B.-K.; Miiller, C.; Krug von Nidda, H.-A.; Keller, T.; Steitz, R.; Sidorenko, A.; Horn, S.; Tidecks, R.; Keimer, B.

    2017-06-01

    We report results of a magnetic characterization of [Cu30Ni70(6nm)/Nb(x)]20(x=1÷7nm) superlattices using Polarized Neutron Reflectometry (PNR) and SQUID magnetometry. The study has shown that the magnetic moment of the structures growths almost linearly from H = 0 to Hsat = 1.3kOe which can be interpreted as evidence of antiferromagnetic (AF) coupling of the magnetic moments in neighbouring layers. PNR, however, did not detect any in-plane AF coupling. Taking into account the out-of-plane easy axis of the Cu30Ni70 layers, this may mean that only the out-of-plane components of the magnetic moments are AF coupled.

  9. Theory of K-edge resonant inelastic x-ray scattering and its application for La0.5Sr1.5MnO4

    NASA Astrophysics Data System (ADS)

    Seman, T. F.; Liu, X.; Hill, J. P.; van Veenendaal, M.; Ahn, K. H.

    2013-03-01

    We present a formula based on tight-binding approach for the calculation of K-edge resonant inelastic x-ray scattering spectrum for transition metal oxides, by extending the previous result [K. H. Ahn, A. J. Fedro, and M. van Veenendaal, Phys. Rev. B 79, 045103 (2009).] to include explicit momentum dependence and a basis with multiple core hole sites. We apply this formula to layered charge, orbital, and spin ordered manganites, La0.5Sr1.5MnO4. The K-edge RIXS spectrum is found not periodic with respect to the actual reciprocal lattice, but approximately periodic with respect to the reciprocal lattice for the hypothetical unit cell with one core hole site. With experimental strcuture and reasonable tight-binding parameters, we obtain good agreement with experimental data, in particular, with regards to the large variation of the intensity with momentum. We find that the screening in La0.5Sr1.5MnO4 is highly localized around the core hole site and demonstrate the potential of K-edge RIXS as a probe for the screening dynamics in materials. Work supported by US.DOE Contr. DE-AC02-98CH10886 (X.L.,J.H.), US.DOE Award DE-FG02-03ER46097 (M.v.V.), CMCSN under Grants DE-FG02-08ER46540 & DE-SC0007091 (T.S.,K.A.,M.v.V.), Argonne XSD Visitor Prog.(K.A.), US.DOE Contr. DE-AC02-06CH11357 (X.L.,J.H).

  10. Experimental versus ab initio x-ray absorption of iron-doped zirconia: Trends in O K -edge spectra as a function of iron doping

    NASA Astrophysics Data System (ADS)

    Douma, D. H.; Ciprian, R.; Lamperti, A.; Lupo, P.; Cianci, E.; Sangalli, D.; Casoli, F.; Nasi, L.; Albertini, F.; Torelli, P.; Debernardi, A.

    2014-11-01

    We present an experimental study of x-ray absorption near edge structure (XANES) at L2 ,3,M2 ,3, and K edges of, respectively, Fe, Zr, and O in iron-doped zirconia (ZrO2:Fe ) for different Fe dopant concentrations x (from x ˜6 % to x ˜25 % at.) and make the comparison with ab initio simulations at the O K -edge. The x-ray magnetic circular dichroism (XMCD) measurements show no evidence of ferromagnetic (FM) order for all the analyzed samples in agreement with our ab initio simulations, which show an antiferromagnetic (AFM) order. We found that substituting Zr with Fe atoms leads to a radical change in the O K -edge XANES spectrum, especially in the pre-edge region where a pre-edge peak appears. This pre-edge peak is ascribed to dipole transitions from O 1 s to O 2 p states that are hybridized with the unoccupied Fe 3 d states. Both theoretical and experimental results reveal that the intensity of the pre-edge peak increases with Fe concentration, suggesting the increase of unoccupied Fe 3 d states. The increase of Fe concentration increases oxygen vacancies as required for charge neutrality and consequently improves AFM ordering. According to our first-principles calculations, the effect of one Fe atom is mostly localized in the first oxygen shell and vanishes as one moves far from it. Thus the increase of the O K -pre-edge peak with increasing Fe concentration is due to the increase of percentage of oxygen atoms that are near neighbors to Fe atoms.

  11. Fe K-edge X-ray resonant magnetic scattering from Ba(Fe1−xCox)2As2 superconductors

    SciTech Connect

    Kim, Min Gyu; Kreyssig, Andreas; Lee, Yongbin; McQueeney, Robert J.; Harmon, Bruce N.; Goldman, Alan I.

    2012-06-15

    We present an X-ray resonant magnetic scattering study at the Fe-K absorption edge of the BaFe2As2 compound. The energy spectrum of the resonant scattering, together with our calculation using the full-potential linear-augmented plane wave method with a local density functional suggests that the observed resonant scattering arises from electric dipole (E1) transitions. We discuss the role of Fe K-edge X-ray resonant magnetic scattering in understanding the relationship between the structure and the antiferromagnetic transition in the doped Ba(Fe1−xCox)2As2 superconductors.

  12. Ligand K-edge XAS, DFT, and TDDFT analysis of pincer linker variations in Rh(i) PNP complexes: reactivity insights from electronic structure.

    PubMed

    Lee, Kyounghoon; Wei, Haochuan; Blake, Anastasia V; Donahue, Courtney M; Keith, Jason M; Daly, Scott R

    2016-06-14

    Here we report P K-edge, Cl K-edge, and Rh L3-edge X-ray absorption spectroscopy (XAS) data for Rh[C5H3N-2,6-(XP(t)Bu2)2]Cl, where X = O ((tBu)PONOP; ) or CH2 ((tBu)PNP; ). Solid-state XAS data for and were compared to density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations to identify how changing the PNP pincer linker from O to CH2 affected electronic structure and bonding at Rh(i). Pronounced differences in XAS peak intensities and energies were observed. The P K-edge XAS data revealed a large increase in Rh 4dx(2)-y(2) and P 3p orbital-mixing (Rh-P σ*) in compared to , and pronounced transition energy variations reflected marked differences in orbital energies and compositions. By comparison, the Cl K-edge XAS data revealed only subtle differences in Rh-Cl covalency, although larger splitting between the Rh-Cl π* and σ* transitions was observed in . Analysis of the occupied MOs from DFT (HOMO, HOMO-1, HOMO-2, and HOMO-3) and comparison to the unoccupied MOs involved in XAS revealed a relatively uniform energy increase (ca. 0.3-0.5 eV) for all five 4d-derived molecular orbitals in Rh((tBu)PNP)Cl () compared to Rh((tBu)PONOP)Cl (). The energy shift was relatively invariant with respect to differences in orbital symmetry, bonding type (σ or π), and orbital mixing, which suggested that the increase could be attributed to electrostatic effects. The change in d-orbital energies are consistent with known reactivity differences of Rh((tBu)PONOP)(+) and Rh((tBu)PNP)(+) towards CO, H2, and CH2Cl2, and are explained here by considering how d-orbital energies affect covalent L → M σ bonding and M → L π backbonding.

  13. Determination of the S-ZnO structural interaction in thiol-capped ZnO nanoparticles: a sulfur K-edge XAS study.

    PubMed

    Guglieri, Clara; Aquilanti, Giuliana; Díaz-Moreno, Sofía; Chaboy, J

    2017-02-03

    ZnO nanoparticles capped with thiol molecules display room temperature ferromagnetism which has been associated with the structural details of the interface formed between the organic molecule and the ZnO core. Although the local order around sulfur atoms at the ZnS/ZnO interface has been related to the occurrence of the ferromagnetic like behavior, no direct structural determination has been obtained yet. We report here a detailed x-ray absorption spectroscopy study performed at the sulfur K-edge to determine the local structure around the sulfur atoms in these systems and how it is modified by varying the length of the organic molecule.

  14. Determination of the S-ZnO structural interaction in thiol-capped ZnO nanoparticles: a sulfur K-edge XAS study

    NASA Astrophysics Data System (ADS)

    Guglieri, Clara; Aquilanti, Giuliana; Díaz-Moreno, Sofía; Chaboy, J.

    2017-02-01

    ZnO nanoparticles capped with thiol molecules display room temperature ferromagnetism which has been associated with the structural details of the interface formed between the organic molecule and the ZnO core. Although the local order around sulfur atoms at the ZnS/ZnO interface has been related to the occurrence of the ferromagnetic like behavior, no direct structural determination has been obtained yet. We report here a detailed x-ray absorption spectroscopy study performed at the sulfur K-edge to determine the local structure around the sulfur atoms in these systems and how it is modified by varying the length of the organic molecule.

  15. Indirect Probing of defects in unipolar resistive switching NiOx thin films by Ni K-edge resonant inelastic x-ray scattering

    SciTech Connect

    Jung, Ranju; Phark, Soo-Hyong; Kim, Dong-Wood; Upton, Mary; Casa, Diego; Gog, Thomas; Kim, Jungho

    2015-02-01

    We present observations of the Ni K-edge resonant inelastic X-ray scattering (RIXS) in NiOx thin films showing unipolar resistive switching (RS). The RIXS spectra of RS NiOx thin films can be described in terms of crystal field (dd) and charge transfer (CT) excitations. We found distorted dd excitations in the films' pristine state before electroforming, and identical excitations for high and low resistance states after electroforming. This suggests that the RS property of NiOx thin film is related to defects in pristine NiOx films, and RS occurs in local nanosized spots too small to be detected by RIXS.

  16. Resonant inelastic x-ray scattering on iso-C₂H₂Cl₂ around the chlorine K-edge: structural and dynamical aspects.

    PubMed

    Kawerk, Elie; Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Piancastelli, Maria Novella; Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok; Kavčič, Matjaž; Céolin, Denis; Khoury, Antonio; Simon, Marc

    2014-10-14

    We report a theoretical and experimental study of the high resolution resonant K(α) X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K(α) emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

  17. Auger electron and photoabsorption spectra of glycine in the vicinity of the oxygen K-edge measured with an X-FEL

    NASA Astrophysics Data System (ADS)

    Sanchez-Gonzalez, A.; Barillot, T. R.; Squibb, R. J.; Kolorenč, P.; Agaker, M.; Averbukh, V.; Bearpark, M. J.; Bostedt, C.; Bozek, J. D.; Bruce, S.; Carron Montero, S.; Coffee, R. N.; Cooper, B.; Cryan, J. P.; Dong, M.; Eland, J. H. D.; Fang, L.; Fukuzawa, H.; Guehr, M.; Ilchen, M.; Johnsson, A. S.; Liekhus-S, C.; Marinelli, A.; Maxwell, T.; Motomura, K.; Mucke, M.; Natan, A.; Osipov, T.; Östlin, C.; Pernpointner, M.; Petrovic, V. S.; Robb, M. A.; Sathe, C.; Simpson, E. R.; Underwood, J. G.; Vacher, M.; Walke, D. J.; Wolf, T. J. A.; Zhaunerchyk, V.; Rubensson, J.-E.; Berrah, N.; Bucksbaum, P. H.; Ueda, K.; Feifel, R.; Frasinski, L. J.; Marangos, J. P.

    2015-12-01

    We report the first measurement of the near oxygen K-edge auger spectrum of the glycine molecule. Our work employed an x-ray free electron laser as the photon source operated with input photon energies tunable between 527 and 547 eV. Complete electron spectra were recorded at each photon energy in the tuning range, revealing resonant and non-resonant auger structures. Finally ab initio theoretical predictions are compared with the measured above the edge auger spectrum and an assignment of auger decay channels is performed.

  18. Submicrometer hyperspectral X-ray imaging of heterogeneous rocks and geomaterials: applications at the Fe k-edge.

    PubMed

    De Andrade, Vincent; Susini, Jean; Salomé, Murielle; Beraldin, Olivier; Rigault, Cecile; Heymes, Thomas; Lewin, Eric; Vidal, Olivier

    2011-06-01

    Because of their complex genesis, rocks and geomaterials are commonly polycrystalline heterogeneous systems, with various scale-level chemical and structural heterogeneities. Like most other μ-analytical techniques relying on scanning instruments with pencil-beam, the X-ray absorption near edge structure (XANES) technique allows elemental oxidation states to be probed with high spatial resolution but suffers from long acquisition times, imposing practical limits on the field of view. Now, regions of interest of sample are generally several orders of magnitude larger than the beam size. Here, we show the potential of coupling XANES and full-field absorption radiographies with a large hard X-ray beam. Thanks to a new setup, which allows both the acquisition of a XANES image stack and the execution of polarization contrast imaging, 1 to 4 mega-pixel crystallographic orientations and Fe oxidation state mapping corrected from polarization effects are obtained in a couple of hours on polycrystalline materials with submicrometric resolution. The demonstration is first carried out on complex metamorphic rocks, where Fe(3+)/Fe(total) images reveal subtle redox variations within single mineralogical phases. A second application concerns a bentonite analogue considered for nuclear waste and CO(2) storage. Proportion mappings of finely mixed phases are extracted from hyperspectral data, imaging the spatial progress of reaction processes essential for the safety of such storage systems.

  19. PMMA interlayer-modulated memory effects by space charge polarization in resistive switching based on CuSCN-nanopyramids/ZnO-nanorods p-n heterojunction

    NASA Astrophysics Data System (ADS)

    Cheng, Baochang; Zhao, Jie; Xiao, Li; Cai, Qiangsheng; Guo, Rui; Xiao, Yanhe; Lei, Shuijin

    2015-12-01

    Resistive switching (RS) devices are commonly believed as a promising candidate for next generation nonvolatile resistance random access memory. Here, polymethylmethacrylate (PMMA) interlayer was introduced at the heterointerface of p-CuSCN hollow nanopyramid arrays and n-ZnO nanorod arrays, resulting in a typical bipolar RS behavior. We propose the mechanism of nanostructure trap-induced space charge polarization modulated by PMMA interlayer. At low reverse bias, PMMA insulator can block charges through the heterointerface, and and trapped states are respectively created on both sides of PMMA, resulting in a high resistance state (HRS) due to wider depletion region. At high reverse bias, however, electrons and holes can cross PMMA interlayer by Fowler-Nordeim tunneling due to a massive tilt of energy band, and then inject into the traps of ZnO and CuSCN, respectively. and trapped states are created, resulting in the formation of degenerate semiconductors on both sides of PMMA. Therefore, quantum tunneling and space charge polarization lead to a low resistance state (LRS). At relatively high forward bias, subsequently, the trapped states of and are recreated due to the opposite injection of charges, resulting in a recovery of HRS. The introduction of insulating interlayer at heterointerface, point a way to develop next-generation nonvolatile memories.

  20. Polarization-dependent infrared reflectivity study of Sr2.5Ca11.5Cu24O41 under pressure: Charge dynamics, charge distribution, and anisotropy

    DOE PAGES

    Frank, S.; Huber, A.; Ammerahl, U.; ...

    2014-12-18

    We present a polarization-dependent infrared reflectivity study of the spin-ladder compound Sr₂̣₅Ca₁₁̣₅Cu₂₄O₄₁ under pressure. The optical response is strongly anisotropic, with the highest reflectivity along the ladders/chains (E∥c) revealing a metallic character. For the polarization direction perpendicular to the ladder plane, an insulating behavior is observed. With increasing pressure the optical conductivity for E∥c shows a strong increase, which is most pronounced below 2000cm⁻¹. According to the spectral weight analysis of the E∥c optical conductivity the hole concentration in the ladders increases with increasing pressure and tends to saturate at high pressure. At ~7.5 GPa the number of holes permore » Cu atom in the ladders has increased by Δδ=0.09(±0.01), and the Cu valence in the ladders has reached the value +2.33. Thus, the optical data suggest that Sr₂̣₅Ca₁₁̣₅Cu₂₄O₄₁ remains electronically highly anisotropic up to high pressure, also at low temperatures.« less

  1. PMMA interlayer-modulated memory effects by space charge polarization in resistive switching based on CuSCN-nanopyramids/ZnO-nanorods p-n heterojunction

    PubMed Central

    Cheng, Baochang; Zhao, Jie; Xiao, Li; Cai, Qiangsheng; Guo, Rui; Xiao, Yanhe; Lei, Shuijin

    2015-01-01

    Resistive switching (RS) devices are commonly believed as a promising candidate for next generation nonvolatile resistance random access memory. Here, polymethylmethacrylate (PMMA) interlayer was introduced at the heterointerface of p-CuSCN hollow nanopyramid arrays and n-ZnO nanorod arrays, resulting in a typical bipolar RS behavior. We propose the mechanism of nanostructure trap-induced space charge polarization modulated by PMMA interlayer. At low reverse bias, PMMA insulator can block charges through the heterointerface, and and trapped states are respectively created on both sides of PMMA, resulting in a high resistance state (HRS) due to wider depletion region. At high reverse bias, however, electrons and holes can cross PMMA interlayer by Fowler-Nordeim tunneling due to a massive tilt of energy band, and then inject into the traps of ZnO and CuSCN, respectively. and trapped states are created, resulting in the formation of degenerate semiconductors on both sides of PMMA. Therefore, quantum tunneling and space charge polarization lead to a low resistance state (LRS). At relatively high forward bias, subsequently, the trapped states of and are recreated due to the opposite injection of charges, resulting in a recovery of HRS. The introduction of insulating interlayer at heterointerface, point a way to develop next-generation nonvolatile memories. PMID:26648249

  2. Energy-Specific Equation-of-Motion Coupled-Cluster Methods for High-Energy Excited States: Application to K-edge X-ray Absorption Spectroscopy.

    PubMed

    Peng, Bo; Lestrange, Patrick J; Goings, Joshua J; Caricato, Marco; Li, Xiaosong

    2015-09-08

    Single-reference techniques based on coupled-cluster (CC) theory, in the forms of linear response (LR) or equation of motion (EOM), are highly accurate and widely used approaches for modeling valence absorption spectra. Unfortunately, these equations with singles and doubles (LR-CCSD and EOM-CCSD) scale as O(N⁶), which may be prohibitively expensive for the study of high-energy excited states using a conventional eigensolver. In this paper, we present an energy-specific non-Hermitian eigensolver that is able to obtain high-energy excited states (e.g., XAS K-edge spectrum) at low computational cost. In addition, we also introduce an improved trial vector for iteratively solving the EOM-CCSD equation with a focus on high-energy eigenstates. The energy-specific EOM-CCSD approach and its low-scaling alternatives are applied to calculations of carbon, nitrogen, oxygen, and sulfur K-edge excitations. The results are compared to other implementations of CCSD for excited states, energy-specific linear response time-dependent density functional theory (TDDFT), and experimental results with multiple statistical metrics are presented and evaluated.

  3. Effect of x-ray energy dispersion in digital subtraction imaging at the iodine K-edge--A Monte Carlo study

    SciTech Connect

    Prino, F.; Ceballos, C.; Cabal, A.; Sarnelli, A.; Gambaccini, M.; Ramello, L.

    2008-01-15

    The effect of the energy dispersion of a quasi-monochromatic x-ray beam on the performance of a dual-energy x-ray imaging system is studied by means of Monte Carlo simulations using MCNPX (Monte Carlo N-Particle eXtended) version 2.6.0. In particular, the case of subtraction imaging at the iodine K-edge, suitable for angiographic imaging application, is investigated. The average energies of the two beams bracketing the iodine K-edge are set to the values of 31.2 and 35.6 keV corresponding to the ones obtained with a compact source based on a conventional x-ray tube and a mosaic crystal monochromator. The energy dispersion of the two beams is varied between 0 and 10 keV of full width at half-maximum (FWHM). The signal and signal-to-noise ratio produced in the simulated images by iodine-filled cavities (simulating patient vessels) drilled in a PMMA phantom are studied as a function of the x-ray energy dispersion. The obtained results show that, for the considered energy separation of 4.4 keV, no dramatic deterioration of the image quality is observed with increasing x-ray energy dispersion up to a FWHM of about 2.35 keV. The case of different beam energies is also investigated by means of fast simulations of the phantom absorption.

  4. Local disorder investigation in NiS(2-x)Se(x) using Raman and Ni K-edge x-ray absorption spectroscopies.

    PubMed

    Marini, C; Joseph, B; Caramazza, S; Capitani, F; Bendele, M; Mitrano, M; Chermisi, D; Mangialardo, S; Pal, B; Goyal, M; Iadecola, A; Mathon, O; Pascarelli, S; Sarma, D D; Postorino, P

    2014-11-12

    We report on Raman and Ni K-edge x-ray absorption investigations of a NiS(2-x)Se(x) (with x = 0.00, 0.50/0.55, 0.60, and 1.20) pyrite family. The Ni K-edge absorption edge shows a systematic shift going from an insulating phase (x = 0.00 and 0.50) to a metallic phase (x = 0.60 and 1.20). The near-edge absorption features show a clear evolution with Se doping. The extended x-ray absorption fine structure data reveal the evolution of the local structure with Se doping which mainly governs the local disorder. We also describe the decomposition of the NiS(2-x)Se(x) Raman spectra and investigate the weights of various phonon modes using Gaussian and Lorentzian profiles. The effectiveness of the fitting models in describing the data is evaluated by means of Bayes factor estimation. The Raman analysis clearly demonstrates the disorder effects due to Se alloying in describing the phonon spectra of NiS(2-x)Se(x) pyrites.

  5. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice

    PubMed Central

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-01-01

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures. PMID:24253589

  6. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice.

    PubMed

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-11-20

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures.

  7. Probing the K-edge of a laser heated aluminum plasma using X-rays from betatron oscillations in a laser wakefield accelerator with femtosecond resolution

    NASA Astrophysics Data System (ADS)

    Behm, Keegan; Hussein, Amina; Zhao, Tony; Hill, Edward; Maksimchuk, Anatoly; Nees, John; Yanovsky, Victor; Mangles, Stuart; Krushelnick, Karl; Thomas, Alexander; CenterUltrafast Optical Science Team; Plasmas Group Team

    2016-10-01

    Presented here are data from a two-beam pump-probe experiment. We used synchrotron-like X-rays created by betatron oscillations to probe a thin metal foil that is pumped by the secondary laser beam. The Hercules Ti:Sapphire laser facility was operated with a pulse duration of 34 fs and a power of 80 TW split. A 75-25 beam splitter was used to drive a laser wakefield accelerator and heat the secondary target. We observed opacity changes around the K-edge of thin aluminum foil as it was heated by an ultrafast pump laser. To understand how the opacity is changing with heating and expansion of the plasma, the delay between the two laser paths was adjusted on a femtosecond time scale from 50 to 400 fs. Experimental data for aluminum shows variation in opacity around the K-edge with changes in the probe delay. The transmitted synchrotron-like spectrum was measured using single photon counting on an X-ray CCD camera and was available on a shot-by-shot basis. The success of this work demonstrates a practical application for X-rays produced from betatron oscillations in a wakefield accelerator. U.S. Department of Energy and the National Nuclear Security Administration.

  8. X-ray Absorption Spectroscopy at the Sulfur K-Edge: A New Tool to Investigate the Biochemical Mechanisms of Neurodegeneration

    PubMed Central

    2012-01-01

    Sulfur containing molecules such as thiols, disulfides, sulfoxides, sulfonic acids, and sulfates may contribute to neurodegenerative processes. However, previous study in this field has been limited by the lack of in situ analytical techniques. This limitation may now be largely overcome following the development of synchrotron radiation X-ray absorption spectroscopy at the sulfur K-edge, which has been validated as a novel tool to investigate and image the speciation of sulfur in situ. In this investigation, we build the foundation required for future application of this technique to study and image the speciation of sulfur in situ within brain tissue. This study has determined the effect of sample preparation and fixation methods on the speciation of sulfur in thin sections of rat brain tissue, determined the speciation of sulfur within specific brain regions (brain stem and cerebellum), and identified sulfur specific markers of peroxidative stress following metal catalyzed reactive oxygen species production. X-ray absorption spectroscopy at the sulfur K-edge is now poised for an exciting new range of applications to study thiol redox, methionine oxidation, and the role of taurine and sulfatides during neurodegeneration. PMID:22860187

  9. Femtosecond probing around the K-edge of a laser heated plasma using X-rays from betatron oscillations in a laser wakefield accelerator

    NASA Astrophysics Data System (ADS)

    Behm, Keegan; Zhao, Tony; Maksimchuk, Anatoly; Yanovsky, Victor; Nees, John; Mangles, Stuart; Krushelnick, Karl; Thomas, Alexander; CenterUltrafast Optical Science Team; Plasmas Group Team

    2015-11-01

    Presented here are data from a two-beam pump-probe experiment. We used synchrotron-like X-rays created by betatron oscillations to probe a thin metal foil that is pumped by the secondary laser beam. The Hercules Ti:Sapph laser facility was operated with a pulse duration of 34 fs and a power of 65 TW split to drive a laser wakefield accelerator and heat the secondary target. We observed opacity changes around the K-edge of thin foils as they were heated by an ultrafast pump laser. To understand how the opacity is changing with heating and expansion of the plasma, the delay between the two laser paths was adjusted on a fs and ps time scale. Experimental data for polyvinylidene chloride (PVDC) and aluminum show variations in opacity around the Cl and Al K-edges with changes in the probe delay. The transmitted synchrotron-like spectrum was measured using single photon counting on an X-ray CCD camera and was available on a shot-by-shot basis. The success of this work demonstrates a practical application for X-rays produced from betatron oscillations in a wakefield accelerator. The compact size of these ``table-top'' accelerators and the ultrashort nature of the generated X-ray pulses allows pump-probe experiments that can probe events that occur on the femtosecond time scale.

  10. Nitrogen K-edge X-ray absorption near edge structure (XANES) spectra of purine-containing nucleotides in aqueous solution

    SciTech Connect

    Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    2014-08-07

    The N K-edge X-ray absorption near edge structure (XANES) spectra of the purine-containing nucleotide, guanosine 5{sup ′}-monophosphate (GMP), in aqueous solution are measured under various pH conditions. The spectra show characteristic peaks, which originate from resonant excitations of N 1s electrons to π* orbitals inside the guanine moiety of GMP. The relative intensities of these peaks depend on the pH values of the solution. The pH dependence is explained by the core-level shift of N atoms at specific sites caused by protonation and deprotonation. The experimental spectra are compared with theoretical spectra calculated by using density functional theory for GMP and the other purine-containing nucleotides, adenosine 5{sup ′}-monophosphate, and adenosine 5{sup ′}-triphosphate. The N K-edge XANES spectra for all of these nucleotides are classified by the numbers of N atoms with particular chemical bonding characteristics in the purine moiety.

  11. Structure of shock compressed model basaltic glass: Insights from O K-edge X-ray Raman scattering and high-resolution 27Al NMR spectroscopy

    SciTech Connect

    Lee, Sung Keun; Park, Sun Young; Kim, Hyo-Im; Tschauner, Oliver; Asimow, Paul; Bai, Ligang; Xiao, Yuming; Chow, Paul

    2012-05-29

    The detailed atomic structures of shock compressed basaltic glasses are not well understood. Here, we explore the structures of shock compressed silicate glass with a diopside-anorthite eutectic composition (Di{sub 64}An{sub 36}), a common Fe-free model basaltic composition, using oxygen K-edge X-ray Raman scattering and high-resolution {sup 27}Al solid-state NMR spectroscopy and report previously unknown details of shock-induced changes in the atomic configurations. A topologically driven densification of the Di{sub 64}An{sub 36} glass is indicated by the increase in oxygen K-edge energy for the glass upon shock compression. The first experimental evidence of the increase in the fraction of highly coordinated Al in shock compressed glass is found in the {sup 27}Al NMR spectra. This unambiguous evidence of shock-induced changes in Al coordination environments provides atomistic insights into shock compression in basaltic glasses and allows us to microscopically constrain the magnitude of impact events or relevant processes involving natural basalts on Earth and planetary surfaces.

  12. Proximity effect between a superconductor and a partially spin-polarized ferromagnet: Case study of the Pb/Cu /Co 2Cr1 -xFexAl trilayer

    NASA Astrophysics Data System (ADS)

    Kamashev, A. A.; Leksin, P. V.; Schumann, J.; Kataev, V.; Thomas, J.; Gemming, T.; Büchner, B.; Garifullin, I. A.

    2017-07-01

    We have studied the proximity effect in thin-film heterostructures composed of the superconducting Pb (S) and of the ferromagnetic Heusler alloy Co2Cr1 -xFexAl (F) with different degrees of the spin polarization of the conduction band. A thin Cu interlayer is inserted in between the S and F layers to ensure the stability of the S/F interface. The analysis of the dependences of the superconducting transition temperatures in such heterostructures on the thickness of the Pb or of the Heusler alloy using the theory by Fominov et al. [Ya. V. Fominov, N. M. Chtchelkatchev, and A. A. Golubov, Phys. Rev. B 66, 014507 (2002), 10.1103/PhysRevB.66.014507] shows that, with increasing the exchange splitting of the conduction band of a ferromagnet and, respectively, of the degree of the spin polarization, the probability of transmission of the superconducting Cooper pairs through the S/F interface decreases. We conclude that the spin imbalance plays a key role in the processes taking place at the interface between a superconductor and a ferromagnet with spin-polarized conduction electrons.

  13. A Monte Carlo simulation study of an improved K-edge log-subtraction X-ray imaging using a photon counting CdTe detector

    NASA Astrophysics Data System (ADS)

    Lee, Youngjin; Lee, Amy Candy; Kim, Hee-Joung

    2016-09-01

    Recently, significant effort has been spent on the development of photons counting detector (PCD) based on a CdTe for applications in X-ray imaging system. The motivation of developing PCDs is higher image quality. Especially, the K-edge subtraction (KES) imaging technique using a PCD is able to improve image quality and useful for increasing the contrast resolution of a target material by utilizing contrast agent. Based on above-mentioned technique, we presented an idea for an improved K-edge log-subtraction (KELS) imaging technique. The KELS imaging technique based on the PCDs can be realized by using different subtraction energy width of the energy window. In this study, the effects of the KELS imaging technique and subtraction energy width of the energy window was investigated with respect to the contrast, standard deviation, and CNR with a Monte Carlo simulation. We simulated the PCD X-ray imaging system based on a CdTe and polymethylmethacrylate (PMMA) phantom which consists of the various iodine contrast agents. To acquired KELS images, images of the phantom using above and below the iodine contrast agent K-edge absorption energy (33.2 keV) have been acquired at different energy range. According to the results, the contrast and standard deviation were decreased, when subtraction energy width of the energy window is increased. Also, the CNR using a KELS imaging technique is higher than that of the images acquired by using whole energy range. Especially, the maximum differences of CNR between whole energy range and KELS images using a 1, 2, and 3 mm diameter iodine contrast agent were acquired 11.33, 8.73, and 8.29 times, respectively. Additionally, the optimum subtraction energy width of the energy window can be acquired at 5, 4, and 3 keV for the 1, 2, and 3 mm diameter iodine contrast agent, respectively. In conclusion, we successfully established an improved KELS imaging technique and optimized subtraction energy width of the energy window, and based on

  14. Pressure Induced Phase Transition in PbTiO3 Studied by X-ray Absorption Spectroscopy at the Ti K edge

    SciTech Connect

    Dhaussy, A. C.; Marinel, S.; Veres, A.; Jaouen, N.; Itie, J. P.; Rogalev, A.

    2007-01-19

    The Ti-K edge X-ray Absorption Near Edge Structure (XANES) for CaTiO3 and PbTiO3 have been measured under high pressure in a diamond anvil cell at room temperature. Despite the huge absorption from the diamond cell and the sample high quality XANES allows us to observe that in CaTiO3 no change occurs when applying pressure, at the opposite of PbTiO3 in which the pre-edge features vary strongly. It allows studying the phase transition from ferroelectric to paraelectric phase in PbTiO3 from the local point of view. Under pressure the change in intensity of the pre-edge indicates qualitatively that the Ti atom is moving toward the centre of the oxygen octahedron along the c-axis.

  15. The Be K-edge in beryllium oxide and chalcogenides: soft x-ray absorption spectra from first-principles theory and experiment.

    PubMed

    Olovsson, W; Weinhardt, L; Fuchs, O; Tanaka, I; Puschnig, P; Umbach, E; Heske, C; Draxl, C

    2013-08-07

    We have carried out a theoretical and experimental investigation of the beryllium K-edge soft x-ray absorption fine structure of beryllium compounds in the oxygen group, considering BeO, BeS, BeSe, and BeTe. Theoretical spectra are obtained ab initio, through many-body perturbation theory, by solving the Bethe-Salpeter equation (BSE), and by supercell calculations using the core-hole approximation. All calculations are performed with the full-potential linearized augmented plane-wave method. It is found that the two different theoretical approaches produce a similar fine structure, in good agreement with the experimental data. Using the BSE results, we interpret the spectra, distinguishing between bound core-excitons and higher energy excitations.

  16. Li K-edge X-ray absorption near edge structure spectra for a library of lithium compounds applied in lithium batteries

    NASA Astrophysics Data System (ADS)

    Wang, Dongniu; Zuin, Lucia

    2017-01-01

    Lithium ion batteries (LIB) have achieved great success as energy supply systems in portable devices and in electrical vehicles. Identifying the local chemical structures of elemental lithium in lithium compounds is beneficial for improving understanding of battery components and performance. Herein, a library of Li K-edge X-ray absorption near edge structure (XANES) of lithium compounds relevant to Li-ion batteries is reported. Materials described include lithium metals (anode), Li-containing cathodes, electrolytes and solid electrolyte interphase (SEI). The results illustrate the characteristic spectral features stemming from the various electronic structures and chemical environment of lithium atoms for each and every possible battery component. XANES spectra of Sn based anode after discharging reveal the appearance of Li2CO3 on electrode surface. X-ray damage on sensitive lithium species is also assessed; the results reveal that more attention should be paid to irradiation effects to conduct XANES measurements for battery materials properly.

  17. Dispersive x-ray absorption studies at the Fe K-edge on the iron chalcogenide superconductor FeSe under pressure.

    PubMed

    Bendele, M; Marini, C; Joseph, B; Simonelli, L; Dore, P; Pascarelli, S; Chikovani, M; Pomjakushina, E; Conder, K; Saini, N L; Postorino, P

    2013-10-23

    The local structure and the electronic properties of FeSe under hydrostatic pressure were studied by means of dispersive x-ray absorption measurements at the Fe K-edge. The pressure dependence of the x-ray absorption near edge structure features seems to follow the behavior of the superconducting transition temperature Tc. The local structure, that has an important impact on the superconducting properties, appears to fall into two regimes: the pressure dependence of the Fe-Fe bond distance shows a clear change in the compressibility at p ∼ 5 GPa; in contrast, the Fe-Se bond distance decreases continuously with increasing pressure with a lower compressibility than the Fe-Fe bond. The results suggest that the pressure dependent changes in Tc of FeSe are closely related to the changes in local structure.

  18. Ag K-edge EXAFS analysis of DNA-templated fluorescent silver nanoclusters: insight into the structural origins of emission tuning by DNA sequence variations.

    PubMed

    Neidig, Michael L; Sharma, Jaswinder; Yeh, Hsin-Chih; Martinez, Jennifer S; Conradson, Steven D; Shreve, Andrew P

    2011-08-10

    DNA-templated silver nanoclusters are promising biological fluorescence probes due to their useful fluorescence properties, including tunability of emission wavelength through DNA template sequence variations. Ag K-edge EXAFS analysis of DNA-templated silver nanoclusters has been used to obtain insight into silver nanocluster bonding, size, and structural correlations to fluorescence. The results indicate the presence of small silver nanoclusters (<30 silver atoms) containing Ag-Ag bonds and Ag-N/O ligations to DNA. The DNA sequence used leads to differences in silver-DNA ligation as well as silver nanocluster size. The results support a model in which cooperative effects of both Ag-DNA ligation and variations in cluster size lead to the tuning of the fluorescence emission of DNA-templated silver nanoclusters.

  19. X-ray absorption spectroscopy by full-field X-ray microscopy of a thin graphite flake: Imaging and electronic structure via the carbon K-edge

    PubMed Central

    Hitchock, Adam P; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Ewels, Chris P; Guttmann, Peter

    2012-01-01

    Summary We demonstrate that near-edge X-ray-absorption fine-structure spectra combined with full-field transmission X-ray microscopy can be used to study the electronic structure of graphite flakes consisting of a few graphene layers. The flake was produced by exfoliation using sodium cholate and then isolated by means of density-gradient ultracentrifugation. An image sequence around the carbon K-edge, analyzed by using reference spectra for the in-plane and out-of-plane regions of the sample, is used to map and spectrally characterize the flat and folded regions of the flake. Additional spectral features in both π and σ regions are observed, which may be related to the presence of topological defects. Doping by metal impurities that were present in the original exfoliated graphite is indicated by the presence of a pre-edge signal at 284.2 eV. PMID:23016137

  20. Morphology-dependent luminescence from ZnO nanostructures - An X-ray excited optical luminescence study at the Zn K-edge

    SciTech Connect

    Lobacheva, Olga; Murphy, Michael W; Ko, Jun Young Peter; Sham, Tsun-Kong

    2009-08-28

    ZnO nanostructures have been synthesized by thermal evaporation on Si substrates. It is found that the morphologies of the nanostructures are governed by growth conditions such as temperature, carrier-gas flow rate, and the nature of the substrate (with and without a catalyst). We report X-ray excited optical luminescence from ZnO nanostructures of distinctly different morphologies in the energy and time domain using excitation photon energies across the Zn K-edge. X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) study has clearly shown the morphology dependence of the ZnO optical properties. A correlation of luminescence with morphology, size, and crystallinity emerges.

  1. Pyrimidine and halogenated pyrimidines near edge x-ray absorption fine structure spectra at C and N K-edges: experiment and theory

    SciTech Connect

    Bolognesi, P.; O'Keeffe, P.; Ovcharenko, Y.; Coreno, M.; Avaldi, L.; Feyer, V.; Plekan, O.; Prince, K. C.; Zhang, W.; Carravetta, V.

    2010-07-21

    The inner shell excitation of pyrimidine and some halogenated pyrimidines near the C and N K-edges has been investigated experimentally by near edge x-ray absorption fine structure spectroscopy and theoretically by density functional theory calculations. The selected targets, 5-Br-pyrimidine, 2-Br-pyrimidine, 2-Cl-pyrimidine, and 5-Br-2-Cl-pyrimidine, allow the effects of the functionalization of the pyrimidine ring to be studied either as a function of different halogen atoms bound to the same molecular site or as a function of the same halogen atom bound to different molecular sites. The results show that the individual characteristics of the different spectra of the substituted pyrimidines can be rationalized in terms of variations in electronic and geometrical structures of the molecule depending on the localization and the electronegativity of the substituent.

  2. Pyrimidine and halogenated pyrimidines near edge x-ray absorption fine structure spectra at C and N K-edges: experiment and theory.

    PubMed

    Bolognesi, P; O'Keeffe, P; Ovcharenko, Y; Coreno, M; Avaldi, L; Feyer, V; Plekan, O; Prince, K C; Zhang, W; Carravetta, V

    2010-07-21

    The inner shell excitation of pyrimidine and some halogenated pyrimidines near the C and N K-edges has been investigated experimentally by near edge x-ray absorption fine structure spectroscopy and theoretically by density functional theory calculations. The selected targets, 5-Br-pyrimidine, 2-Br-pyrimidine, 2-Cl-pyrimidine, and 5-Br-2-Cl-pyrimidine, allow the effects of the functionalization of the pyrimidine ring to be studied either as a function of different halogen atoms bound to the same molecular site or as a function of the same halogen atom bound to different molecular sites. The results show that the individual characteristics of the different spectra of the substituted pyrimidines can be rationalized in terms of variations in electronic and geometrical structures of the molecule depending on the localization and the electronegativity of the substituent.

  3. X-ray natural linear dichroism of graphitic materials across the carbon K-edge: Correction for perturbing high-order harmonics

    NASA Astrophysics Data System (ADS)

    Jansing, C.; Mertins, H. C.; Gaupp, A.; Sokolov, A.; Gilbert, M. C.; Wahab, H.; Timmers, H.

    2016-05-01

    Reflectivity measurements on graphitic materials such as graphene at energies across the carbon K-edge are frustrated by significant intensity loss due to adventitious carbon on beamline mirrors. Such intensity reduction enhances effects due to perturbing high-order harmonics in the beam. These effects distort the actual structure of the reflectance curve. In order to overcome this limitation, a correction technique has been developed and demonstrated first with measurements for highly ordered pyrolytic graphite. The same approach may be applied to other graphitic materials such as graphene and it may be used with other synchrotron beamlines. The fraction of high-order harmonics was determined by passing the incident beam through a 87 nm thin silicon nitride absorber that can be well modeled. Using the corrected measurements the x-ray natural linear dichroism of the sample has been determined.

  4. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; Sparks, Dennis E.; Shafer, Wilson D.; Khalid, Syed; Xiao, Qunfeng; Hu, Yongfeng; Davis, Burtron H.

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts is explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.

  5. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    DOE PAGES

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; ...

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts ismore » explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.« less

  6. Tetrahalide Complexes of the [U(NR)(2)]2+ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy

    SciTech Connect

    Spencer, Liam P.; Yang, Ping; Minasian, Stefan G.; Jilek, Robert E.; Batista, Enrique R.; Boland, Kevin S.; Boncella, James M.; Conradson, S. D.; Clark, David L.; Hayton, Trevor W.; Kozimor, Stosh A.; Martin, Richard L.; MacInnes, Molly M.; Olson, Angela C.; Scott, Brian L.; Shuh, D. K.; Wilkerson, Marianne P.

    2013-02-13

    Synthetic routes to salts containing uranium bisimido tetrahalide anions [U(NR)(2)X-4](2-) (X = Cl-, Br-) and non-coordinating NEt4+ and PPh4+ countercations are reported. In general, these compounds can be prepared from U(NR)(2)I-2(THF)(x) (x = 2 and R = 'Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl-, the [U(NMe)(2)](2 +) cation also reacts with Br- to form stable [NEt4](2)[U(NMe)(2)Br-4] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO2](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh4](2)[U((NBu)-Bu-t)(2)Cl-4] and [PPh4](2)[UO2Cl4]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

  7. Insights into molecular chemistry of Chiapas amber using infrared-light microscopy, PIXE/RBS, and sulfur K-edge XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Riquelme, Francisco; Northrup, Paul; Ruvalcaba-Sil, José Luis; Stojanoff, Vivian; Peter Siddons, D.; Alvarado-Ortega, Jesús

    2014-07-01

    Chiapas amber is a natural occurring fossil resin structurally composed of long macromolecule chains with semicrystalline phases associated with both fossil and polymerization process. The most conspicuous characteristic of this fossil polymer is that it preserves ancient organic inclusions. In the present work, PIXE/RBS spectrometry (particle-induced X-ray emission/Rutherford backscattering) were combined with complementary K-edge XANES spectroscopy (X-ray absorption near-edge structure) to identify the amount of sulfur in Chiapas amber. Initially, the amber samples were examined using infrared reflected photomicrography. Amber is transparent to infrared light and so embedded plants and animals are easily visible, showing them in extraordinary detail, as if they were immersed in a water-like solution. The PIXE/RBS data show that the proportion of sulfur in amber is significantly higher than that found in recently formed resins, consistent with the biogeochemical process that transforms the resin into amber during long-term burial in geological deposits. The sulfur K-edge XANES spectra from amber confirm the sulfur abundance and reveal sulfur species in the reduced and intermediate oxidation states in amber. Almost no oxidized sulfur was found, whereas the recent resins show mostly oxidized sulfur fractions. This indicates that labile oxidized sulfur decays during fossilization and resin maturation must occur under conditions of oxygen depletion. The implications of the presence of sulfur in amber for organic preservation is also discussed here. Sulfur compounds work as a polymer additive that promotes intense resin solidification. This restricts the early oxidant-specific biodegradation of the embedded biomatter and, over geological time, provides greater stability against chemical changes.

  8. Sulfur K-Edge XAS and DFT Calculations on NitrileHydratase: Geometric and Electronic Structure of the Non-heme Iron Active Site

    SciTech Connect

    Dey, Abhishek; Chow, Marina; Taniguchi, Kayoko; Lugo-Mas, Priscilla; Davin, Steven; Maeda, Mizuo; Kovacs, Julie A.; Odaka, Masafumi; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; /SLAC, SSRL

    2006-09-28

    The geometric and electronic structure of the active site of the non-heme iron enzyme nitrile hydratase (NHase) is studied using sulfur K-edge XAS and DFT calculations. Using thiolate (RS{sup -})-, sulfenate (RSO{sup -})-, and sulfinate (RSO{sub 2}{sup -})-ligated model complexes to provide benchmark spectral parameters, the results show that the S K-edge XAS is sensitive to the oxidation state of S-containing ligands and that the spectrum of the RSO- species changes upon protonation as the S-O bond is elongated (by {approx}0.1 {angstrom}). These signature features are used to identify the three cysteine residues coordinated to the low-spin Fe{sup III} in the active site of NHase as CysS{sup -}, CysSOH, and CysSO{sub 2}{sup -} both in the NO-bound inactive form and in the photolyzed active form. These results are correlated to geometry-optimized DFT calculations. The pre-edge region of the X-ray absorption spectrum is sensitive to the Z{sub eff} of the Fe and reveals that the Fe in [FeNO]{sup 6} NHase species has a Z{sub eff} very similar to that of its photolyzed Fe{sup III} counterpart. DFT calculations reveal that this results from the strong {pi} back-bonding into the {pi}* antibonding orbital of NO, which shifts significant charge from the formally t{sub 2}{sup 6} low-spin metal to the coordinated NO.

  9. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; Sparks, Dennis E.; Shafer, Wilson D.; Khalid, Syed; Xiao, Qunfeng; Hu, Yongfeng; Davis, Burtron H.

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts is explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.

  10. Ligand K-edge X-ray absorption spectroscopy and DFT calculations on [Fe3S4]0,+ clusters: delocalization, redox, and effect of the protein environment.

    PubMed

    Dey, Abhishek; Glaser, Thorsten; Moura, Jose J-G; Holm, Richard H; Hedman, Britt; Hodgson, Keith O; Solomon, Edward I

    2004-12-29

    Ligand K-edge XAS of an [Fe3S4]0 model complex is reported. The pre-edge can be resolved into contributions from the mu(2)S(sulfide), mu(3)S(sulfide), and S(thiolate) ligands. The average ligand-metal bond covalencies obtained from these pre-edges are further distributed between Fe(3+) and Fe(2.5+) components using DFT calculations. The bridging ligand covalency in the [Fe2S2]+ subsite of the [Fe3S4]0 cluster is found to be significantly lower than its value in a reduced [Fe2S2] cluster (38% vs 61%, respectively). This lowered bridging ligand covalency reduces the superexchange coupling parameter J relative to its value in a reduced [Fe2S2]+ site (-146 cm(-1) vs -360 cm(-1), respectively). This decrease in J, along with estimates of the double exchange parameter B and vibronic coupling parameter lambda2/k(-), leads to an S = 2 delocalized ground state in the [Fe3S4]0 cluster. The S K-edge XAS of the protein ferredoxin II (Fd II) from the D. gigas active site shows a decrease in covalency compared to the model complex, in the same oxidation state, which correlates with the number of H-bonding interactions to specific sulfur ligands present in the active site. The changes in ligand-metal bond covalencies upon redox compared with DFT calculations indicate that the redox reaction involves a two-electron change (one-electron ionization plus a spin change of a second electron) with significant electronic relaxation. The presence of the redox inactive Fe(3+) center is found to decrease the barrier of the redox process in the [Fe3S4] cluster due to its strong antiferromagnetic coupling with the redox active Fe2S2 subsite.

  11. Photoelectrical properties of surfactant-free kesterite Cu2ZnSnSe4 hydrophilic nanocrystal ink and the stability in polar solvents

    NASA Astrophysics Data System (ADS)

    Kush, Priya; Deka, Sasanka

    2014-09-01

    Colloidal semiconductor nanocrystals (NCs) with surfactant/ligand capping have easy solubility in nonpolar organic solvents but have hindered charge transport, diminishing the electrical efficiency of the material. In the present article, synthesis of bare Cu2ZnSnSe4 NCs of 20-30 nm average diameter with high quality and phase purity has been demonstrated by a simple hydrothermal route, without using any surfactant and hazardous organic solvents. As-synthesized samples can be easily dispersed in polar solvents by electrostatic stabilization and utilized for thin film fabrication. Photovoltaic cell made from the fine high-quality bare Cu2ZnSnSe4 NCs shows accountable fourfold photoresponse electrical conductivity upon illumination (AM 1.5) attributed to ligand-free nature of the synthesized nanoparticles. The dispersibility of the material in a variety of solvents providing electrostatic stabilization has been explored for application purpose which is useful for the material utilization without any pre- or post-deposition treatment for low-cost photovoltaic applications.

  12. Crystal-field polarization and the insulating gap in FeO, CoO, NiO, and La sub 2 CuO sub 4 (US). [FeO; CoO; NiO; La d2CuO d ix

    SciTech Connect

    Norman, M.R. )

    1991-07-15

    An orbital polarization correction to local spin density (LSD) theory is developed in a crystal field basis, and applied to FeO, CoO, NiO, and La{sub 2}CuO{sub 4}. The result is a substantial enhancement of the LSD band gap for NiO, and the creation of an insulating ground state for FeO, CoO, and La{sub 2}CuO{sub 4}.

  13. Angle-resolved photoemission with circularly polarized light in the nodal mirror plane of underdoped Bi2Sr2CaCu2O8+δ superconductor

    NASA Astrophysics Data System (ADS)

    He, Junfeng; Mion, Thomas R.; Gao, Shang; Myers, Gavin T.; Arita, Masashi; Shimada, Kenya; Gu, G. D.; He, Rui-Hua

    2016-10-01

    Unraveling the nature of pseudogap phase in high-temperature superconductors holds the key to understanding their superconducting mechanisms and potentially broadening their applications via enhancement of their superconducting transition temperatures. Angle-resolved photoemission spectroscopy (ARPES) experiments using circularly polarized light have been proposed to detect possible symmetry breaking state in the pseudogap phase of cuprates. The presence (absence) of an electronic order which breaks mirror symmetry of the crystal would in principle induce a finite (zero) circular dichroism in photoemission. Different orders breaking reflection symmetries about different mirror planes can also be distinguished by the momentum dependence of the measured circular dichroism. Here, we report ARPES experiment on an underdoped Bi2Sr2CaCu2O8+δ (Bi2212) superconductor in the Γ (0,0)-Y (π,π) nodal mirror plane using circularly polarized light. No circular dichroism is observed on the level of ˜2% at low temperature, which places a clear constraint on the forms of possible symmetry breaking orders in this sample. Meanwhile, we find that the geometric dichroism remains substantial very close to its perfect extinction such that a very small sample angular offset is sufficient to induce a sizeable dichroic signal. It highlights the importance to establish a perfect extinction of geometric dichroism as a prerequisite for the identification of any intrinsic circular dichroism in this material.

  14. Micro-Structural Properties of YBa2Cu3O(7-x)/ZnO Nanorods on SrTiO3.

    PubMed

    Jin, Zhenlan; Park, Changin; Song, Kyu Jeong; Kang, Sukil; Ko, Kyeong-Eun; Park, Chan; Ko, Rock Kil; Han, S W

    2015-01-01

    We examined the local structural and the interfacial properties of YBa2Cu3O(7-x) (YBCO)/ZnO nanorods on SrTiO3 (STO) substrates using various measurements. Vertically aligned ZnO nanorods were synthesized on STO substrates using a catalyst-free metal-organic chemical vapor deposition. YBCO films were deposited ex-situ on the ZnO nanorods/STO templates using a DC magnetron sputtering deposition. X-ray diffraction revealed that the YBCO films were crystallized along their c-axes on the ZnO nanorods/STO templates. Transmission electron microscopy measurements demonstrated that YBCO filled the space between ZnO nanorods and that both interfaces of YBCO/ZnO nanorods and ZnO nanorods/STO were quite clean with no disorder. Polarization-dependent extended X-ray absorption fine structure measurements at the Cu K edge showed extra disorder in the CuO2 planes of YBCO/ZnO nanorods/STO, compared with that of YBCO/STO. The superconductivity transition temperature (T(c)) of YBCO/ZnO nanorods/STO was approximately 50 K whereas that of YBCO/STO was 93 K. The decrease of T(c) of YBCO/ZnO nanorods/STO was ascribed to the structural disorder of CuO2 planes as well as grain boundaries in the YBCO films.

  15. Induction of DNA strand breaks, base lesions and clustered damage sites in hydrated plasmid DNA films by ultrasoft X rays around the phosphorus K edge.

    PubMed

    Yokoya, Akinari; Cunniffe, Siobhan M T; Watanabe, Ritsuko; Kobayashi, Katsumi; O'Neill, Peter

    2009-09-01

    To characterize the DNA damage induced by K-shell ionization of phosphorus atom in DNA backbone on the level of hydration, the yields of DNA strand breaks and base lesions arising from the interaction of ultrasoft X rays with energies around the phosphorus K edge were determined using dry and fully hydrated pUC18 plasmid DNA samples. Base lesions and bistranded clustered DNA damage sites were revealed by postirradiation treatment with the base excision repair proteins endonuclease III (Nth) and formamidopyrimidine-DNA glycosylase (Fpg). The yield of prompt single-strand breaks (SSBs) with dry DNA irradiated at the phosphorus K resonance energy (2153 eV) is about one-third that below the phosphorus K edge (2147 eV). The yields of prompt double-strand breaks (DSBs) were found to be less dependent on the X-ray energy, with the yields being about two times lower when irradiated at 2153 eV. Heat-labile sites were not produced in detectable amounts. The yields of base lesions were dependent on the energy of the X rays, especially when the DNA was fully hydrated. Bistranded clustered DNA damage sites, revealed enzymatically as additional DSBs, were produced in dry as well as in hydrated DNA with all three energies of X rays. The yields of these enzyme-sensitive sites were also lower when irradiated at the phosphorus K resonance energy. On the other hand, the yields of prompt SSBs and enzyme-sensitive sites for the two off-resonance energies were, larger than those determined previously for gamma radiation. The results indicate that the photoelectric effect caused by X rays and dense ionization and excitation events along the tracks of low-energy secondary electrons are more effective at inducing SSBs and enzyme-sensitive sites. The complex types of damage, prompt and enzymatically induced DSBs, are preferentially induced by phosphorus K resonance at 2153 eV rather than simple SSBs and isolated base lesions, particularly in hydrated conditions. It is concluded that not

  16. Local atomic structure investigation of AlFeCuCrMgx (0.5, 1, 1.7) high entropy alloys: X-ray absorption spectroscopy study

    NASA Astrophysics Data System (ADS)

    Maulik, Ornov; Patra, N.; Bhattacharyya, D.; Jha, S. N.; Kumar, Vinod

    2017-02-01

    The present paper reports local atomic structure investigation of novel AlFeCuCrMgx (x=0.5, 1, 1.7) high entropy alloys (HEAs) produced by mechanical alloying using Fe, Cr and Cu K-edge X-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure (EXAFS) spectroscopy. XANES spectra measured at Fe and Cr K-edges resemble that of the respective pure metal foils, while the spectrum measured at Cu K-edge manifests the presence of some other phases in the as-milled alloys. The radial distribution functions (RDFs) obtained from Fourier transformation of EXAFS spectra support the formation of disordered BCC structure.

  17. Redox Reaction in Silicate Melts Monitored by ``Static'' In-Situ Fe K-Edge XANES up to 1180°C

    NASA Astrophysics Data System (ADS)

    Wilke, Max; Partzsch, Georg M.; Welter, Edmund; Farges, François

    2007-02-01

    A new experimental setup to measure in-situ kinetics of redox reactions in silicate melts is presented. To study the progress of the Fe-redox reaction, the variation of the signal is recorded at an energy, where the difference between the spectra of the oxidized and reduced Fe in the melt is largest ("static XANES"). To control the redox conditions, the gas atmosphere could be changed between to types of gases using computer-controlled valves (N2:H2 and air, respectively). In this way, a number of reduction/oxidation cycles can be monitored in-situ and continuously. Applied at the Fe K-edge in molten silicates, we obtained a set of high quality data, which includes the very first steps of the redox reaction. An Avrami-type equation is used to investigate rate-controlling parameters for the iron oxidation/reduction kinetics for two melts (basaltic and Na trisilicate) for temperatures up to 1180°C.

  18. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    SciTech Connect

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  19. Low-temperature spin-state transition in LaCoO{sub 3} investigated using resonant x-ray absorption at the Co K edge

    SciTech Connect

    Medarde, M.; Pomjakushina, E.; Conder, K.; Dallera, C.; Grioni, M.; Voigt, J.; Podlesnyak, A.; Neisius, Th.; Tjernberg, O.; Barilo, S. N.

    2006-02-01

    LaCoO{sub 3} displays two broad anomalies in the DC magnetic susceptibility {chi}{sup DC}, occurring, respectively, around 50 K and 500 K. We have investigated the first of them within the 10 KK-edge XAS reports, our data show the existence of abrupt changes around 50 K which can be nicely correlated with the anomaly in {chi}{sup DC}. To our knowledge, this is the first time that a clear, quantitative relationship between the temperature dependence of the magnetic susceptibility and that of the XAS spectra is reported. The intensity changes in the preedge region, which are consistent with a transition from a lower to a higher spin state, have been analyzed using a minimal model including the Co 3d and O 2p hybridization in the initial state. The temperature dependence of the Co magnetic moment obtained from the estimated e{sub g} and t{sub 2g} occupations could be satisfactorily reproduced. Also, the decrease of the Co 3d and O 2p hybridization by increasing temperature obtained from this simple model compares favorably with the values estimated from thermal evolution of the crystallographic structure.

  20. Solvation Effects on S K-edge XAS Spectra of Fe-S Proteins: Normal and Inverse Effects on WT and Mutant Rubredoxin

    PubMed Central

    Sun, Ning; Dey, Abhishek; Xiao, Zhiguang; Wedd, Anthony G.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

    2010-01-01

    S K-edge X-ray Absorption Spectroscopy (XAS) was performed on wild type Cp rubredoxin and its Cys->Ser mutants in both solution and lyophilized forms. For wild type rubredoxin and for the mutants where an interior cysteine residue (C6 or C39) is substituted by serine, a normal solvent effect is observed, that is, the S covalency increases upon lyophilization. For the mutants where a solvent accessible surface cysteine residue is substituted by serine, the S covalency decreases upon lyophilization which is an inverse solvent effect. Density functional theory (DFT) calculations reproduce these experimental results and show that the normal solvent effect reflects the covalency decrease due to solvent H-bonding to the surface thiolates and that the inverse solvent effect results from the covalency compensation from the interior thiolates. With respect to the Cys->Ser substitution, the S covalency decreases. Calculations indicate that the stronger bonding interaction of the alkoxide with the Fe relative to that of thiolate increases the energy of the Fe d orbitals and reduces their bonding interaction with the remaining cysteines. The solvent effects support a surface solvent tuning contribution to electron transfer and the Cys->Ser result provides an explanation for the change in properties of related iron-sulfur sites with this mutation. PMID:20726554

  1. Retention Mechanisms of Citric Acid in Ternary Kaolinite-Fe(III)-Citrate Acid Systems Using Fe K-edge EXAFS and L3,2-edge XANES Spectroscopy

    PubMed Central

    Yang, Jianjun; Wang, Jian; Pan, Weinan; Regier, Tom; Hu, Yongfeng; Rumpel, Cornelia; Bolan, Nanthi; Sparks, Donald

    2016-01-01

    Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. These findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils. PMID:27212680

  2. Adsorption of boric acid on pure and humic acid coated am-Al(OH)3: A boron K-edge XANES study.

    PubMed

    Xu, Dani; Peak, Derek

    2007-02-01

    The fate and mobility of boric acid in the environment is largely controlled by adsorption reactions with soil organic matter and soil minerals to form surface complexes (Soil Sci Soc. Am. J. 1991, 55, 1582; Geochim. Cosmochim. Acta 2002, 67, 2551; Soil Sci. Soc. Am. J. 1995, 59, 405; Environ. Sci. Technol. 1995, 29, 302). In this study, boric acid adsorption on pure am-Al(OH)3 and 5% (w/w) humic acid (HA) coated am-Al(OH)3 were investigated both as a function of pH (4.5-11) and initial boric acid concentration (0-4.5 mmol L(-1)). Batch adsorption isotherm experiments were also conducted with samples exposed to atmospheric CO2 and anaerobic (N2) conditions to examine the effects of dissolved CO2 on boric acid adsorption. Boron (B) K-edge X-ray absorption near-edge structure (XANES) spectroscopy was used to investigate the coordination of boric acid adsorbed at mineral/water interfaces. The XANES spectra of boric acid adsorption samples showed that both trigonally and tetrahedrally coordinated B complexes were present on the mineral surface. Both macroscopic and spectroscopic experiments revealed that the combination of HA coating on am-Al(OH)3 and dissolved CO2 decreased boric acid adsorption compared to adsorption on pure am-Al(OH)3.

  3. Dual-energy fluorescent x-ray computed tomography system with a pinhole design: Use of K-edge discontinuity for scatter correction

    PubMed Central

    Sasaya, Tenta; Sunaguchi, Naoki; Thet-Lwin, Thet-; Hyodo, Kazuyuki; Zeniya, Tsutomu; Takeda, Tohoru; Yuasa, Tetsuya

    2017-01-01

    We propose a pinhole-based fluorescent x-ray computed tomography (p-FXCT) system with a 2-D detector and volumetric beam that can suppress the quality deterioration caused by scatter components. In the corresponding p-FXCT technique, projections are acquired at individual incident energies just above and below the K-edge of the imaged trace element; then, reconstruction is performed based on the two sets of projections using a maximum likelihood expectation maximization algorithm that incorporates the scatter components. We constructed a p-FXCT imaging system and performed a preliminary experiment using a physical phantom and an I imaging agent. The proposed dual-energy p-FXCT improved the contrast-to-noise ratio by a factor of more than 2.5 compared to that attainable using mono-energetic p-FXCT for a 0.3 mg/ml I solution. We also imaged an excised rat’s liver infused with a Ba contrast agent to demonstrate the feasibility of imaging a biological sample. PMID:28272496

  4. Dual-energy fluorescent x-ray computed tomography system with a pinhole design: Use of K-edge discontinuity for scatter correction

    NASA Astrophysics Data System (ADS)

    Sasaya, Tenta; Sunaguchi, Naoki; Thet-Lwin, Thet-; Hyodo, Kazuyuki; Zeniya, Tsutomu; Takeda, Tohoru; Yuasa, Tetsuya

    2017-03-01

    We propose a pinhole-based fluorescent x-ray computed tomography (p-FXCT) system with a 2-D detector and volumetric beam that can suppress the quality deterioration caused by scatter components. In the corresponding p-FXCT technique, projections are acquired at individual incident energies just above and below the K-edge of the imaged trace element; then, reconstruction is performed based on the two sets of projections using a maximum likelihood expectation maximization algorithm that incorporates the scatter components. We constructed a p-FXCT imaging system and performed a preliminary experiment using a physical phantom and an I imaging agent. The proposed dual-energy p-FXCT improved the contrast-to-noise ratio by a factor of more than 2.5 compared to that attainable using mono-energetic p-FXCT for a 0.3 mg/ml I solution. We also imaged an excised rat’s liver infused with a Ba contrast agent to demonstrate the feasibility of imaging a biological sample.

  5. Combined sulfur K-edge XANES-EXAFS study of the effect of protonation on the sulfate tetrahedron in solids and solutions.

    PubMed

    Pin, S; Huthwelker, T; Brown, M A; Vogel, F

    2013-09-05

    Sulfur K-edge X-ray absorption spectroscopy (XAS) has been used to distinguish between aqueous and solid sulfates and to investigate changes in their speciation. Data have been collected for tetrahedrally coordinated S in K2SO4 and KHSO4 solids and aqueous solutions. With a first qualitative analysis of the X-ray absorption near-edge structure (XANES) spectra, it has been observed that those for solids are much more structured and distinguishable from those of aqueous solutions. The protonation state has a strong effect on the white line of sulfates and has been assigned to the different charge delocalization in the samples, the effect of the solvating water molecules and multiple scattering effects. In the extended X-ray absorption fine structure (EXAFS) spectra, the backscattering from the first O shell dominated the EXAFS fine structure function, χ(k), but the nonlinear multiple scattering contributions occurring in the first coordination shell are significant and must be considered in the EXAFS analysis. The intensity of these contributions strongly depend on the symmetry of the system. For a distorted tetrahedron, the intensity of the multiple scattering contributions is less than that found in a regular tetrahedron. The FEFF code has been used to model the contributions of the multiple-scattering processes. The observed experimental evidence in the XAS data can be used to distinguish between sulfates in solids and liquids. This is applicable to many chemical, geochemical, and biological systems.

  6. Sulfur K-Edge XAS Studies of the Effect of DNA Binding on the [Fe 4 S 4 ] Site in EndoIII and MutY

    DOE PAGES

    Ha, Yang; Arnold, Anna R.; Nuñez, Nicole N.; ...

    2017-07-18

    S K-edge X-ray absorption spectroscopy (XAS) was used to study the [Fe4S4] clusters in the DNA repair glycosylases EndoIII and MutY to evaluate the effects of DNA binding and solvation on Fe–S bond covalencies (i.e., the amount of S 3p character mixed into the Fe 3d valence orbitals). Increased covalencies in both iron–thiolate and iron–sulfide bonds would stabilize the oxidized state of the [Fe4S4] clusters. Our results are compared to those on previously studied [Fe4S4] model complexes, ferredoxin (Fd), and to new data on high-potential iron–sulfur protein (HiPIP). A limited decrease in covalency is observed upon removal of solvent watermore » from EndoIII and MutY, opposite to the significant increase observed for Fd, where the [Fe4S4] cluster is solvent exposed. Importantly, in EndoIII and MutY, a large increase in covalency is observed upon DNA binding, which is due to the effect of its negative charge on the iron–sulfur bonds. Furthermore, in EndoIII, this change in covalency can be quantified and makes a significant contribution to the observed decrease in reduction potential found experimentally in DNA repair proteins, enabling their HiPIP-like redox behavior.« less

  7. Measurement of sulfur L2,3 and carbon K edge XANES in a polythiophene film using a high harmonic supercontinuum.

    PubMed

    Johnson, A S; Miseikis, L; Wood, D A; Austin, D R; Brahms, C; Jarosch, S; Strüber, C S; Ye, P; Marangos, J P

    2016-11-01

    We use a high harmonic generated supercontinuum in the soft X-ray region to measure X-ray absorption near edge structure (XANES) spectra in polythiophene (poly(3-hexylthiophene)) films at multiple absorption edges. A few-cycle carrier-envelope phase-stable laser pulse centered at 1800 nm was used to generate a stable soft X-ray supercontinuum, with amplitude gating limiting the generated pulse duration to a single optical half-cycle. We report a quantitative transmission measurement of the sulfur L2,3 edge over the range 160-200 eV and the carbon K edge from 280 to 330 eV. These spectra show all the features previously reported in the XANES spectra of polythiophene, but for the first time they are measured with a source that has an approximately 1 fs pulse duration. This study opens the door to measurements that can fully time-resolve the photoexcited electronic dynamics in these systems.

  8. Improving material separation of high-flux whole-body photon counting computed tomography by K-edge pre-filtration

    NASA Astrophysics Data System (ADS)

    Polster, C.; Gutjahr, R.; Berner, M.; Flohr, T.; Hertel, M.; Kappler, S.; Stierstorfer, K.; Dietrich, O.

    2017-03-01

    Photon-counting detectors in computed tomography (CT) allow for measuring the energy of the incident xray photons within certain energy windows. This information can be used to enhance contrast or reconstruct CT images of different material bases. Compared to energy-integrating CT-detectors, pixel dimensions have to be smaller to limit the negative effect of pulse pile-up at high X-ray fluxes. Unfortunately, reducing the pixel size leads to increased K-escape and charge sharing effects. As a consequence, an incident X-ray may generate more than one detector signal, and with deteriorated energy information. In earlier simulation studies it has been shown that these limitations can be mitigated by optimizing the X-ray spectrum using K-edge pre-filtration. In the current study, we have used a whole-body research CT scanner with a high-flux capable photon-counting detector, in which for the first time a pre-patient hafnium filter was installed. Our measurement results demonstrate substantial improvement of the material decomposition capability at comparable dose levels. The results are in agreement with the predictions provided in simulations.

  9. Evolution of phosphorus complexation and mineralogy during (hydro)thermal treatments of activated and anaerobically digested sludge: Insights from sequential extraction and P K-edge XANES.

    PubMed

    Huang, Rixiang; Tang, Yuanzhi

    2016-09-01

    (Hydro)thermal treatments of sewage sludge is a promising option that can simultaneously target safe waste disposal, energy recovery, and nutrient recovery/recycling. The speciation of phosphorus (P) in sludge is of great relevance to P reclamation/recycling and soil application of sludge-derived products, thus it is critical to understand the effects of different treatment techniques and conditions on P speciation. This study systematically characterized P speciation (i.e. complexation and mineral forms) in chars derived from pyrolysis and hydrothermal carbonization (HTC) of municipal sewage sludges. Combined sequential extraction and P K-edge X-ray absorption near edge structure (XANES) spectroscopy analysis revealed the dependence of P transformation on treatment conditions and metal composition in the feedstocks. Pyrolysis of sludges decreased the relative abundance of phytic acid while increased the abundance of Al-associated P. HTC thoroughly homogenized and exposed P for interaction with various metals/minerals, with the final P speciation closely related to the composition/speciation of metals and their affinities to P. Results from this study revealed the mechanisms of P transformation during (hydro)thermal treatments of sewage sludges, and might be applicable to other biosolids. It also provided fundamental knowledge basis for the design and selection of waste management strategies for better P (re)cycling and reclamation.

  10. In situ site-selective transition metal K-edge XAS: a powerful probe of the transformation of mixed-valence compounds.

    PubMed

    Bordage, Amélie; Trannoy, Virgile; Proux, Olivier; Vitoux, Hugo; Moulin, Robinson; Bleuzen, Anne

    2015-07-14

    We present herein the first in situ site-selective XAS experiment performed on a proof-of-principle transformation of a mixed-valence compound: the calcination of the K0.1Co(II)4[Co(III)(CN)6]2.7·20H2O Prussian Blue analogue (containing Co(2+) and Co(3+) ions in two different Oh sites) into Co3O4 (containing Co(2+) ions in a Td site and Co(3+) in an Oh site). By recording the Co K-edge X-ray absorption spectra using a spectrometer aligned at the Co Kβ1,3 emission line, the evolution of each species was singly monitored from 20 °C up to the oxide formation. The experimental spectrum of the Co(2+)(Td) and Co(3+) (Oh) species in Co3O4 is reported for the first time. Our results demonstrate the possibilities offered by site-selective XAS for the investigation of chemical transformations and the study of materials under working conditions whenever the chemical element of interest is present in several states and/or sites.

  11. An unambiguous signature in molecular frame photoelectron angular distributions of core hole localization in fluorine K-edge photoionization of CF4

    NASA Astrophysics Data System (ADS)

    McCurdy, C. W.; Rescigno, T. N.; Trevisan, C. S.; Lucchese, R. R.

    2016-05-01

    Molecular Frame Photoelectron Angular Distributions (MFPADs) are calculated using the Complex Kohn variational method for core-hole ionization of the carbon and fluorines in CF4 at photoelectron energies below 15 eV. The angular distributions for localized versus delocalized core-hole creation on the four equivalent fluorines are radically different. A strong propensity for the dissociation to take place via the mechanism hν +CF4 -->CF 4 + +e- -->CF 3 + +F(1s-1) -->CF 3 + +F+ + 2e- in which a core excited neutral fluorine atom ionizes during or after dissociation creates the conditions for experimental observation of core hole localization. Comparison with recent unpublished experiments at the Advanced Light Source that measured the Recoil Frame Photoelectron Angular Distributions (averaged over CF3 rotations around the recoil axis) for fluorine K-edge ionization gives unambiguous evidence that these experiments directly observed the creation of an almost completely localized core hole on the dissociating fluorine atom when the molecule was initially photoionized. Work supported by USDOE, OBES Chemical Sciences, Geosciences, and Biosciences Division.

  12. Measurement of sulfur L2,3 and carbon K edge XANES in a polythiophene film using a high harmonic supercontinuum

    PubMed Central

    Johnson, A. S.; Miseikis, L.; Wood, D. A.; Austin, D. R.; Brahms, C.; Jarosch, S.; Strüber, C. S.; Ye, P.; Marangos, J. P.

    2016-01-01

    We use a high harmonic generated supercontinuum in the soft X-ray region to measure X-ray absorption near edge structure (XANES) spectra in polythiophene (poly(3-hexylthiophene)) films at multiple absorption edges. A few-cycle carrier-envelope phase-stable laser pulse centered at 1800 nm was used to generate a stable soft X-ray supercontinuum, with amplitude gating limiting the generated pulse duration to a single optical half-cycle. We report a quantitative transmission measurement of the sulfur L2,3 edge over the range 160–200 eV and the carbon K edge from 280 to 330 eV. These spectra show all the features previously reported in the XANES spectra of polythiophene, but for the first time they are measured with a source that has an approximately 1 fs pulse duration. This study opens the door to measurements that can fully time-resolve the photoexcited electronic dynamics in these systems. PMID:27822487

  13. Ce K edge XAS of ceria-based redox materials under realistic conditions for the two-step solar thermochemical dissociation of water and/or CO2.

    PubMed

    Rothensteiner, Matthäus; Sala, Simone; Bonk, Alexander; Vogt, Ulrich; Emerich, Hermann; van Bokhoven, Jeroen A

    2015-10-28

    X-ray absorption spectroscopy was used to characterise ceria-based materials under realistic conditions present in a reactor for solar thermochemical two-step water and carbon dioxide splitting. A setup suitable for in situ measurements in transmission mode at the cerium K edge from room temperature up to 1773 K is presented. Time-resolved X-ray absorption near-edge structure (XANES) data, collected for a 10 mol% hafnium-doped ceria sample (Ce0.9Hf0.1O2-δ) during reduction at 1773 K in a flow of inert gas and during re-oxidation by CO2 at 1073 K, enables the quantitative determination of the non-stoichiometry δ of the fluorite-type structure. XANES analysis suggests the formation of the hexagonal Ce2O3 phase upon reduction in 2% hydrogen/helium at 1773 K. We discuss the experimental limitations and possibilities of high-temperature in situ XAS at edges of lower energy as well as the importance of the technique for understanding and improving the properties of ceria-based oxygen storage materials for thermochemical solar energy conversion.

  14. Investigation of soil legacy phosphorus transformation in long-term agricultural fields using sequential fractionation, P K-edge XANES and solution P NMR spectroscopy.

    PubMed

    Liu, Jin; Hu, Yongfeng; Yang, Jianjun; Abdi, Dalel; Cade-Menun, Barbara J

    2015-01-06

    Understanding legacy phosphorus (P) build-up and draw-down from long-term fertilization is essential for effective P management. Using replicated plots from Saskatchewan, Canada, with P fertilization from 1967 to 1995 followed by either P fertilization or P cessation (1995-2010), soil P was characterized in surface and subsurface layers using sequential fractionation, P K-edge X-ray absorption near-edge structure (XANES) and solution (31)P nuclear magnetic resonance (P NMR) spectroscopy. Legacy P from a 28-year build-up was sufficient for 15 years of wheat cultivation, resulting in no significant differences in crop yield in 2010. In surface soils, soil test (Olsen) P decreased significantly in unfertilized plots compared with 1995, which was reflected in declining aluminum (hydr)oxide-associated inorganic P by fractionation and XANES. Furthermore, XANES analysis revealed a decrease of calcium-associated P in 2010-unfertilized soils at both depths and an increase of Fe (hydr)oxides-associated P in the 2010-fertilized and -unfertilized surface soils relative to the 1995 soils. Increased total organic P and orthophosphate diesters by P NMR and accumulated inositol hexaphosphate by XANES were observed in surface soils with P fertilization cessation. In subsurface soils, few legacy P transformations were detected. These results provide important information about legacy P to improve agricultural sustainability while mitigating water quality deterioration.

  15. Retention Mechanisms of Citric Acid in Ternary Kaolinite-Fe(III)-Citrate Acid Systems Using Fe K-edge EXAFS and L3,2-edge XANES Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yang, Jianjun; Wang, Jian; Pan, Weinan; Regier, Tom; Hu, Yongfeng; Rumpel, Cornelia; Bolan, Nanthi; Sparks, Donald

    2016-05-01

    Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. These findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.

  16. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    SciTech Connect

    Getsoian, Andrew "Bean"; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-06-13

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  17. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    DOE PAGES

    Getsoian, Andrew "Bean"; Das, Ujjal; Camacho-Bunquin, Jeffrey; ...

    2016-06-13

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order tomore » better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

  18. New methodological approach for the vanadium K-edge X-ray absorption near-edge structure interpretation: application to the speciation of vanadium in oxide phases from steel slag.

    PubMed

    Chaurand, Perrine; Rose, Jérôme; Briois, Valérie; Salome, Murielle; Proux, Olivier; Nassif, Vivian; Olivi, Luca; Susini, Jean; Hazemann, Jean-Louis; Bottero, Jean-Yves

    2007-05-17

    This paper presents a comparison between several methods dedicated to the interpretation of V K-edge X-ray absorption near-edge structure (XANES) features. V K-edge XANES spectra of several V-bearing standard compounds were measured in an effort to evaluate advantages and limits of each method. The standard compounds include natural minerals and synthetic compounds containing vanadium at various oxidation state (from +3 to +5) and in different symmetry (octahedral, tetrahedral, and square pyramidal). Correlations between normalized pre-edge peak area and its centroid position have been identified as the most reliable method for determining quantitative and accurate redox and symmetry information for vanadium. This methodology has been previously developed for the Fe K edge. It is also well adapted for the V K edge and is less influenced by the standard choice than other methods. This methodology was applied on an "environmental sample," i.e., a well-crystallized leached steel slag containing vanadium as traces. Micro-XANES measurements allowed elucidating the microdistribution of vanadium speciation in leached steel slag. The vanadium exhibits an important evolution from the unaltered to the altered phases. Its oxidation state increases from +3 to +5 together with the decrease of its symmetry (from octahedral to tetrahedral).

  19. Visible-light photocatalysis in Cu2Se nanowires with exposed {111} facets and charge separation between (111) and (1[combining macron]1[combining macron]1[combining macron]) polar surfaces.

    PubMed

    Liu, Bin; Ning, Lichao; Zhao, Hua; Zhang, Congjie; Yang, Heqing; Liu, Shengzhong Frank

    2015-05-28

    The search for active narrow band gap semiconductor photocatalysts that directly split water or degrade organic pollutants under solar irradiation remains an open issue. We synthesized Cu2Se nanowires with exposed {111} facets using ethanol and glycerol as morphology controlling agents. The {111} facets were found to be the active facets for decomposing organic contaminants in the entire solar spectrum. Based on the polar structure of the Cu2Se {111} facets, a charge separation model between polar (111) and (1[combining macron]1[combining macron]1[combining macron]) surfaces is proposed. The internal electric field between polar (111) and (1[combining macron]1[combining macron]1[combining macron]) surfaces created by spontaneous polarization drives charge separation. The reduction and oxidation reactions occur on the positive (111) and negative (1[combining macron]1[combining macron]1[combining macron]) polar surfaces, respectively. This suggests the surface-engineering of narrow band gap semiconductors as a strategy to fabricate photocatalysts with high reactivity in the entire solar spectrum. The charge separation model can deepen the understanding of charge transfer in other semiconductor nanocrystals with high photocatalytic activities and offer guidance to design more effective photocatalysts as well as new types of solar cells, photoelectrodes and photoelectric devices.

  20. Spin polarization and transport in the manganite La0.85Te0.15Mn0.9Cu0.1O3

    NASA Astrophysics Data System (ADS)

    Ang, R.; Sun, Y. P.; Yang, J.; Zhu, X. B.; Song, W. H.

    2006-11-01

    The resistivity ρ(T), and thermoelectric power (TEP) S(T,H) in the manganite La0.85Te0.15Mn0.9Cu0.1O3 have been investigated systematically in the absence and presence of magnetic fields. A large negative magnetoresistance (MR) appears up to 5 T. In addition, S(T) of the sample shows an anomalous peak, which is suggested to be related to the contribution of phonon drag. Particularly, the thermally induced and the field-induced sign change of S below the Curie temperature T is observed, implying the importance of spin polarization. In terms of the change of electronic structure, the orbital degree of freedom of the e carriers can be responsible for the effective lifting of the degenerate e band. Additionally, based on the fitting results of ρ(T) and S(T), the transport mechanism for the sample in the paramagnetic (PM) insulting region and low-temperature ferromagnetic (FM) insulating region below T is suggested to be dominated by variable-range-hopping (VRH) conduction. However, in the intermediate-temperature FM metallic region below T, the transport mechanism is considered to be dominated mainly electron magnon scattering.

  1. Observation of the segregation and the dissolution of the Co and the Cu in CoCu metastable alloys.

    PubMed

    Fdez-Gubieda, M L; García Prieto, A; García Arribas, A; Meneghini, C; Mobilio, S

    2001-03-01

    Metastable Co(x)Cu100-x(x=5, 10, 15, 20) alloys have been annealed at increasing temperatures in order to study the evolution of the Co cluster and its relation with the magnetotransport properties. The structure was investigated by X-ray Absorption Spectroscopy on the Co K-edge as a function of composition and annealing temperature. An anomalous trend in the structural evolution has been evidenced and related to the preculiar features observed in the magnetotransport properties.

  2. X-ray absorption near edge spectroscopy at the Mn K-edge in highly homogeneous GaMnN diluted magnetic semiconductors

    NASA Astrophysics Data System (ADS)

    Sancho-Juan, O.; Cantarero, A.; Martínez-Criado, G.; Olguín, D.; Garro, N.; Cros, A.; Salomé, M.; Susini, J.; Dhar, S.; Ploog, K.

    We have studied by X-ray absorption spectroscopy the local environment of Mn in highly homogeneous Ga1-xMnxN (0.06 < x < 0.14) thin epilayers grown by molecular beam epitaxy on [0001] SiC substrates. The measurements were performed in fluorescence mode around the Ga and Mn K-edges. In this report, we focus our attention to the X-ray absorption near edge spectroscopy (XANES) results. The comparison of the XANES spectra corresponding to the Ga and Mn edges indicates that Mn is substitutional to Ga in all samples studied. The XANES spectra measured at the Mn absorption edge shows in the near-edge region a double peak and a shoulder below the absorption edge and the main absorption peak after the edge, separated around 15 eV above the pre-edge structure. We have compared the position of the edge with that of MnO (Mn2+) and Mn2O3 (Mn3+). All samples studied present the same Mn oxidation state, 2+. In order to interprete the near-edge structure, we have performed ab initio calculations with a 2 × 2 × 1 supercell (?6% Mn) using the full potential linear augmented plane wave method as implemented in the Wien2k code. The calculations show the appearance of Mn anti-bonding t2g bands, which are responsible for the pre-edge absorption. The shoulder and main absorption peaks are due to transitions from the valence band 1s-states of Mn to the p-contributions of the conduction bands.

  3. Imaging Taurine in the Central Nervous System Using Chemically Specific X-ray Fluorescence Imaging at the Sulfur K-Edge

    SciTech Connect

    Hackett, Mark J.; Paterson, Phyllis G.; Pickering, Ingrid J.; George, Graham N.

    2016-11-15

    A method to image taurine distributions within the central nervous system and other organs has long been sought. Since taurine is small and mobile, it cannot be chemically “tagged” and imaged using conventional immuno-histochemistry methods. Combining numerous indirect measurements, taurine is known to play critical roles in brain function during health and disease and is proposed to act as a neuro-osmolyte, neuro-modulator, and possibly a neuro-transmitter. Elucidation of taurine’s neurochemical roles and importance would be substantially enhanced by a direct method to visualize alterations, due to physiological and pathological events in the brain, in the local concentration of taurine at or near cellular spatial resolution in vivo or in situ in tissue sections. We thus have developed chemically specific X-ray fluorescence imaging (XFI) at the sulfur K-edge to image the sulfonate group in taurine in situ in ex vivo tissue sections. To our knowledge, this represents the first undistorted imaging of taurine distribution in brain at 20 μm resolution. We report quantitative technique validation by imaging taurine in the cerebellum and hippocampus regions of the rat brain. Further, we apply the technique to image taurine loss from the vulnerable CA1 (cornus ammonis 1) sector of the rat hippocampus following global brain ischemia. The location-specific loss of taurine from CA1 but not CA3 neurons following ischemia reveals osmotic stress may be a key factor in delayed neurodegeneration after a cerebral ischemic insult and highlights the significant potential of chemically specific XFI to study the role of taurine in brain disease.

  4. Probing the electronic and geometric structure of ferric and ferrous myoglobins in physiological solutions by Fe K-edge absorption spectroscopy.

    PubMed

    Lima, Frederico A; Penfold, Thomas J; van der Veen, Renske M; Reinhard, Marco; Abela, Rafael; Tavernelli, Ivano; Rothlisberger, Ursula; Benfatto, Maurizio; Milne, Christopher J; Chergui, Majed

    2014-01-28

    We present an iron K-edge X-ray absorption study of carboxymyoglobin (MbCO), nitrosylmyoglobin (MbNO), oxymyoglobin (MbO2), cyanomyoglobin (MbCN), aquomet myoglobin (metMb) and unligated myoglobin (deoxyMb) in physiological media. The analysis of the XANES region is performed using the full-multiple scattering formalism, implemented within the MXAN package. This reveals trends within the heme structure, absent from previous crystallographic and X-ray absorption analysis. In particular, the iron-nitrogen bond lengths in the porphyrin ring converge to a common value of about 2 Å, except for deoxyMb whose bigger value is due to the doming of the heme. The trends of the Fe-Nε (His93) bond length is found to be consistent with the effect of ligand binding to the iron, with the exception of MbNO, which is explained in terms of the repulsive trans effect. We derive a high resolution description of the relative geometry of the ligands with respect to the heme and quantify the magnitude of the heme doming in the deoxyMb form. Finally, time-dependent density functional theory is used to simulate the pre-edge spectra and is found to be in good agreement with the experiment. The XAS spectra typically exhibit one pre-edge feature which arises from transitions into the unoccupied dσ and dπ - πligand* orbitals. 1s → dπ transitions contribute weakly for MbO2, metMb and deoxyMb. However, despite this strong Fe d contribution these transitions are found to be dominated by the dipole (1s → 4p) moment due to the low symmetry of the heme environment.

  5. Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L3,2-edge XANES spectroscopy

    DOE PAGES

    Yang, Jianjun; Wang, Jian; Pan, Weinan; ...

    2016-05-23

    Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L-3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/ormore » coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.« less

  6. In-operando synchronous time-multiplexed O K-edge x-ray absorption spectromicroscopy of functioning tantalum oxide memristors

    SciTech Connect

    Kumar, Suhas; Graves, Catherine E.; Strachan, John Paul Williams, R. Stanley; Kilcoyne, A. L. David; Tyliszczak, Tolek; Nishi, Yoshio

    2015-07-21

    Memristors are receiving keen interest because of their potential varied applications and promising large-scale information storage capabilities. Tantalum oxide is a memristive material that has shown promise for high-performance nonvolatile computer memory. The microphysics has been elusive because of the small scale and subtle physical changes that accompany conductance switching. In this study, we probed the atomic composition, local chemistry, and electronic structure of functioning tantalum oxide memristors through spatially mapped O K-edge x-ray absorption. We developed a time-multiplexed spectromicroscopy technique to enhance the weak and possibly localized oxide modifications with spatial and spectral resolutions of <30 nm and 70 meV, respectively. During the initial stages of conductance switching of a micrometer sized crosspoint device, the spectral changes were uniform within the spatial resolution of our technique. When the device was further driven with millions of high voltage-pulse cycles, we observed lateral motion and separation of ∼100 nm-scale agglomerates of both oxygen interstitials and vacancies. We also demonstrate a unique capability of this technique by identifying the relaxation behavior in the material during electrical stimuli by identifying electric field driven changes with varying pulse widths. In addition, we show that changes to the material can be localized to a spatial region by modifying its topography or uniformity, as against spatially uniform changes observed here during memristive switching. The goal of this report is to introduce the capability of time-multiplexed x-ray spectromicroscopy in studying weak-signal transitions in inhomogeneous media through the example of the operation and temporal evolution of a memristor.

  7. Imaging Taurine in the Central Nervous System Using Chemically Specific X-ray Fluorescence Imaging at the Sulfur K-Edge.

    PubMed

    Hackett, Mark J; Paterson, Phyllis G; Pickering, Ingrid J; George, Graham N

    2016-11-15

    A method to image taurine distributions within the central nervous system and other organs has long been sought. Since taurine is small and mobile, it cannot be chemically "tagged" and imaged using conventional immuno-histochemistry methods. Combining numerous indirect measurements, taurine is known to play critical roles in brain function during health and disease and is proposed to act as a neuro-osmolyte, neuro-modulator, and possibly a neuro-transmitter. Elucidation of taurine's neurochemical roles and importance would be substantially enhanced by a direct method to visualize alterations, due to physiological and pathological events in the brain, in the local concentration of taurine at or near cellular spatial resolution in vivo or in situ in tissue sections. We thus have developed chemically specific X-ray fluorescence imaging (XFI) at the sulfur K-edge to image the sulfonate group in taurine in situ in ex vivo tissue sections. To our knowledge, this represents the first undistorted imaging of taurine distribution in brain at 20 μm resolution. We report quantitative technique validation by imaging taurine in the cerebellum and hippocampus regions of the rat brain. Further, we apply the technique to image taurine loss from the vulnerable CA1 (cornus ammonis 1) sector of the rat hippocampus following global brain ischemia. The location-specific loss of taurine from CA1 but not CA3 neurons following ischemia reveals osmotic stress may be a key factor in delayed neurodegeneration after a cerebral ischemic insult and highlights the significant potential of chemically specific XFI to study the role of taurine in brain disease.

  8. In-operando synchronous time-multiplexed O K-edge x-ray absorption spectromicroscopy of functioning tantalum oxide memristors

    NASA Astrophysics Data System (ADS)

    Kumar, Suhas; Graves, Catherine E.; Strachan, John Paul; Kilcoyne, A. L. David; Tyliszczak, Tolek; Nishi, Yoshio; Williams, R. Stanley

    2015-07-01

    Memristors are receiving keen interest because of their potential varied applications and promising large-scale information storage capabilities. Tantalum oxide is a memristive material that has shown promise for high-performance nonvolatile computer memory. The microphysics has been elusive because of the small scale and subtle physical changes that accompany conductance switching. In this study, we probed the atomic composition, local chemistry, and electronic structure of functioning tantalum oxide memristors through spatially mapped O K-edge x-ray absorption. We developed a time-multiplexed spectromicroscopy technique to enhance the weak and possibly localized oxide modifications with spatial and spectral resolutions of <30 nm and 70 meV, respectively. During the initial stages of conductance switching of a micrometer sized crosspoint device, the spectral changes were uniform within the spatial resolution of our technique. When the device was further driven with millions of high voltage-pulse cycles, we observed lateral motion and separation of ˜100 nm-scale agglomerates of both oxygen interstitials and vacancies. We also demonstrate a unique capability of this technique by identifying the relaxation behavior in the material during electrical stimuli by identifying electric field driven changes with varying pulse widths. In addition, we show that changes to the material can be localized to a spatial region by modifying its topography or uniformity, as against spatially uniform changes observed here during memristive switching. The goal of this report is to introduce the capability of time-multiplexed x-ray spectromicroscopy in studying weak-signal transitions in inhomogeneous media through the example of the operation and temporal evolution of a memristor.

  9. Analysis of Flame Retardancy in Polymer Blends by Synchrotron X-ray K-edge Tomography and Interferometric Phase Contrast Movies.

    PubMed

    Olatinwo, Mutairu B; Ham, Kyungmin; McCarney, Jonathan; Marathe, Shashidhara; Ge, Jinghua; Knapp, Gerry; Butler, Leslie G

    2016-03-10

    Underwriters Laboratories 94 test bars have been imaged with X-ray K-edge tomography between 12 and 32 keV to assess the bromine and antimony concentration gradient across char layers of partially burnt samples. Phase contrast tomography on partially burnt samples showed gas bubbles and dark-field scattering ascribed to residual blend inhomogeneity. In addition, single-shot grating interferometry was used to record X-ray movies of test samples during heating (IR and flame) intended to mimic the UL 94 plastics flammability test. The UL 94 test bars were formulated with varying concentrations of a brominated flame retardant, Saytex 8010, and a synergist, Sb2O3, blended into high-impact polystyrene (HIPS). Depending on the sample composition, samples will pass or fail the UL 94 plastics flammability test. Tomography and interferometry imaging show differences that correlate with UL 94 performance. Key features such as char layer, gas bubble formation, microcracks, and dissolution of the flame retardant in the char layer regions are used in understanding the efficiency of the flame retardant and synergist. The samples that pass the UL 94 test have a thick, highly visible char layer as well as an interior rich in gas bubbles. Growth of gas bubbles from flame-retardant thermal decomposition is noted in the X-ray phase contrast movies. Also noteworthy is an absence of bubbles near the burning surface of the polymer; dark-field images after burning suggest a microcrack structure between interior bubbles and the surface. The accepted mechanism for flame retardant activity includes free radical quenching in the flame by bromine and antimony species. The imaging supports this as well as provides a fast inspection of other parameters, such as viscosity and surface tension.

  10. Pressure study of local tilts and their correlation to stripe order in single crystal La1.875Ba0.125CuO4

    NASA Astrophysics Data System (ADS)

    Fabbris, Gilberto; Hücker, Markus; Gu, Genda; Tranquada, John; Haskel, Daniel

    2012-02-01

    The strong Tc suppression in LaBaCuO at x=0.125 is widely believed to be related to formation of static stripes, at least partially driven by a strong electron-lattice coupling in a low temperature tetragonal (LTT) phase (Tranquada et al., Nature 375, 561 (1995)). A recent high-pressure experiment appears to challenge this view as it was observed that static stripe order persists to pressures higher than required to induce LTT to HTT transition (Hucker et al., PRL 104, 057004 (2010)). We carried out high-pressure La K-edge polarized XAFS measurements in LaBaCuO (x=0.125) single crystals in a diamond anvil cell to probe local CuO6 tilts. We observe that the local tilts remain LTT-like at high pressure, even though the macroscopic structure is HTT. The results suggest a significant order-disorder component to this pressure-induced phase transition, whereby the local LTT tilts remain present in the local scale but disorder over long range resulting in HTT symmetry seen by diffraction. The result may help explain why the stripe order is largely unaffected by the LTT to HTT pressure-induced transition. Work at Argonne (BNL) is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357 (DE-AC02-98CH10886).

  11. Optimization of K-edge imaging for vulnerable plaques using gold nanoparticles and energy resolved photon counting detectors: a simulation study.

    PubMed

    Alivov, Yahya; Baturin, Pavlo; Le, Huy Q; Ducote, Justin; Molloi, Sabee

    2014-01-06

    We investigated the effect of different imaging parameters, such as dose, beam energy, energy resolution and the number of energy bins, on the image quality of K-edge spectral computed tomography (CT) of gold nanoparticles (GNP) accumulated in an atherosclerotic plaque. A maximum likelihood technique was employed to estimate the concentration of GNP, which served as a targeted intravenous contrast material intended to detect the degree of the plaque's inflammation. The simulation studies used a single-slice parallel beam CT geometry with an x-ray beam energy ranging between 50 and 140 kVp. The synthetic phantoms included small (3 cm in diameter) cylinder and chest (33 × 24 cm(2)) phantoms, where both phantoms contained tissue, calcium and gold. In the simulation studies, GNP quantification and background (calcium and tissue) suppression tasks were pursued. The x-ray detection sensor was represented by an energy resolved photon counting detector (e.g., CdZnTe) with adjustable energy bins. Both ideal and more realistic (12% full width at half maximum (FWHM) energy resolution) implementations of the photon counting detector were simulated. The simulations were performed for the CdZnTe detector with a pixel pitch of 0.5-1 mm, which corresponds to a performance without significant charge sharing and cross-talk effects. The Rose model was employed to estimate the minimum detectable concentration of GNPs. A figure of merit (FOM) was used to optimize the x-ray beam energy (kVp) to achieve the highest signal-to-noise ratio with respect to the patient dose. As a result, the successful identification of gold and background suppression was demonstrated. The highest FOM was observed at the 125 kVp x-ray beam energy. The minimum detectable GNP concentration was determined to be approximately 1.06 µmol mL(-1) (0.21 mg mL(-1)) for an ideal detector and about 2.5 µmol mL(-1) (0.49 mg mL(-1)) for a more realistic (12% FWHM) detector. The studies show the optimal

  12. Sulfur K-edge X-ray absorption spectroscopy and density functional theory calculations on superoxide reductase: role of the axial thiolate in reactivity.

    PubMed

    Dey, Abhishek; Jenney, Francis E; Adams, Michael W W; Johnson, Michael K; Hodgson, Keith O; Hedman, Britt; Solomon, Edward I

    2007-10-17

    Superoxide reductase (SOR) is a non-heme iron enzyme that reduces superoxide to peroxide at a diffusion-controlled rate. Sulfur K-edge X-ray absorption spectroscopy (XAS) is used to investigate the ground-state electronic structure of the resting high-spin and CN- bound low-spin FeIII forms of the 1Fe SOR from Pyrococcus furiosus. A computational model with constrained imidazole rings (necessary for reproducing spin states), H-bonding interaction to the thiolate (necessary for reproducing Fe-S bond covalency of the high-spin and low-spin forms), and H-bonding to the exchangeable axial ligand (necessary to reproduce the ground state of the low-spin form) was developed and then used to investigate the enzymatic reaction mechanism. Reaction of the resting ferrous site with superoxide and protonation leading to a high-spin FeIII-OOH species and its subsequent protonation resulting in H2O2 release is calculated to be the most energetically favorable reaction pathway. Our results suggest that the thiolate acts as a covalent anionic ligand. Replacing the thiolate with a neutral noncovalent ligand makes protonation very endothermic and greatly raises the reduction potential. The covalent nature of the thiolate weakens the FeIII bond to the proximal oxygen of this hydroperoxo species, which raises its pKa by an additional 5 log units relative to the pKa of a primarily anionic ligand, facilitating its protonation. A comparison with cytochrome P450 indicates that the stronger equatorial ligand field from the porphyrin results in a low-spin FeIII-OOH species that would not be capable of efficient H2O2 release due to a spin-crossing barrier associated with formation of a high-spin 5C FeIII product. Additionally, the presence of the dianionic porphyrin pi ring in cytochrome P450 allows O-O heterolysis, forming an FeIV-oxo porphyrin radical species, which is calculated to be extremely unfavorable for the non-heme SOR ligand environment. Finally, the 5C FeIII site that results

  13. Optimization of the K-edge imaging for vulnerable plaques using gold nanoparticles and energy-resolved photon counting detectors: a simulation study

    PubMed Central

    Alivov, Yahya; Baturin, Pavlo; Le, Huy Q.; Ducote, Justin; Molloi, Sabee

    2014-01-01

    We investigated the effect of different imaging parameters such as dose, beam energy, energy resolution, and number of energy bins on image quality of K-edge spectral computed tomography (CT) of gold nanoparticles (GNP) accumulated in an atherosclerotic plaque. Maximum likelihood technique was employed to estimate the concentration of GNP, which served as a targeted intravenous contrast material intended to detect the degree of plaque's inflammation. The simulations studies used a single slice parallel beam CT geometry with an X-ray beam energy ranging between 50 and 140 kVp. The synthetic phantoms included small (3 cm in diameter) cylinder and chest (33x24 cm2) phantom, where both phantoms contained tissue, calcium, and gold. In the simulation studies GNP quantification and background (calcium and tissue) suppression task were pursued. The X-ray detection sensor was represented by an energy resolved photon counting detector (e.g., CdZnTe) with adjustable energy bins. Both ideal and more realistic (12% FWHM energy resolution) implementations of photon counting detector were simulated. The simulations were performed for the CdZnTe detector with pixel pitch of 0.5-1 mm, which corresponds to the performance without significant charge sharing and cross-talk effects. The Rose model was employed to estimate the minimum detectable concentration of GNPs. A figure of merit (FOM) was used to optimize the X-ray beam energy (kVp) to achieve the highest signal-to-noise ratio (SNR) with respect to patient dose. As a result, the successful identification of gold and background suppression was demonstrated. The highest FOM was observed at 125 kVp X-ray beam energy. The minimum detectable GNP concentration was determined to be approximately 1.06 μmol/mL (0.21 mg/mL) for an ideal detector and about 2.5 μmol/mL (0.49 mg/mL) for more realistic (12% FWHM) detector. The studies show the optimal imaging parameters at lowest patient dose using an energy resolved photon counting detector

  14. S K-edge X-ray absorption studies of tetranuclear iron-sulfur clusters: mu-sulfide bonding and its contribution to electron delocalization.

    PubMed

    Glaser, T; Rose, K; Shadle, S E; Hedman, B; Hodgson, K O; Solomon, E I

    2001-01-24

    X-ray absorption spectroscopy (XAS) at the sulfur ( approximately 2470 eV) and chlorine ( approximately 2822 eV) K-edges has been applied to a series of 4Fe-4S model complexes. These are compared to 2Fe-2S model complexes to obtain insight into the localized ground state in the mixed-valence dimer versus the delocalized ground state in the mixed-valence tetramer. The preedges of hypothetical delocalized mixed-valence dimers [Fe(2)S(2)](+) are estimated using trends from experimental data and density functional calculations, for comparison to the delocalized mixed-valence tetramer [Fe(4)S(4)](2+). The differences between these two mixed-valence sites are due to the change of the sulfide-bridging mode from micro(2) to micro(3). The terminal chloride and thiolate ligands are used as spectator ligands for the electron density of the iron center. From the intensity of the preedge, the covalency of the terminal ligands is found to increase in the tetramer as compared to the dimer. This is associated with a higher effective nuclear charge on the iron in the tetramer (derived from the energies of the preedge). The micro(3)-bridging sulfide in the tetramer has a reduced covalency per bond (39%) as compared to the micro(2)-bridging sulfide in the dimer (51%). A simple perturbation model is used to derive a quadratic dependence of the superexchange coupling constant J on the covalency of the metal ions with the bridging ligands. This relationship is used to estimate the superexchange contribution in the tetramer (J = -156 cm(-)(1)) as compared to the mixed-valence dimer (J = -360 cm(-)(1)). These results, combined with estimates for the double exchange and the vibronic coupling contributions of the dimer sub-site of the tetramer, lead to a delocalized S(t) = (9)/(2) spin ground state for the mixed-valence dimer in the tetramer. Thus, the decrease in the covalency, hence the superexchange pathway associated with changing the bridging mode of the sulfides from micro(2) to micro

  15. Mn K-edge XANES studies of La1-xAxMnO3 systems (A=Ca, Ba, Pb)

    NASA Astrophysics Data System (ADS)

    Bridges, F.; Booth, C. H.; Anderson, M.; Kwei, G. H.; Neumeier, J. J.; Snyder, J.; Mitchell, J.; Gardner, J. S.; Brosha, E.

    2001-06-01

    We present Mn K-edge x-ray absorption near-edge structure (XANES) data for a number of manganite systems as a function of temperature. The 1s absorption edge for the Ca-substituted samples is very sharp, almost featureless, and shifts uniformly upwards with increasing Ca content. The interpretation of this result is controversial because the lack of structure appears difficult to reconcile with a mixture of Mn+3 and Mn+4 ions or with several different Mn-O bond lengths at high T. We propose a possible solution in terms of covalency and considerable overlap of the Mn p states (mostly Mn 4p). The manganite preedge structure is quite similar to that for a large number of other Mn compounds, with two or three small peaks that are ascribed to 1s-3d weakly allowed dipole transitions plus possibly a small quadrupole component. The weak dipole transitions are explained as arising from a hybridization of the Mn 4p state of the excited atom with an odd symmetry combination of Mn 3d states on adjacent Mn atoms. The first preedge peak A1 has a small shift to higher energy with increasing valence while the next peak A2 is nearly independent of dopant concentration at 300 K. However, for the colossal magnetoresistance (CMR) samples the A2 preedge peak shifts to a lower energy below the ferromagnetic transition temperature Tc, resulting in a decrease in the A2-A1 splitting by ~0.4 eV. This indicates a change in the higher-energy 3d bands, most likely the minority spin eg, plus some change in covalency. In addition, the amplitudes are temperature dependent for the CMR materials, with the change in A1, A2 correlated with the change in sample magnetization. For the charge ordered (CO) sample, the analysis suggests that the change in the preedge is produced by a distortion that increases below TCO. We discuss these results in terms of some of the theoretical models that have been proposed and other recent XANES studies.

  16. The effect of site geometry, Ti content and Ti oxidation state on the Ti K-edge XANES spectrum of synthetic hibonite

    NASA Astrophysics Data System (ADS)

    Doyle, P. M.; Berry, A. J.; Schofield, P. F.; Mosselmans, J. F. W.

    2016-08-01

    The Al-rich oxide hibonite (CaAl12O19) is modeled to be the second mineral to condense from a gas of solar composition and is found within calcium-aluminum-rich inclusions and the matrix of chondritic meteorites. Both Ti3+ and Ti4+ are reported in meteoritic hibonite, so hibonite has been proposed as a single mineral oxybarometer that could be used to elucidate conditions within the first 0.2 Myrs of the Solar System. Synthetic hibonites with Ti3+/(Ti3+ + Ti4+) (hereafter Ti3+/ΣTi) ranging between 0 and 1 were prepared as matrix-matched standards for meteoritic hibonite. The largest yield of both Ti-free and Ti-bearing hibonite at ∼1300 and ∼1400 °C was obtained by a single sinter under reducing conditions. In situ micro-beam Ti K-edge X-ray absorption near edge structure (XANES) spectra were recorded from the synthetic hibonites, as well as from terrestrial hibonite. Spectral features in the post-crest region were shown to correlate with the Ti4+ content. Furthermore, Ti4+ on the M2 trigonal bipyramidal and the adjoining M4 octahedral sites appears to cause variability in the post-crest region as a function of orientation. For this suite of synthetic hibonites it was observed that the pre-edge peak region is not influenced by orientation, but is controlled by Ti3+/ΣTi, site geometry and/or Ti concentration. In particular, the pre-edge peak intensities reflect Ti coordination environment and distortion of the M4 octahedral site. Therefore, although pre-edge peak intensities have previously been used to determine Ti3+/ΣTi in meteoritic minerals, we excluded use of the pre-edge peak intensities for quantifying Ti valence states in hibonite. The energy of the absorption edge at a normalized intensity of 0.8 (E0.8) and the energy of the minimum between the pre-edge region and the absorption edge (Em1) were found to vary systematically with Ti3+/ΣTi. Ti3+/ΣTi in hibonite as a function of Em1 was modeled by a quadratic function that may be used to quantify Ti3

  17. Atomic structure of PtCu nanoparticles in PtCu/C catalysts prepared by simultaneous and sequential deposition of components on carbon support

    NASA Astrophysics Data System (ADS)

    Bugaev, L. A.; Srabionyan, V. V.; Pryadchenko, V. V.; Bugaev, A. L.; Avakyan, L. A.; Belenov, S. V.; Guterman, V. E.

    2016-05-01

    Nanocatalysts PtCu/C with different distribution of components in bimetallic PtCu nanoparticles (NPs) were synthesized by simultaneous and sequential deposition of Cu and Pt on carbon support. Electrochemical stability of the obtained samples PtCu/C was studied using the cyclic voltammetry. Characterization of atomic structure of as prepared PtCu NPs and obtained after acid treatment was performed by Pt L 3- and Cu K-edge EXAFS using the technique for determining local structure parameters of the absorbing atom under strong correlations among them. EXAFS derived parameters were used for generation of structural models of PtCu NPs by the method of cluster simulations. Within this approach, the models of atomic structure of PtCu NPs obtained by the two methods of synthesis, before and after post treatment and after two months from their preparation were revealed.

  18. Estimation of basis line-integrals in a spectral distortion-modeled photon counting detector using low-rank approximation-based x-ray transmittance modeling: K-edge imaging application.

    PubMed

    Lee, Okkyun; Kappler, Steffen; Polster, Christoph; Taguchi, Katsuyuki

    2017-08-29

    Photon counting detectors (PCD) provide multiple energy-dependent measurements for estimating basis lineintegrals. However, the measured spectrum is distorted from the spectral response effect (SRE) via charge sharing, K-fluorescence emission, etc. Thus, in order to avoid bias and artifacts in images, the SRE needs to be compensated. For this purpose, we recently developed a computationally efficient three-step algorithm for PCD-CT without contrast agents by approximating smooth x-ray transmittance using low-order polynomial bases. It compensated the SRE by incorporating the SRE model in a linearized estimation process and achieved nearly the minimum variance and unbiased (MVU) estimator. In this paper, we extend the three-step algorithm to K-edge imaging applications by designing optimal bases using a low-rank approximation to model x-ray transmittances with arbitrary shapes (i.e., smooth without the K-edge or discontinuous with the K-edge). The bases can be used to approximate the x-ray transmittance and to linearize the PCD measurement modeling and then the three-step estimator can be derived as in the previous approach: Estimating the xray transmittance in the first step, estimating basis line-integrals including that of the contrast agent in the second step, and correcting for a bias in the third step. We demonstrate that the proposed method is more accurate and stable than the low-order polynomial-based approaches with extensive simulation studies using gadolinium for the K-edge imaging application. We also demonstrate that the proposed method achieves nearly MVU estimator, and is more stable than the conventional maximum likelihood estimator in high attenuation cases with fewer photon counts.

  19. Atomistic origins of pressure-induced changes in the O K -edge x-ray Raman scattering features of Si O2 and MgSi O3 polymorphs: Insights from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Yi, Yoo Soo; Lee, Sung Keun

    2016-09-01

    Despite its fundamental importance in condensed matter physics and geophysical implications, establishing the systematic and direct link between the pressure-induced structural changes in crystalline and noncrystalline low-z oxides and their corresponding evolution in O K -edge core-electron excitation features under extreme compression has been challenging. Here we calculated the site-resolved partial density of states and O K -edge x-ray Raman scattering (XRS) spectra for two of the important oxide phases in the Earth's lower mantle, MgSi O3 bridgmanite and post-bridgmanite, up to 120 GPa using ab initio calculations, revealing the electronic origins of the O K -edge features for oxides under compression. The absorption threshold (EA) and band gap increase linearly with a decrease in the O-O distance in diverse Si O2 and MgSi O3 high-pressure phases [EA(eV ) ≈-10.9 dO-O(Å ) +34.4 ] , providing a predictive relationship between the EA and the O-O distances in the oxide at high pressure. Despite densification, upon isobaric phase transition from bridgmanite to post-bridgmanite at 120 GPa, a decrease in band gap results in a decrease in edge energy because of an increase in O-O distance. The oxygen proximity is a useful structural proxy of oxide densification upon compression, as it explains the pressure-induced changes in O K -edge XRS features of crystalline and amorphous Si O2 and MgSi O3 at high pressures. These results can be applied to studies of the pressure-bonding transitions in a wide range of oxides under extreme compression.

  20. Effects of Pb(Zr0.52Ti0.48)O3 polarization on the YBa2Cu3O7‑x electrical transport and magnetization

    NASA Astrophysics Data System (ADS)

    Jia, Jiqiang; Zhao, Gaoyang; Lei, Li

    2017-03-01

    The YBa2Cu3O7‑x (YBCO) superconducting film of 70 nm thickness was prepared on a LaAlO3 (LAO) substrate via the sol–gel method, following which the Pb(Zr0.52Ti0.48)O3 (PZT) ferroelectric film possessing interfacial coherent structure was grown via pulsed laser deposition (PLD) method, and then the Pt top electrode was deposited onto the PZT film by DC sputtering, resulting in the Pt/PZT/YBCO tri-layer structure. The ferroelectric hysteresis characteristics and the effects of ferroelectric polarization field of PZT on the electrical properties and magnetization of YBCO were studied for the temperature range of 50–300 K. Results reveal that as the temperature decreases, the remanent polarization of Pt/PZT/YBCO remains nearly constant, while the coercive field increased. The R–T curve of YBCO shifts upwards (positive polarization) or downwards (negative polarization) due to the influence of PZT polarization, indicating that the ferroelectric polarization of PZT modulates the R–T curve of YBCO. When YBCO is in the superconducting state, the magnetization of YBCO decreases with increasing polarization of PZT, indicating that the polarization field of PZT has a modulation effect on the magnetization of YBCO. Further investigation on the J–V curve of Pt/PZT/YBCO revealed a threshold conduction voltage (V t) and when the applied bias voltage was lower than V t, the leakage current of Pt/PZT/YBCO was small, and when the applied voltage was higher than V t, the leakage current rapidly increased. Meanwhile, the V t increased with decreasing temperature and then markedly changes at the superconducting transition temperature of YBCO.

  1. Hole concentration in the three-CuO 2-plane copper-oxide superconductor Cu-1223

    NASA Astrophysics Data System (ADS)

    Karppinen, M.; Yamauchi, H.; Morita, Y.; Kitabatake, M.; Motohashi, T.; Liu, R. S.; Lee, J. M.; Chen, J. M.

    2004-03-01

    Strongly overdoped samples of the three-CuO 2-plane copper-oxide superconductor, CuBa 2Ca 2Cu 3O 8+ z or Cu-1223, were obtained through high-pressure synthesis and post-annealed to various hole-doping levels so as to have the value of Tc range from 65 to 118 K. A concomitant decrease in the average valence of copper from ˜2.20 to ˜2.05 was evidenced by means of wet-chemical and thermogravimetric analyses and Cu L-edge X-ray absorption near-edge structure (XANES) spectroscopy. The valence value as low as ˜2.05 that corresponds to the highest Tc (=118 K) may be understood by taking into account multiple ways for holes to be distributed among the different Cu-O layers. In terms of actual chemical composition of the Cu-1223 phase, both Cu L-edge and O K-edge XANES results suggest that some portion of charge-reservoir copper atoms may have been replaced by CO, i.e., (Cu 1- xC x)Ba 2Ca 2Cu 3O 8+ x+ z. The variation range of excess oxygen was estimated at Δ z≈0.3.

  2. Atomic Resolution Mapping of the Excited-State Electronic Structure of Cu2O with Time-Resolved X-Ray Absorption Spectroscopy

    SciTech Connect

    Hillyard, Patrick B.; Kuchibhatla, Satyanarayana V N T; Glover, T. E.; Hertlein, M. P.; Huse, N.; Nachimuthu, Ponnusamy; Saraf, Laxmikant V.; Thevuthasan, Suntharampillai; Gaffney, Kelly J.

    2009-09-29

    We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the O K-edge and the Cu L3-edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that that the conduction band and valence band edges have very similar Cu 3d and O 2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the Cu L3- and O K-edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process.

  3. Atomic resolution mapping of the excited-state electronic structure of Cu2O with time-resolved x-ray absorption spectroscopy

    SciTech Connect

    Hillyard, P. W.; Kuchibhatla, S. V. N. T.; Glover, T. E.; Hertlein, M. P.; Huse, Nils; Nachimuthu, P.; Saraf, L. V.; Thevuthasan, S.; Gaffney, K. J.

    2010-05-02

    We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the O K-edge and the Cu L3-edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that the conduction-band and valence-band edges have very similar Cu 3d and O 2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the Cu L3- and O K-edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process.

  4. Mn K-Edge X-ray Absorption Studies of Oxo- and Hydroxo-manganese(IV) Complexes: Experimental and Theoretical Insights into Pre-Edge Properties

    PubMed Central

    2015-01-01

    Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [MnII(Cl)2(Me2EBC)], [MnIV(OH)2(Me2EBC)]2+, and [MnIV(O)(OH)(Me2EBC)]+, which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [MnIV(O)(OH)(Me2EBC)]+ revealed Mn–O scatterers at 1.71 and 1.84 Å and Mn–N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [MnII(Cl)2(Me2EBC)] and [MnIV(OH)2(Me2EBC)]2+ are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn–O(H) distances and pre-edge peak areas of MnIV=O and MnIV–OH complexes, but this trend was strongly modulated by the MnIV coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn–O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal MnIV=O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn=O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn=O σ* molecular orbital (MO) but also show intense transitions to 3dx2–y2 and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal MnIV=O adducts. These results underscore the importance of reporting experimental pre-edge areas

  5. Mn K-edge X-ray absorption studies of oxo- and hydroxo-manganese(IV) complexes: experimental and theoretical insights into pre-edge properties.

    PubMed

    Leto, Domenick F; Jackson, Timothy A

    2014-06-16

    Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [Mn(II)(Cl)2(Me2EBC)], [Mn(IV)(OH)2(Me2EBC)](2+), and [Mn(IV)(O)(OH)(Me2EBC)](+), which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [Mn(IV)(O)(OH)(Me2EBC)](+) revealed Mn-O scatterers at 1.71 and 1.84 Å and Mn-N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [Mn(II)(Cl)2(Me2EBC)] and [Mn(IV)(OH)2(Me2EBC)](2+) are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn-O(H) distances and pre-edge peak areas of Mn(IV)═O and Mn(IV)-OH complexes, but this trend was strongly modulated by the Mn(IV) coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn-O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal Mn(IV)═O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn═O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn═O σ* molecular orbital (MO) but also show intense transitions to 3dx(2)-y(2) and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal Mn(IV)═O adducts. These results underscore the importance of

  6. Resonant inelastic x-ray scattering on iso-C{sub 2}H{sub 2}Cl{sub 2} around the chlorine K-edge: Structural and dynamical aspects

    SciTech Connect

    Kawerk, Elie E-mail: ekawerk@units.it; Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Simon, Marc; Piancastelli, Maria Novella; Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok; and others

    2014-10-14

    We report a theoretical and experimental study of the high resolution resonant K{sub α} X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K{sub α} emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

  7. Mn K-edge XANES and Kbeta XES studies of two Mn-oxo binuclear complexes: investigation of three different oxidation states relevant to the oxygen-evolving complex of photosystem II.

    PubMed

    Visser, H; Anxolabéhère-Mallart, E; Bergmann, U; Glatzel, P; Robblee, J H; Cramer, S P; Girerd, J J; Sauer, K; Klein, M P; Yachandra, V K

    2001-07-25

    Two structurally homologous Mn compounds in different oxidation states were studied to investigate the relative influence of oxidation state and ligand environment on Mn K-edge X-ray absorption near-edge structure (XANES) and Mn Kbeta X-ray emission spectroscopy (Kbeta XES). The two manganese compounds are the di-mu-oxo compound [L'2Mn(III)O2Mn(IV)L'2](ClO4)3, where L' is 1,10-phenanthroline (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623-6630) and the linear mono-mu-oxo compound [LMn(III)OMn(III)L](ClO4)2, where L- is the monoanionic N,N-bis(2-pyridylmethyl)-N'-salicylidene-1,2-diaminoethane ligand (Horner, O.; Anxolabéhère-Mallart, E.; Charlot, M. F.; Tchertanov, L.; Guilhem, J.; Mattioli, T. A.; Boussac, A.; Girerd, J.-J. Inorg. Chem. 1999, 38, 1222-1232). Preparative bulk electrolysis in acetonitrile was used to obtain higher oxidation states of the compounds: the Mn(IV)Mn(IV) species for the di-mu-oxo compound and the Mn(III)Mn(IV) and Mn(IV)Mn(IV) species for the mono-mu-oxo compound. IR, UV/vis, EPR, and EXAFS spectra were used to determine the purity and integrity of the various sample solutions. The Mn K-edge XANES spectra shift to higher energy upon oxidation when the ligand environment remains similar. However, shifts in energy are also observed when only the ligand environment is altered. This is achieved by comparing the di-mu-oxo and linear mono-mu-oxo Mn-Mn moieties in equivalent oxidation states, which represent major structural changes. The magnitude of an energy shift due to major changes in ligand environment can be as large as that of an oxidation-state change. Therefore, care must be exercised when correlating the Mn K-edge energies to manganese oxidation states without taking into account the nature of the ligand environment and the overall structure of the compound. In contrast to Mn K-edge XANES, Kbeta XES spectra show less dependence on ligand environment. The Kbeta1,3 peak energies are comparable for the di-mu-oxo and mono

  8. A new structural motif for biological iron: iron K-edge XAS reveals a [Fe4-mu-(OR)5(OR)(9-10)] cluster in the ascidian Perophora annectens.

    PubMed

    Frank, Patrick; DeTomaso, Anthony; Hedman, Britt; Hodgson, Keith O

    2006-05-15

    The Phlebobranch ascidian Perophora annectens surprisingly exhibited a biological Fe/V ratio of approximately 15:1 on multichannel X-ray fluorescence analysis of two independent collections of organisms. Iron K-edge X-ray absorption spectroscopy (XAS) indicated a single form of iron. The XAS K-edge of the first collection of blood cells was shifted approximately +1 eV relative to that of the second, indicating redox activity with average iron oxidation states of 2.67+ and 2.60+. The first-derivative iron XAS K-edge features at 7120.5, 7124, and 7128 eV resembled the XAS of magnetite but not of ferritin or of dissolved Fe(II) or Fe(III). Pseudo-Voigt fits to blood-cell iron K-edge XAS spectra yielded 12.4 integrated units of preedge intensity, indicating a noncentrosymmetric environment. The non-phase-corrected extended X-ray absorption fine structure (EXAFS) Fourier transform spectrum showed a first-shell O/N peak at 1.55 angstroms and an intense Fe-Fe feature at 2.65 angstroms. Fits to the EXAFS required a split first shell with two O at 1.93 angstroms and three O at 2.07 angstroms, consistent with terminal and bridging alkoxide ligands, respectively. More distant shells included three C at 2.87 angstroms, two Fe at 3.08 angstroms, three O at 3.29 angstroms, and one Fe at 3.8 angstroms. Structural models consistent with these findings include a [Fe4(OR)13](2-/3-) broken-edged Fe4O5 cuboid or a [Fe4(OR)14](3-/4-) "Jacob's ladder" with three edge-fused Fe2(OR)2 rhombs. Either of these models represents an entirely new structural motif for biological iron. Vanadium domination of blood-cell metals cannot be a defining trait of Phlebobranch tunicates so long as P. annectens is included among them.

  9. Electronic structure of CuTPP and CuTPP(F) complexes: a combined experimental and theoretical study II.

    PubMed

    Mangione, Giulia; Sambi, Mauro; Carlotto, Silvia; Vittadini, Andrea; Ligorio, Giovanni; Timpel, Melanie; Pasquali, Luca; Giglia, Angelo; Nardi, Marco Vittorio; Casarin, Maurizio

    2016-09-28

    The unoccupied electronic structure of thick films of tetraphenylporphyrin and tetrakis(pentafluorophenyl)porphyrin Cu(ii) complexes (hereafter, CuTPP and CuTPP(F)) deposited on Au(111) has been studied by combining the outcomes of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy with those of spin-unrestricted time-dependent density functional (TD-DFT) calculations carried out either within the scalar relativistic zeroth order regular approximation (ZORA) framework (C, N and F K-edges) or by using the Tamm-Dancoff approximation coupled to ZORA and including spin-orbit effects (Cu L2,3-edges). Similarly to the modelling of NEXAFS outcomes pertaining to other Cu(ii) complexes, the agreement between theory and experiment is more than satisfactory, thus confirming the open-shell TD-DFT to be a useful tool to look into NEXAFS results pertinent to Cu(ii) compounds. The combined effect of metalation and phenyl (Ph) fluorine decoration is found to favour an extensive mixing between (Ph)σ* and pristine porphyrin macrocyle (pmc) (pmc)π* virtual levels. The lowest lying excitation in the C and N K-edge spectra of both CuTPP and CuTPP(F) is associated with a ligand-to-metal-charge-transfer transition, unambiguously revealed in the (CuTPP)N K-edge spectral pattern. Moreover, the comparison with literature data pertaining to the modelling of the (Cu(II))L2,3 features in the phthalocyanine-Cu(ii) (CuPc) complex provided further insights into how metal-to-ligand-charge-transfer transitions associated with excitations from 2p(Cu(II)) AOs to low-lying, ligand-based π* MOs may contribute to the Cu(ii) L2,3-edge intensity and thus weaken its believed relationship with the Cu(ii)-ligand symmetry-restricted covalency. Despite the coordinative pocket of CuTPP/CuTPP(F) mirroring CuPc, the ligand-field strength exerted by the phthalocyanine ligand on the Cu(ii) centre is experimentally found and theoretically confirmed to be slightly stronger than that experienced by Cu

  10. Quantifying point defects in Cu2ZnSn(S,Se)4 thin films using resonant x-ray diffraction

    NASA Astrophysics Data System (ADS)

    Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.; Teeter, Glenn; Repins, Ingrid L.; Toney, Michael F.

    2016-10-01

    Cu2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu2ZnSnS4 (8.6% efficiency) and Cu2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level of CuZn and ZnCu defects on the 2c and 2d Wyckoff positions. We observe a significantly lower concentration of ZnSn defects and Cu or Zn vacancies.

  11. Quantifying point defects in Cu 2 ZnSn(S,Se) 4 thin films using resonant x-ray diffraction

    DOE PAGES

    Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.; ...

    2016-10-17

    Cu 2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu 2ZnSnS4 (8.6% efficiency) and Cu 2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level ofmore » Cu Zn and Zn Cu defects on the 2c and 2d Wyckoff positions. We observe a significantly lower concentration of Zn Sn defects and Cu or Zn vacancies.« less

  12. Quantifying point defects in Cu2ZnSn(S,Se)4 thin films using resonant x-ray diffraction

    SciTech Connect

    Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.; Teeter, Glenn; Repins, Ingrid L.; Toney, Michael F.

    2016-10-17

    Cu 2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu 2ZnSnS4 (8.6% efficiency) and Cu 2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level of Cu Zn and Zn Cu defects on the 2c and 2d Wyckoff positions. We observe a significantly lower concentration of Zn Sn defects and Cu or Zn vacancies.

  13. Energy-discrimination X-ray computed tomography system utilizing a silicon-PIN detector and its application to 2.0-keV-width K-edge imaging

    NASA Astrophysics Data System (ADS)

    Hagiwara, Osahiko; Watanabe, Manabu; Sato, Eiichi; Matsukiyo, Hiroshi; Osawa, Akihiro; Enomoto, Toshiyuki; Nagao, Jiro; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

    2011-05-01

    Demonstration of narrow-energy-width computed tomography (CT) was carried out by means of energy-discrimination. An X-ray CT system is of a first-generation type and consists of an X-ray generator, a turntable, a translation stage, a two-stage controller, a silicon-PIN detector system with amplifiers, a multi-channel analyzer (MCA), a counter card (CC), and a personal computer (PC). CT is accomplished by repeating the translation and the rotation of an object, and projection curves of the object are obtained by the translation of the moving object. Both photon-energy level and energy width are determined by the MCA, and the pulses of the discriminated event signal from the MCA are counted by CC in conjunction with PC. The maximum count rate was approximately 300 cps (counts per second) with energy widths of 2.0 keV, and energy-discrimination CT was carried out with a photon-energy resolution of 0.15 keV. To perform iodine K-edge CT, X-ray photons with an energy range from 33.2 to 35.2 keV were used. Next, to carry out cerium K-edge CT, an energy range from 40.3 to 42.3 keV was selected.

  14. Full multiple scattering analysis of XANES at the Cd L3 and O K edges in CdO films combined with a soft-x-ray emission investigation

    SciTech Connect

    Demchenko, I. N.; Denlinger, J. D.; Chernyshova, M.; Yu, K. M.; Speaks, D. T.; Olalde-Velasco, P.; Hemmers, O.; Walukiewicz, W.; Derkachova, A.; Lawniczak-Jablonska, K.

    2010-07-05

    X-ray absorption near edge structure (XANES) at the cadmium L3 and oxygen K edges for CdO thin films grown by pulsed laser deposition method, is interpreted within the real-space multiple scattering formalism, FEFF code. The features in the experimental spectra are well reproduced by calculations for a cluster of about six and ten coordination shells around the absorber for L3 edge of Cd and K edge of O, respectively. The calculated projected electronic density of states is found to be in good agreement with unoccupied electronic states in experimental data and allows to conclude that the orbital character of the lowest energy of the conductive band is Cd-5s-O-2p. The charge transfer has been quantified and not purely ionic bonding has been found. Combined XANES and resonant inelastic x-ray scattering measurements allow us to determine the direct and indirect band gap of investigated CdO films to be {approx}2.4-eV and {approx}0.9-eV, respectively.

  15. Electron yield XAFS study of evaporated Co/Pd multilayers with various thickness ratios of Co to Pd sublayers: Simulations of the Co K-edge XAFS and fourier transforms

    SciTech Connect

    Choi, M. . Dept. of Physics); Joo, J.H. . Materials Design Lab.); Kim, S.K.; Kang, J.S.; Lee, Y.P. ); Shin, S.C. ); Heald, S.M.

    1992-01-01

    Electron-yield XAFS measurements using the NSLS were made on e-beam evaporated Co/Pd multilayers with various sublayer thicknesses and different thickness ratios of Co to Pd sublayers. The Co K-edge and the Pd K-edge XAFS data were obtained for the Co/Pd multilayers with sublayer thicknesses of 3[Angstrom]/ 4[Angstrom], 15[Angstrom]/4[Angstrom], 3[Angstrom]/15[Angstrom], 2.1[Angstrom]/13.5[Angstrom], and 2.2[Angstrom]/4.5[Angstrom]. Fourier transforms of Co K XAFS for most samples show a splitting of major peak, and the magnitude ratio of these split peaks varies systematically with the thickness ratio of the Pd sublayer to the Co sublayer, whereas the Fourier transforms of the Pd K XAFS for the same samples do not show a splitting of peaks. As a preliminary analysis, the Co K XAFS and the split peaks in the Fourier transform for the Co/Pd(3[Angstrom]/4[Angstrom]) case were simulated by using the FEFF calculations, and the Co K XAFS and the major peak in the fourier transform for the Co/Pd(15[Angstrom]/4[Angstrom]) case were also simulated consistently.

  16. Electron yield XAFS study of evaporated Co/Pd multilayers with various thickness ratios of Co to Pd sublayers: Simulations of the Co K-edge XAFS and fourier transforms

    SciTech Connect

    Choi, M.; Joo, J.H.; Kim, S.K.; Kang, J.S.; Lee, Y.P.; Shin, S.C.; Heald, S.M.

    1992-11-01

    Electron-yield XAFS measurements using the NSLS were made on e-beam evaporated Co/Pd multilayers with various sublayer thicknesses and different thickness ratios of Co to Pd sublayers. The Co K-edge and the Pd K-edge XAFS data were obtained for the Co/Pd multilayers with sublayer thicknesses of 3{Angstrom}/ 4{Angstrom}, 15{Angstrom}/4{Angstrom}, 3{Angstrom}/15{Angstrom}, 2.1{Angstrom}/13.5{Angstrom}, and 2.2{Angstrom}/4.5{Angstrom}. Fourier transforms of Co K XAFS for most samples show a splitting of major peak, and the magnitude ratio of these split peaks varies systematically with the thickness ratio of the Pd sublayer to the Co sublayer, whereas the Fourier transforms of the Pd K XAFS for the same samples do not show a splitting of peaks. As a preliminary analysis, the Co K XAFS and the split peaks in the Fourier transform for the Co/Pd(3{Angstrom}/4{Angstrom}) case were simulated by using the FEFF calculations, and the Co K XAFS and the major peak in the fourier transform for the Co/Pd(15{Angstrom}/4{Angstrom}) case were also simulated consistently.

  17. Water-window soft x-ray high-harmonic generation up to the nitrogen K-edge driven by a kHz, 2.1 μm OPCPA source

    NASA Astrophysics Data System (ADS)

    Stein, Gregory J.; Keathley, Phillip D.; Krogen, Peter; Liang, Houkun; Siqueira, Jonathas P.; Chang, Chun-Lin; Lai, Chien-Jen; Hong, Kyung-Han; Laurent, Guillaume M.; Kärtner, Franz X.

    2016-08-01

    We report the generation of coherent water-window soft x-ray harmonics in a neon-filled semi-infinite gas cell driven by a femtosecond multi-mJ mid-infrared optical parametric chirped-pulse amplification (OPCPA) system at a 1 kHz repetition rate. The cutoff energy was extended to ∼450 eV with a 2.1 μm driver wavelength and a photon flux of ∼ 1.5× {10}6 photons/s/1% bandwidth was obtained at 350 eV. A comparable photon flux of ∼ 1.0× {10}6 photons/s/1% bandwidth was observed at the nitrogen K-edge of 410 eV. This is the first demonstration of water-window harmonic generation up to the nitrogen K-edge from a kHz OPCPA system. Finally, this system is suitable for time-resolved soft x-ray near-edge absorption spectroscopy. Further scaling of the driving pulse's energy and repetition rate is feasible due to the availability of high-power picosecond Yb-doped pump laser technologies, thereby enabling ultrafast, tabletop water-window x-ray imaging.

  18. A XANES study of Cu speciation in high-temperature brines using synthetic fluid inclusions

    SciTech Connect

    Berry, Andrew J.; Hack, Alistair C.; Mavrogenes, John A.; Newville, Matthew; Sutton, Stephen R.

    2010-12-03

    Cu K-edge X-ray absorption near edge structure (XANES) spectra were recorded from individual synthetic brine fluid inclusions as a function of temperature up to 500 C. The inclusions serve as sample cells for high-temperature spectroscopic studies of aqueous Cu-Cl speciation. Cu{sup +} and Cu{sup 2+} can both be identified from characteristic pre-edge features. Mixed oxidation states can be deconvoluted using linear combinations of Cu{sup +} and Cu{sup 2+} spectra. This work illustrates how complex Cu XANES spectra can be interpreted successfully. Cu{sup 2+} is the stable oxidation state in solution at room temperature and Cu{sup +} at high temperatures. The change in oxidation state with temperature was completely reversible. Cu{sup +} was found to occur exclusively as the linear species [CuCl{sub 2}]{sup -} in solutions containing KCl with Cu:Cl ratios up to 1:6. In the absence of K{sup +}, there is evidence for higher order coordination of Cu{sup +}, in particular the tetrahedral complex [CuCl{sub 4}]{sup 3-}. The importance of such complexes in natural ore-forming fluids is yet to be determined, but may explain the vapor-phase partitioning of Cu as a Cl complex from a Cl-rich brine.

  19. Properties of impurity-bearing ferrihydrite II: Insights into the surface structure and composition of pure, Al- and Si-bearing ferrihydrite from Zn(II) sorption experiments and Zn K-edge X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Cismasu, A. Cristina; Levard, Clément; Michel, F. Marc; Brown, Gordon E.

    2013-10-01

    Naturally occurring ferrihydrite often contains impurities such as Al and Si, which can impact its chemical reactivity with respect to metal(loid) adsorption and (in)organic or microbially induced reductive dissolution. However, the surface composition of impure ferrihydrites is not well constrained, and this hinders our understanding of the factors controlling the surface reactivity of these nanophases. In this study, we conducted Zn(II) adsorption experiments combined with Zn K-edge X-ray absorption spectroscopy measurements on pure ferrihydrite (Fh) and Al- or Si-bearing ferrihydrites containing 10 and 20 mol% Al or Si (referred to as 10AlFh, 20AlFh and 10SiFh, 20SiFh) to evaluate Zn(II) uptake in relation to Zn(II) speciation at their surfaces. Overall, Zn(II) uptake at the surface of AlFh is similar to that of pure Fh, and based on Zn K-edge EXAFS data, Zn(II) speciation at the surface of Fh and AlFh also appears similar. Binuclear bidentate IVZn-VIFe complexes (at ∼3.46 Å (2C[1]) and ∼3.25 Å (2C[2])) were identified at low Zn(II) surface coverages from Zn K-edge EXAFS fits. With increasing Zn(II) surface coverage, the number of second-neighbor Fe ions decreased, which was interpreted as indicating the formation of IVZn polymers at the ferrihydrite surface, and a deviation from Langmuir uptake behavior. Zn(II) uptake at the surface of SiFh samples was more significant than at Fh and AlFh surfaces, and was attributed to the formation of outer-sphere complexes (on average 24% of sorbed Zn). Although similar Zn-Fe/Zn distances were obtained for the Zn-sorbed SiFh samples, the number of Fe second neighbors was lower in comparison with Fh. The decrease in second-neighbor Fe is most pronounced for sample 20SiFh, suggesting that the amount of reactive surface Fe sites diminishes with increasing Si content. Although our EXAFS results shown here do not provide evidence for the existence of Zn-Al or Zn-Si complexes, their presence is not excluded for Zn-sorbed Al

  20. Spin-polarized quasiparticle injection effect in MOCVD-grown YBa 2Cu 3O 7/SrTiO 3/La 1- xSr xMnO 3 heterostructures

    NASA Astrophysics Data System (ADS)

    Plausinaitiene, V.; Abrutis, A.; Vengalis, B.; Butkute, R.; Senateur, J. P.; Saltyte, Z.; Kubilius, V.

    2001-03-01

    Metal oxide heterostructures consisting of the ferromagnetic La 1- xSr xMnO 3 ( x≈0.3) underlayer, thin ( d≅5-10 nm) SrTiO 3 barrier layer and YBa 2Cu 3O 7 cap layer were grown on single crystal LaAlO 3 (1 0 0) substrates at 825°C under oxygen pressure of about 200 Pa by single source pulsed injection MOCVD method. The technological conditions were optimized in order to improve crystallinity and surface quality of the constituent layers. Wet etching was applied to form tape-like superconducting films for investigation of both longitudinal and transverse electrical transport in the heterostructures. Significant suppression of supercurrent has been found by injecting tunneling spin-polarized current from the underlying FM layer.

  1. Contribution of molecular dynamics simulations and ab initio calculations to the interpretation of Mg K-edge experimental XANES in K(2)O-MgO-3SiO(2) glass.

    PubMed

    Trcera, Nicolas; Rossano, Stéphanie; Madjer, Karim; Cabaret, Delphine

    2011-06-29

    The structural environment of Mg in a K-bearing silicate glass of composition K(2)MgSi(3)O(8) is investigated by x-ray absorption near-edge structure (XANES) spectroscopy at the Mg K-edge. XANES calculations are performed using a plane-wave electronic structure code, and a structural model obtained by classical molecular dynamics coupled to ab initio relaxation. Bond valence theory is used to validate plausible environments within the structural models. Comparison between the experimental and calculated spectra enables us to conclude that the Mg atoms are located in distorted tetrahedral sites. Site distortions are found to be correlated to the theoretical shift of the XANES edge position.

  2. Theoretical analysis of x-ray-absorption near-edge fine structure at the O and metal K edges of LaFeO{sub 3} and LaCoO{sub 3}

    SciTech Connect

    Wu, Z.Y.; Pedio, M.; Cimino, R.; Mobilio, S. |; Barman, S.R. |; Maiti, K.; Sarma, D.D. |

    1997-07-01

    We present experimental x-ray-absorption spectra at the oxygen and 3d transition-metal K edges of LaFeO{sub 3} and LaCoO{sub 3}. We interpret the experimental results in terms of detailed theoretical calculations based on multiple-scattering theory. Along with providing an understanding of the origin of various experimental features, we investigate the effects of structural distortions and the core-hole potential in determining the experimental spectral shape. The results indicate that the core-hole potential as well as many-body effects within the valence electrons do not have any strong effect on the spectra suggesting that the spectral features can be directly interpreted in terms of the electronic structure of such compounds. {copyright} {ital 1997} {ital The American Physical Society}

  3. Vanadium K-edge X-ray-absorption spectroscopy of the functioning and thionine-oxidized forms of the VFe-protein of the vanadium nitrogenase from Azotobacter chroococcum.

    PubMed Central

    Arber, J M; Dobson, B R; Eady, R R; Hasnain, S S; Garner, C D; Matsushita, T; Nomura, M; Smith, B E

    1989-01-01

    Vanadium K-edge X-ray-absorption spectra were collected for samples of thionine-oxidized, super-reduced (during enzyme turnover) and dithionite-reduced VFe-protein of the vanadium nitrogenase of Azotobacter chroococcum (Acl*). Both the e.x.a.f.s and the x.a.n.e.s. (X-ray-absorption near-edge structure) are consistent with the vanadium being present as part of a VFeS cluster; the environment of the vanadium is not changed significantly in different oxidation states of the protein. The vanadium atom is bound to three oxygen (or nitrogen), three sulphur and three iron atoms at 0.215(3), 0.231(3) and 0.275(3) nm respectively. PMID:2730564

  4. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3.

    PubMed

    Marini, C; Noked, O; Kantor, I; Joseph, B; Mathon, O; Shuker, R; Kennedy, B J; Pascarelli, S; Sterer, E

    2016-02-03

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb(5+) towards Nb(4+) above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ∼14.5 GPa.

  5. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3

    NASA Astrophysics Data System (ADS)

    Marini, C.; Noked, O.; Kantor, I.; Joseph, B.; Mathon, O.; Shuker, R.; Kennedy, B. J.; Pascarelli, S.; Sterer, E.

    2016-02-01

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb5+ towards Nb4+ above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ˜14.5 GPa.

  6. In situ X-ray Absorption Spectroscopic Investigation of the Electrochemical Conversion Reactions of CuF2-MoO3 Nanocomposite

    SciTech Connect

    A Mansour; F Badway; W Yoon; K Chung; G Amatucci

    2011-12-31

    We have used X-ray absorption spectroscopy at the Cu K-edge to investigate the electrochemical conversion reaction of 20 nm size 85 wt% CuF{sub 2}-15 wt% MoO{sub 3} nanocomposite under in situ conditions. The nanocomposite was prepared by high energy milling. Upon discharge, the lithiation reaction with the nanocomposite resulted in the formation of nanophase metallic Cu, which is consistent with the conversion of CuF{sub 2} into Cu and LiF. Based on XANES and Fourier transforms of EXAFS spectra, we show that the discharge process proceeded via the formation of highly dispersed Cu particles. Based on the coordination number of the first shell of Cu, the average size of the Cu particles was estimated to be in the 1-3 nm range in the fully discharged state.

  7. Quantifying point defects in Cu 2 ZnSn(S,Se) 4 thin films using resonant x-ray diffraction

    SciTech Connect

    Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.; Teeter, Glenn; Repins, Ingrid L.; Toney, Michael F.

    2016-10-17

    Cu 2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu 2ZnSnS4 (8.6% efficiency) and Cu 2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level of Cu Zn and Zn Cu defects on the 2c and 2d Wyckoff positions. We observe a significantly lower concentration of Zn Sn defects and Cu or Zn vacancies.

  8. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using X-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  9. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using X-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  10. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using x-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  11. Angle-resolved photoemission with circularly polarized light in the nodal mirror plane of underdoped Bi2Sr2CaCu2O8+δ superconductor

    DOE PAGES

    He, Junfeng; Mion, Thomas R.; Gao, Shang; ...

    2016-10-31

    Unraveling the nature of pseudogap phase in high-temperature superconductors holds the key to understanding their superconducting mechanisms and potentially broadening their applications via enhancement of their superconducting transition temperatures. Angle-resolved photoemission spectroscopy (ARPES) experiments using circularly polarized light have been proposed to detect possible symmetry breaking state in the pseudogap phase of cuprates. Here, the presence (absence) of an electronic order which breaks mirror symmetry of the crystal would in principle induce a finite (zero) circular dichroism in photoemission. Different orders breaking reflection symmetries about different mirror planes can also be distinguished by the momentum dependence of the measured circularmore » dichroism.« less

  12. Using Solution- and Solid-State S K-edge X-ray Absorption Spectroscopy with Density Functional Theory to Evaluate M–S Bonding for MS42- (M = Cr, Mo, W) Dianions

    PubMed Central

    Olson, Angela C.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Daly, Scott R.; Kozimor, Stosh A.; MacInnes, Molly M.; Martin, Richard L.; Scott, Brian L.

    2014-01-01

    Herein, we have evaluated relative changes in M–S electronic structure and orbital mixing in Group 6 MS42- dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t2* electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as 1A1 → 1T2 transitions. For MoS42-, both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS42-, solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t2* orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO42- dianions, which allowed M–S and M–O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M–E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M–S bonds, but increased appreciably for M–O interactions. For the t2* orbitals (σ* + π*), mixing decreased slightly for M–S bonding and increased only slightly for the M–O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME42- (E = O, S) dianions. PMID:25311904

  13. Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M-S bonding for MS4(2-) (M = Cr, Mo, W) dianions.

    PubMed

    Olson, Angela C; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Daly, Scott R; Kozimor, Stosh A; MacInnes, Molly M; Martin, Richard L; Scott, Brian L

    2014-12-14

    Herein, we have evaluated relative changes in M-S electronic structure and orbital mixing in Group 6 MS4(2-) dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as (1)A1 → (1)T2 transitions. For MoS4(2-), both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS4(2-), solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO4(2-) dianions, which allowed M-S and M-O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M-E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M-S bonds, but increased appreciably for M-O interactions. For the t orbitals (σ* + π*), mixing decreased slightly for M-S bonding and increased only slightly for the M-O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME4(2-) (E = O, S) dianions.

  14. Cadmium (II) and lead (II) transport in a polymer inclusion membrane using tributyl phosphate as mobile carrier and CuFeO(2) as a polarized photo electrode.

    PubMed

    Arous, Omar; Amara, Mourad; Trari, Mohamed; Bouguelia, Aissa; Kerdjoudj, Hacène

    2010-08-15

    In this work, a development of polymeric inclusion membranes for the cations separation is reported. The membrane was made up of cellulose triacetate (CTA) with a tributyl phosphate (TBP) incorporated into the polymer as metal ions carrier. The transport of lead (II) and cadmium (II) ions in two membrane systems polymer inclusion membrane (PIM), PIM coupled with photo-chemical electrode using TBP as carrier and 2-nitro phenyl octyl ether (NPOE) or tris ethylhexyl phosphate (TEHP) as plasticizer have been investigated. The membranes: polymer+plasticizer+carrier were synthesized and characterized by FTIR, X-ray diffraction and scanning electron microscopy (SEM). Transports of lead and cadmium have been studied using these systems and the results were compared to commercial cation exchange membrane (CRA). The obtained results showed that for Pb(2+) ion, the concentrations of the strip phase increases using synthesized membranes. The conduction band of the delafossite CuFeO(2) (-1.25 V(SCE)) yields a thermodynamically M(2+) (=Pb(2+), Cd(2+)) photo electrodeposition and speeds up the diffusion process. In all the cases, the potential of the electrode M/M(2+) in the feed compartment increases until a maximum value, reached at approximately 100 min above which it undergoes a diminution. Copyright 2010 Elsevier B.V. All rights reserved.

  15. Film/substrate registry as measured by anomalous x-ray scattering at a reacted, epitaxial Cu/Si(111) interface

    NASA Astrophysics Data System (ADS)

    Walker, F. J.; Specht, E. D.; McKee, R. A.

    1991-11-01

    We used anomalous x-ray-diffraction methods to measure the contribution of an epitaxial copper overlayer on silicon to the crystal truncation rods (CTR's). The intensities of the CTR's are analyzed to determine interface structure; the epitaxy of a large-misfit system, Cu on Si(111), can be described in relationship to this structure. Anomalous scattering observed at the Cu K edge along a Si CTR demonstrates copper atoms to be in registry with the Si(111) surface. The copper-atom registry at the interface can be modeled based on the known bulk η-Cu3Si structure and observed epitaxy.

  16. Orbital hybridization and magnetic coupling of the A-site Cu spins in CaCu3B4O12 (B = Ti, Ge, and Sn) perovskites.

    PubMed

    Mizumaki, M; Saito, T; Shiraki, H; Shimakawa, Y

    2009-04-20

    X-ray absorption spectroscopy (XAS) spectra near the O K-edge of A-site-ordered perovskite with A-site Cu(2+) (S = (1)/(2)) spins were measured. The spectra of ferromagnetic CaCu(3)Ge(4)O(12) and CaCu(3)Sn(4)O(12) showed hybridization between Cu 3d and O 2p orbitals, but magnetic circular dichroism measurement revealed that the O 2p orbital played a less important role in magnetic interaction. The XAS spectra of antiferromagnetic CaCu(3)Ti(4)O(12), on the other hand, showed strong hybridization of the Cu 3d, Ti 3d, and O 2p orbitals. These results demonstrated that direct exchange interaction of the Cu(2+) spins primarily determined the ferromagnetic ordering of CaCu(3)Ge(4)O(12) and CaCu(3)Sn(4)O(12), whereas the involvement of Ti 3d orbitals induced the antiferromagnetic property in CaCu(3)Ti(4)O(12).

  17. Directional Dichroism of X-ray Absorption in a Polar Ferrimagnet GaFeO3

    NASA Astrophysics Data System (ADS)

    Igarashi, Jun-ichi; Nagao, Tatsuya

    2010-01-01

    We study the directional dichroic absorption spectra in the x-ray region in a polar ferrimagnet GaFeO3. The directional dichroism on the absorption spectra at the Fe pre-K-edge arises from the E1-E2 interference process through the hybridization between the 4p and 3d states in the noncentrosymmetric environment of Fe atoms. We perform a microscopic calculation of the spectra on a model of FeO6 with reasonable parameter values for Coulomb interaction and hybridizations. We obtain the difference in the absorption coefficients when the magnetic field is applied parallel and antiparallel to the c-axis. The spectra thus obtained have similar shapes to the experimental curves as a function of photon energy in the Fe pre-K-edge region, although they have opposite signs.

  18. Theoretical study of the electron affinities of Cu, Cu2, and Cu3

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

    1988-01-01

    The modified pair functional method is used here to compute the electron affinities of the negative ions of Cu, Cu2, and Cu3 to equal relative accuracy. The results show that, while the extra electron in Cu2(-) occupies a sigma(u) antibonding orbital, the orbital is polarized to reduce the density in the internuclear rergion. The calculations also show that Cu3(-) is a closed-shell linear molecule in its ground state, and that there is an excited triplet state about 0.7 eV higher in energy. This strongly suggests that photodetachment from the excited triplet state is responsible for the low energy structure observed in the photoelectron spectrum of Cu3(-).

  19. Sulfur K-Edge XAS and DFT Calculations on [Fe4S4]2+Clusters: Effects of H-bonding and Structural Distortion on Covalency and SpinTopology

    SciTech Connect

    Dey, A.; Roche, C.L.; Walters, M.A.; Hodgson, K.O.; B., Hedman; Solomon, E.I.; /Stanford U., Chem. Dept. /SLAC, SSRL

    2006-09-28

    Sulfur K-edge X-ray absorption spectroscopy of a hydrogen-bonded elongated [Fe{sub 4}S{sub 4}]{sup 2+} cube is reported. The data show that this synthetic cube is less covalent than a normal compressed cube with no hydrogen bonding. DFT calculations reveal that the observed difference in electronic structure has significant contributions from both the cluster distortion and from hydrogen bonding. The elongated and compressed Fe{sub 4}S{sub 4} structures are found to have different spin topologies (i.e., orientation of the delocalized Fe{sub 2}S{sub 2} subclusters which are antiferromagnetically coupled to each other). It is suggested that the H-bonding interaction with the counterion does not contribute to the cluster elongation. A magneto-structural correlation is developed for the Fe{sub 4}S{sub 4} cube that is used to identify the redoxactive Fe{sub 2}S{sub 2} subclusters in active sites of HiPIP and ferredoxin proteins involving these clusters.

  20. Chemical kinetics of Cs species in an alkali-activated municipal solid waste incineration fly ash and pyrophyllite-based system using Cs K-edge in situ X-ray absorption fine structure analysis

    NASA Astrophysics Data System (ADS)

    Shiota, Kenji; Nakamura, Takafumi; Takaoka, Masaki; Nitta, Kiyofumi; Oshita, Kazuyuki; Fujimori, Takashi; Ina, Toshiaki

    2017-05-01

    We conducted in situ X-ray absorption fine structure (in situ XAFS) analysis at the Cs K-edge to investigate the chemical kinetics of Cs species during reaction in an alkali-activated municipal solid waste incineration fly ash (MSWIFA) and pyrophyllite-based system. Understanding the kinetics of Cs is essential to the design of appropriate conditions for Cs stabilization. In situ XAFS analysis of four pastes, prepared from NaOHaq, sodium silicate solution, pyrophyllite, and MSWIFA with the addition of CsCl, was conducted in custom-built reaction cells at four curing temperatures (room temperature, 60 °C, 80 °C, 105 °C) for approximately 34 h. The results indicated that the change in Cs species during reaction at room temperature was small, while changes at higher temperatures were faster and more extreme, with the fastest conversion to pollucite occurring at 105 °C. Further analysis using a leaching test and a simple reaction model for Cs species during reaction showed that the pollucite formation rate was dependent on the curing temperature and had a significant negative correlation with Cs leaching. The activation energy of pollucite formation was estimated to be 31.5 kJ/mol. These results revealed that an important change in the chemical state of Cs occurs during reaction in the system.

  1. High-resolution Measurement of Contact Ion-pair Structures in Aqueous RbCl Solutions from the Simultaneous Corefinement of their Rb and Cl K-edge XAFS and XRD Spectra

    SciTech Connect

    Pham, Van-Thai; Fulton, John L.

    2016-06-21

    In concentrated solutions of aqueous RbCl, all of the Rb+ and Cl- ions exist as contact ion pairs. This full structural assessment is derived from the refinement of three independent experimental measurements: the Rb and Cl K-edge x-ray absorption fine structure (XAFS) and the x-ray diffraction spectra (XRD). This simultaneous refinement of the XAFS and XRD data provides high accuracy since each method probes the structure of different local regions about the ions with high sensitivity. At high RbCl concentration (6 m (mol/kg )) the solution is dominated by Rb+ - Cl- contact ion pairs yielding an average of 1.5 pairs at an Rb-Cl distance of 3.24 Å. Upon formation of these ion pairs, approximately 1.1 waters molecules are displaced from the Rb+ and 1.4 water molecules from Cl-. The hydration shells about both the cation and anion are also determined. These results greatly improve the understanding of monovalent ions and provide a basis for testing the Rb+-Cl- interaction potentials used in molecular dynamics (MD) simulation. This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

  2. Investigation of X-ray natural circular dichroism in a CsCuCl3 single crystal: Theory and experiment

    NASA Astrophysics Data System (ADS)

    Rogalev, A.; Goulon, J.; Wilhelm, F.; Kozlovskaya, K. A.; Ovchinnikova, E. N.; Soboleva, L. V.; Konstantinova, A. F.; Dmitrienko, V. E.

    2008-05-01

    X-ray natural circular dichroism in the near-Cu K edge in a CsCuCl3 single crystal, caused by dipole-quadrupole ( E1 E2) transitions between electronic states of different parity, has been experimentally and theoretically investigated. Numerical simulation of the experimental X-ray absorption spectrum and circular dichroism has been performed. It is established that a circular dichroism signal is observed in the pre-edge spectral region; therefore, it is mainly due to the localized electronic p-d states.

  3. A grazing incidence surface X-ray absorption fine structure (GIXAFS) study of alkanethiols adsorbed on Au, Ag, and Cu

    NASA Astrophysics Data System (ADS)

    Floriano, Pierre N.; Schlieben, Olaf; Doomes, Edward E.; Klein, Ingo; Janssen, J.; Hormes, Josef; Poliakoff, E. D.; McCarley, Robin L.

    2000-04-01

    Self-assembled monolayers of n-alkanethiols, CH 3-(CH 2) x-SH, on Au, Ag, and Cu have been studied with GIXAFS at the sulfur K-edge. For both pentanethiol and decanethiol monolayers on Ag and Cu, the three-fold hollow site is found to be the most probable sulfur binding site. However, observations for octadecanethiol indicate that the three-fold hollow site is not the exclusive binding site. In addition, the possible existence of disulfide bonds on the metal surface (adsorbed dialkyldisulfides) is not supported by the data. Preliminary results from monolayers on Au are also reported.

  4. Polarized cells, polar actions.

    PubMed

    Maddock, J R; Alley, M R; Shapiro, L

    1993-11-01

    The recognition of polar bacterial organization is just emerging. The examples of polar localization given here are from a variety of bacterial species and concern a disparate array of cellular functions. A number of well-characterized instances of polar localization of bacterial proteins, including the chemoreceptor complex in both C. crescentus and E. coli, the maltose-binding protein in E. coli, the B. japonicum surface attachment proteins, and the actin tail of L. monocytogenes within a mammalian cell, involve proteins or protein complexes that facilitate bacterial interaction with the environment, either the extracellular milieux or that within a plant or mammalian host. The significance of this observation remains unclear. Polarity in bacteria poses many problems, including the necessity for a mechanism for asymmetrically distributing proteins as well as a mechanism by which polar localization is maintained. Large structures, such as a flagellum, are anchored at the pole by means of the basal body that traverses the peptidoglycan wall. But for proteins and small complexes, whether in the periplasm or the membrane, one must invoke a mechanism that prevents the diffusion of these proteins away from the cell pole. Perhaps the periplasmic proteins are retained at the pole by the presence of the periseptal annulus (35). The constraining features for membrane components are not known. For large aggregates, such as the clusters of MCP, CheA, and CheW complexes, perhaps the size of the aggregate alone prevents displacement. In most cases of cellular asymmetry, bacteria are able to discriminate between the new pole and the old pole and to utilize this information for localization specificity. The maturation of new pole to old pole appears to be a common theme as well. Given numerous examples reported thus far, we propose that bacterial polarity displays specific rules and is a more general phenomenon than has been previously recognized.

  5. Local structure study of (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} thin films using x-ray absorption spectroscopy

    SciTech Connect

    Ren, Yuan; Xing, Yaya; Ma, Guanxiong; Wang, Shiqi; An, Yukai Liu, Jiwen; Zhao, Xingliang

    2015-07-15

    The (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} (x = 0.06, 0.08, 0.15, and 0.20) films prepared by RF-magnetron sputtering were investigated by the combination of x-ray absorption spectroscopy (XAS) at Fe, Cu, and O K-edge. Although the Fe and O K-edge XAS spectra show that the Fe atoms substitute for the In sites of In{sub 2}O{sub 3} lattice for all the films, the Cu K-edge XAS spectra reveal that the codoped Cu atoms are separated to form the Cu metal clusters. After being annealed in air, the Fe atoms are still substitutionally incorporated into the In{sub 2}O{sub 3} lattice, while the Cu atoms form the CuO secondary phases. With the increase of Fe concentration, the bond length R{sub Fe-O} shortens and the Debye–Waller factor σ{sup 2}{sub Fe-O} increases in the first coordination shell of Fe, which are attributed to the relaxation of oxygen environment around the substitutional Fe ions. The forming of Cu relating secondary phases in the films is due to high ionization energy of Cu atoms, leading that the Cu atoms are energetically much harder to be oxidized to substitute for the In sites of In{sub 2}O{sub 3} lattice than Fe atoms. These results provide new experimental guidance in the preparation of the codoped In{sub 2}O{sub 3} based dilute magnetic oxides.

  6. EXAFS analysis of a human Cu,Zn SOD isoform focused using non-denaturing gel electrophoresis

    NASA Astrophysics Data System (ADS)

    Chevreux, Sylviane; Solari, Pier Lorenzo; Roudeau, Stéphane; Deves, Guillaume; Alliot, Isabelle; Testemale, Denis; Hazemann, Jean Louis; Ortega, Richard

    2009-11-01

    Isoelectric point isoforms of a metalloprotein, copper-zinc superoxide dismutase (CuZnSOD), separated on electrophoresis gels were analyzed using X-ray Absorption Spectroscopy. Mutations of this protein are involved in familial cases of amyotrophic lateral sclerosis. The toxicity of mutants could be relied to defects in the metallation state. Our purpose is to establish analytical protocols to study metallation state of protein isoforms such as those from CuZnSOD. We previously highlighted differences in the copper oxidation state between CuZnSOD isoforms using XANES. Here, we present the first results for EXAFS analyses performed at Cu and Zn K-edge on the majoritary expressed isoform of human CuZnSOD separated on electrophoresis gels.

  7. Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L3,2-edge XANES spectroscopy

    SciTech Connect

    Yang, Jianjun; Wang, Jian; Pan, Weinan; Regier, Tom; Hu, Yongfeng; Rumpel, Cornelia; Bolan, Nanthi; Sparks, Donald

    2016-05-23

    Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L-3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.

  8. Mn K-edge XANES spectroscopy of a photosynthetic O2-evolving complex. High-quality pre-edge features and distinct fine structures in the S1- and S2-states.

    PubMed

    Kusunoki, M; Ono, T; Matsushita, T; Oyanagi, H; Inoue, Y

    1990-10-01

    High-resolution XANES (X-ray Absorption Near Edge Structure) spectroscopy for Mn in the S1 and S2 states of the spinach photosynthetic O2-evolving complex revealed distinct features in K-edge spectra, when a high signal-to-noise (S/N) ratio of ca. 80 with a low and constant background-to-signal (B/S) ratio of 0.15 to 0.18 was attained. Six features resolved in each S-state spectrum involve a pre-edge feature due to 1s----3d transitions, a main-edge feature possibly due to 1s----4s transitions and four fine structures superimposed on the principal absorption bands due to 1s----4p* transitions. The high-quality pre-edge features were analyzed according to a parametric ligand-field theory in comparison with those of some typical authentic Mn complexes. It was deduced that i) all of the four Mn ions in the S1-state are octahedrally coordinated and two of them constitute a di-mu-oxo bridged Mn(III, III) dimeric subunit; ii) the bridged Mn(III) ions are further bridged by a deprotonated water dimer, (HOHOH)-, and coordinated by imidazole-N and carboxylate-O- on the opposite side of the Mn atom from the di-mu-oxo bridge; iii) the other two Mn ions exist in the form of Mn(III) monomeric subunits; and iv) upon the S1----S2 transition, only the bridged Mn(III,III) is oxidized to Mn(III,IV). The distinct change in the principal absorption band shape upon the S1----S2 transition is briefly discussed to obtain the XANES evidence for a tetrameric Mn-cluster.

  9. Low-Dose-Rate Computed Tomography System Utilizing 25 mm/s-Scan Silicon X-ray Diode and Its Application to Iodine K-Edge Imaging Using Filtered Bremsstrahlung Photons

    NASA Astrophysics Data System (ADS)

    Matsushita, Ryo; Sato, Eiichi; Yanbe, Yutaka; Chiba, Hiraku; Maeda, Tomoko; Hagiwara, Osahiko; Matsukiyo, Hiroshi; Osawa, Akihiro; Enomoto, Toshiyuki; Watanabe, Manabu; Kusachi, Shinya; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

    2013-03-01

    A low-dose-rate X-ray computed tomography (CT) system is useful for reducing absorbed dose for patients. The CT system with a tube current of sub-mA was developed using a silicon X-ray diode (Si-XD). The Si-XD is a high-sensitivity Si photodiode (PD) selected for detecting X-ray photons, and the X-ray sensitivity of the Si-XD was twice as high as that of Si-PD cerium-doped yttrium aluminum perovskite [YAP(Ce)]. X-ray photons are directly detected using the Si-XD without a scintillator, and the photocurrent from the diode is amplified using current-voltage and voltage-voltage amplifiers. The output voltage is converted into logical pulses using a voltage-frequency converter with a maximum frequency of 500 kHz, and the frequency is proportional to the voltage. The pulses from the converter are sent to the differentiator with a time constant of 500 ns to generate short positive pulses for counting, and the pulses are counted using a counter card. Tomography is accomplished by repeated linear scans and rotations of an object, and projection curves of the object are obtained by the linear scan. The exposure time for obtaining a tomogram was 5 min at a scan step of 0.5 mm and a rotation step of 3.0°. The tube current and voltage were 0.55 mA and 60 kV, respectively, and iodine K-edge CT was carried out using filtered bremsstrahlung X-ray spectra with a peak energy of 38 keV.

  10. Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors.

    PubMed

    Shakeri Yekta, Sepehr; Gustavsson, Jenny; Svensson, Bo H; Skyllberg, Ulf

    2012-01-30

    The effect of sequential extraction of trace metals on sulfur (S) speciation in anoxic sludge samples from two lab-scale biogas reactors augmented with Fe was investigated. Analyses of sulfur K-edge X-ray absorption near edge structure (S XANES) spectroscopy and acid volatile sulfide (AVS) were conducted on the residues from each step of the sequential extraction. The S speciation in sludge samples after AVS analysis was also determined by S XANES. Sulfur was mainly present as FeS (≈ 60% of total S) and reduced organic S (≈ 30% of total S), such as organic sulfide and thiol groups, in the anoxic solid phase. Sulfur XANES and AVS analyses showed that during first step of the extraction procedure (the removal of exchangeable cations), a part of the FeS fraction corresponding to 20% of total S was transformed to zero-valent S, whereas Fe was not released into the solution during this transformation. After the last extraction step (organic/sulfide fraction) a secondary Fe phase was formed. The change in chemical speciation of S and Fe occurring during sequential extraction procedure suggests indirect effects on trace metals associated to the FeS fraction that may lead to incorrect results. Furthermore, by S XANES it was verified that the AVS analysis effectively removed the FeS fraction. The present results identified critical limitations for the application of sequential extraction for trace metal speciation analysis outside the framework for which the methods were developed. Copyright © 2011 Elsevier B.V. All rights reserved.

  11. Antiferromagnetically Spin Polarized Oxygen Observed in Magneto-electric TbMn2O5

    SciTech Connect

    Wilkins, S.B.; Beale, T.A.W.; Johnson, R.D.; Bland, S.R.; Joly, Y.; Forrest, T.R.; McMorrow, D.F.; Yakhou, F.; Prabhakaran, D.; Boothroyd, A.T.; Hatton, P.D.

    2010-08-18

    We report the direct measurement of antiferromagnetic spin polarization at the oxygen sites in the multiferroic TbMn{sub 2}O{sub 5}, through resonant soft x-ray magnetic scattering. This supports recent theoretical models suggesting that the oxygen spin polarization is key to the magnetoelectric coupling mechanism. The spin polarization is observed through a resonantly enhanced diffraction signal at the oxygen K edge at the commensurate antiferromagnetic wave vector. Using the fdmnes code we have accurately reproduced the experimental data. We have established that the resonance arises through the spin polarization on the oxygen sites hybridized with the square based pyramid Mn{sup 3+} ions. Furthermore we have discovered that the position of the Mn{sup 3+} ion directly influences the oxygen spin polarization.

  12. Polarization measurement through combination polarizers

    NASA Astrophysics Data System (ADS)

    Bai, Yunfeng; Li, Linjun; He, Zhelong; Liu, Yanwei; Ma, Cheng; Shi, Guang; Liu, Lu

    2014-02-01

    Polarization measurement approaches only using polarizer and grating is present. The combination polarizers consists of two polarizers: one is γ degree with the X axis; the other is along the Y axis. Binary grating is covered by the combination polarizers, and based on Fraunhofer diffraction, the diffraction intensity formula is deduced. The polarization state of incident light can be gotten by fitting the diffraction pattern with the deduced formula. Compared with the traditional polarization measurement method, this measurement only uses polarizer and grating, therefore, it can be applied to measure a wide wavelength range without replacing device in theory.

  13. Local Cu and Br environments and their relationship to superconductivity restoration in brominated YBa{sub 2}Cu{sub 3}O{sub y}

    SciTech Connect

    Potrepka, D.M.; Fenner, D.B.; Balasubramanian, M.; Hines, W.A.; Budnick, J.I.

    1998-08-01

    {sup 63,65}Cu nuclear quadrupole resonance (NQR) and Br {ital k}-edge x-ray absorption fine structure (XAFS) have been used to study the local structures in well-characterized samples of deoxygenated and brominated YBa{sub 2}Cu{sub 3}O{sub y}(YBCO). NQR shows that after bromination of YBa{sub 2}Cu{sub 3}O{sub 6.1} at 260thinsp{degree}C, oxygen has repopulated the chain sites. From XAFS, it is concluded that Br does not enter the YBCO lattice, but rather precipitates out as small nanoscale particles of BaBr{sub 2}. These results provide clear evidence of the role of Br in reoxygenating the YBCO structure and an explanation for the partial restoration of superconductivity in the YBCO system. {copyright} {ital 1998 American Institute of Physics.}

  14. X-ray absorption spectroscopic study of new high-Tc superconducting intercalation compound of (HgX2)0.5Bi2Sr2CaCu2Oy(X=Br,I)

    NASA Astrophysics Data System (ADS)

    Choy, Jin-Ho; Park, Nam-Gyu; Hwang, Seong-Ju; Hwang, Sung-Ho; Kim, Dong-Hoon

    1996-06-01

    We have systematically performed x-ray absorption spectroscopic (XAS) studies on the new mercuric halide intercalated superconductors, (HgX2)0.5Bi2Sr2CaCu2Oy with X equals Br and I, in order to investigate the electronic and crystal structure of these compounds. The present Hg LIII-edge EXAFS results indicate that the mercury is coordinated with two bromide or iodide ligands with bond length of 2.46 angstrom for the HgBr2-intercalate and 2.65 angstrom for the HgI2-one. This is the first example of linear molecular salt of HgX2 stabilized in the solid lattice. According to the I LI- and Br K-edge x-ray absorption near edge structure (XANES) spectroscopic studies, a small amount of electron transfer from the intercalant HgX2 to the host lattice could be observed upon intercalation, resulting in the negatively charged state of (HgX2)(delta -). The Cu K-edge EXAFS analysis reveals that the bond distance of Cu-Oaxial is slightly shortened upon intercalation, reflecting the oxidation of (Cu-O) layer, which is well consistent with the I LI- and Br K-edge XANES results.

  15. Local Cu and Br Environments and Their Relationship to Superconductivity Restoration in Brominated YBa_2Cu_3O_6.1

    NASA Astrophysics Data System (ADS)

    Potrepka, D. M.; Budnick, J. I.; Fenner, D. B.; Balasubramanian, M.; Hines, W. A.

    1998-03-01

    ^63,65Cu NQR and Br K-edge XAFS are used to study the local structures of Cu and Br in YBa_2Cu_3O_7-δ, YBa_2Cu_3O_6.1, and brominated YBa_2Cu_3O_6.1 samples. The results answer the long standing question of how Br restores superconductivity in deoxygenated YBa_2Cu_3O_7-δ. Past studies led one to consider that the Br occupies regions near chain oxygen sites with a redistribution of chain oxygens.(H.B. Radousky et al., Phys. Rev. B 41 11140 (1990); M. Mokhtari et al., Solid State Commun. 93 487 (1995).) The Br XAFS data presented here provides compelling evidence for the formation of nanoscale BaBr2 precipitates resulting from local destruction of the YBa_2Cu_3O_6.1 phase. On the basis of the Cu NQR experiments, it is concluded that through this nanoscale decomposition reaction, oxygen is liberated which goes into the nearby chain sites thus restoring superconductivity. (Support from Conn. Critical Technologies, DOE, and initially AFOSR-SBIR)

  16. Impact of S fertilizers on pore-water Cu dynamics and transformation in a contaminated paddy soil with various flooding periods.

    PubMed

    Yang, Jianjun; Zhu, Shenhai; Zheng, Cuiqing; Sun, Lijuan; Liu, Jin; Shi, Jiyan

    2015-04-09

    Impact of S fertilization on Cu mobility and transformation in contaminated paddy soils has been little reported. In this study, we investigated the dynamics and transformation of dissolved and colloidal Cu in the pore water of a contaminated paddy soil after applying ammonium sulphate (AS) and sulfur coated urea (SCU) with various flooding periods (1, 7 and 60 days). Compared to the control soil, the AS-treated soil released more colloidal and dissolved Cu over the entire flooding period, while the SCU-treated soil had lower colloidal Cu after 7-day flooding but higher colloidal and dissolved Cu after 60-day flooding. Microscopic X-ray fluorescence (μ-XRF) analysis found a close relationship between Fe and Cu distribution on soil colloids after 60-day flooding, implying the formation of colloidal Fe/Cu sulphide coprecipitates. Cu K-edge X-ray absorption near-edge structure (XANES) spectroscopy directly revealed the transformation of outer-sphere complexed Cu(II) species to Cu(II) sulphide and reduced Cu2O in the colloids of S-treated soils after 60-day flooding. These results demonstrated the great influence of S fertilization on pore-water Cu mobility by forming Cu sulphide under flooding conditions, which facilitated our understanding and control of Cu loss in contaminated paddy soils under S fertilization. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. High covalence in CuSO4 and the radicalization of sulfate: an X-ray absorption and density functional study.

    PubMed

    Szilagyi, Robert K; Frank, Patrick; DeBeer George, Serena; Hedman, Britt; Hodgson, Keith O

    2004-12-27

    Sulfur K-edge X-ray absorption spectroscopy (XAS) of anhydrous CuSO(4) reveals a well-resolved preedge transition feature at 2478.8 eV that has no counterpart in the XAS spectra of anhydrous ZnSO(4) or copper sulfate pentahydrate. Similar but weaker preedge features occur in the sulfur K-edge XAS spectra of [Cu(itao)SO(4)] (2478.4 eV) and [Cu[(CH(3))(6)tren]SO(4)] (2477.7 eV). Preedge features in the XAS spectra of transition metal ligands are generally attributed to covalent delocalization of a metal d-orbital hole into a ligand-based orbital. Copper L-edge XAS of CuSO(4) revealed that 56% of the Cu(II) 3d hole is delocalized onto the sulfate ligand. Hybrid density functional calculations on the two most realistic models of the covalent delocalization pathways in CuSO(4) indicate about 50% electron delocalization onto the sulfate oxygen-based 2p orbitals; however, at most 14% of that can be found on sulfate sulfur. Both experimental and computational results indicated that the high covalence of anhydrous CuSO(4) has made sulfate more like the radical monoanion, inducing an extensive mixing and redistribution of sulfur 3p-based unoccupied orbitals to lower energy in comparison to sulfate in ZnSO(4). It is this redistribution, rather than a direct covalent interaction between Cu(II) and sulfur, that is the origin of the observed sulfur XAS preedge feature. From pseudo-Voigt fits to the CuSO(4) sulfur K-edge XAS spectrum, a ground-state 3p character of 6% was quantified for the orbital contributing to the preedge transition, in reasonable agreement with the DFT calculation. Similar XAS fits indicated 2% sulfur 3p character for the preedge transition orbitals in [Cu(itao)SO(4)] and [Cu[(CH(3))(6)tren]SO(4)]. The covalent radicalization of ligands similar to sulfate, with consequent energy redistribution of the virtual orbitals, represents a new mechanism for the induction of ligand preedge XAS features. The high covalence of the Cu sites in CuSO(4) was found to be

  18. Characterization of atmospheric aerosols using Synchroton radiation total reflection X-ray fluorescence and Fe K-edge total reflection X-ray fluorescence-X-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Fittschen, U. E. A.; Meirer, F.; Streli, C.; Wobrauschek, P.; Thiele, J.; Falkenberg, G.; Pepponi, G.

    2008-12-01

    In this study a new procedure using Synchrotron total reflection X-ray fluorescence (SR-TXRF) to characterize elemental amounts in atmospheric aerosols down to particle sizes of 0.015 um is presented. The procedure was thoroughly evaluated regarding bounce off effects and blank values. Additionally the potential of total reflection X-ray fluorescence-X-ray absorption near edge structure (SR-TXRF-XANES) for speciation of FeII/III down to amounts of 34 pg in aerosols which were collected for 1 h is shown. The aerosols were collected in the city of Hamburg with a low pressure Berner impactor on Si carriers covered with silicone over time periods of 60 and 20 min each. The particles were collected in four and ten size fractions of 10.0-8.0 μm, 8.0-2.0 μm, 2.0-0.13 μm 0.13-0.015 μm (aerodynamic particle size) and 15-30 nm, 30-60 nm, 60-130 nm, 130-250 nm, 250-500 nm, 0.5-1 μm, 1-2 μm, 2-4 μm, 4-8 μm, 8-16 μm. Prior to the sampling "bounce off" effects on Silicone and Vaseline coated Si carriers were studied with total reflection X-ray fluorescence. According to the results silicone coated carriers were chosen for the analysis. Additionally, blank levels originating from the sampling device and the calibration procedure were studied. Blank levels of Fe corresponded to 1-10% of Fe in the aerosol samples. Blank levels stemming from the internal standard were found to be negligible. The results from the Synchroton radiation total reflection X-ray fluorescence analysis of the aerosols showed that 20 min of sampling time gave still enough sample material for elemental determination of most elements. For the determination of the oxidation state of Fe in the aerosols different Fe salts were prepared as a reference from suspensions in isopropanol. The results from the Fe K-edge Synchroton radiation total reflection X-ray fluorescence-X-ray absorption near-edge structure analysis of the aerosol samples showed that mainly Fe(III) was present in all particle size fractions.

  19. Electronic structure differences between H(2)-, Fe-, Co-, and Cu-phthalocyanine highly oriented thin films observed using NEXAFS spectroscopy.

    PubMed

    Willey, T M; Bagge-Hansen, M; Lee, J R I; Call, R; Landt, L; van Buuren, T; Colesniuc, C; Monton, C; Valmianski, I; Schuller, Ivan K

    2013-07-21

    Phthalocyanines, a class of macrocyclic, square planar molecules, are extensively studied as semiconductor materials for chemical sensors, dye-sensitized solar cells, and other applications. In this study, we use angular dependent near-edge x-ray absorption fine structure (NEXAFS) spectroscopy as a quantitative probe of the orientation and electronic structure of H2-, Fe-, Co-, and Cu-phthalocyanine molecular thin films. NEXAFS measurements at both the carbon and nitrogen K-edges reveal that phthalocyanine films deposited on sapphire have upright molecular orientations, while films up to 50 nm thick deposited on gold substrates contain prostrate molecules. Although great similarity is observed in the carbon and nitrogen K-edge NEXAFS spectra recorded for the films composed of prostrate molecules, the H2-phthalocyanine exhibits the cleanest angular dependence due to its purely out-of-plane π* resonances at the absorption onset. In contrast, organometallic-phthalocyanine nitrogen K-edges have a small in-plane resonance superimposed on this π* region that is due to a transition into molecular orbitals interacting with the 3dx(2)-y(2) empty state. NEXAFS spectra recorded at the metal L-edges for the prostrate films reveal dramatic variations in the angular dependence of specific resonances for the Cu-phthalocyanines compared with the Fe-, and Co-phthalocyanines. The Cu L3,2 edge exhibits a strong in-plane resonance, attributed to its b1g empty state with dx(2)-y(2) character at the Cu center. Conversely, the Fe- and Co- phthalocyanine L3,2 edges have strong out-of-plane resonances; these are attributed to transitions into not only b1g (dz(2)) but also eg states with dxz and dyz character at the metal center.

  20. Negative thermal expansion in CuCl: An extended x-ray absorption fine structure study

    SciTech Connect

    Vaccari, M.; Grisenti, R.; Fornasini, P.; Rocca, F.; Sanson, A.

    2007-05-01

    Extended x-ray absorption fine structure (EXAFS) has been measured from liquid helium to ambient temperature at the Cu K edge of copper chloride (CuCl) to investigate the local origin of negative thermal expansion. A quantitative analysis of the first coordination shell, performed by the cumulant method, reveals that the nearest-neighbor Cu-Cl interatomic distance undergoes a strong positive expansion, contrasting with the much weaker negative expansion of the crystallographic distance between average atomic positions below 100 K. The anisotropy of relative thermal vibrations, monitored by the ratio {gamma} between perpendicular and parallel mean square relative displacements, is considerably high, while the diffraction thermal factors are isotropic. The relative perpendicular vibrations measured by EXAFS are related to the tension mechanism and to the transverse acoustic modes, which are considered responsible for negative thermal expansion in zinc-blende structures.

  1. XANES and EXAFS study of Au-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1990-01-01

    The near-edge structure (XANES) of the Au L3 and Cu K edges of YBa2Au(0.3)Cu(2.7)O(7-delta) was studied. X ray diffraction suggests that Au goes on the Cu(1) site and XANES shows that this has little effect on the oxidation state of the remaining copper. The gold L3 edge develops a white line feature whose position lies between that of trivalent gold oxide (Au2O3) and monovalent potassium gold cyanide (KAu(CN)2) and whose intensity relative to the edge step is smaller than in the two reference compounds. The L3 EXAFS for Au in the superconductor resembles that of Au2O3. However, differences in the envelope of the Fourier filtered component for the first shell suggest that the local structure of the Au in the superconductor is not equivalent to Au2O3.

  2. Local atomic structure and oxidation processes of Cu(I) binding site in amyloid beta peptide: XAS Study

    NASA Astrophysics Data System (ADS)

    Kremennaya, M. A.; Soldatov, M. A.; Streltsov, V. A.; Soldatov, A. V.

    2016-05-01

    There are two different motifs of X-ray absorption spectra for Cu(I) K-edge in amyloid-β peptide which could be due to two different configurations of local Cu(I) environment. Two or three histidine ligands can coordinate copper ion in varying conformations. On the other hand, oxidation of amyloid-β peptide could play an additional role in local copper environment. In order to explore the peculiarities of local atomic and electronic structure of Cu(I) binding sites in amyloid-β peptide the x-ray absorption spectra were simulated for various Cu(I) environments including oxidized amyloid-β and compared with experimental data.

  3. Spectroscopic Evidence for a 3d(10) Ground State Electronic Configuration and Ligand Field Inversion in [Cu(CF3)4](1-).

    PubMed

    Walroth, Richard C; Lukens, James T; MacMillan, Samantha N; Finkelstein, Kenneth D; Lancaster, Kyle M

    2016-02-17

    The contested electronic structure of [Cu(CF3)4](1-) is investigated with UV/visible/near IR spectroscopy, Cu K-edge X-ray absorption spectroscopy, and 1s2p resonant inelastic X-ray scattering. These data, supported by density functional theory, multiplet theory, and multireference calculations, support a ground state electronic configuration in which the lowest unoccupied orbital is of predominantly trifluoromethyl character. The consensus 3d(10) configuration features an inverted ligand field in which all five metal-localized molecular orbitals are located at lower energy relative to the trifluoromethyl-centered σ orbitals.

  4. X-ray Absorption Spectroscopic and Computational Investigation of a Possible S···S Interaction in the [Cu3S2]3+ Core

    PubMed Central

    Sarangi, Ritimukta; Yang, Lei; Winikoff, Stuart G.; Gagliardi, Laura; Cramer, Christopher J.; Tolman, William B.; Solomon, Edward I.

    2011-01-01

    The electronic structure of the [Cu3S2]3+ core of [(LCu)3(S)2]3+ (L = N,N,N′,N′-tetramethyl-2R,3R-cyclohexanediamine) is investigated using a combination of Cu and S K-edge X-ray absorption spectroscopy and calculations at the density functional and multireference second-order perturbation levels of theory. The results show that the [Cu3S2]3+ core is best described as having all copper centers close to, but more oxidized than, Cu2+, while the charge on the S2 fragment is between that of a sulfide (S2−) and a subsulfide (S23−) species. The [Cu3S2]3+ core thus is different from a previously described, analogous [Cu3O2]3+ core, which has a localized [(Cu3+Cu2+Cu2+)(O2−)2]3+ electronic structure. The difference in electronic structure between the two analogues is attributed to increased covalent overlap between the Cu 3d and S 3p orbitals and the increased radial distribution function of the S 3p orbital (relative to O 2p). These features result in donation of electron density from the S-S σ* to the Cu and result in some bonding interaction between the two S atoms at ~ 2.69 Å in [Cu3S2]3+, stabilizing a delocalized S=1 ground state. PMID:21923178

  5. Preparation and characterization of a (Cu,Zn)-pMMO from Methylococcus capsulatus (Bath).

    PubMed

    Chen, Chang-Li; Chen, Kelvin H-C; Ke, Shyue-Chu; Yu, Steve S-F; Chan, Sunney I

    2004-12-01

    We report the preparation of a (Cu,Zn)-particulate methane monooxygenase (pMMO) in which the bulk of the copper ions of the electron-transfer clusters (E-clusters) has been replaced by divalent Zn ions. The Cu and Zn contents in the (Cu,Zn)-pMMO were determined by both inductively coupled plasma mass spectroscopy (ICP-MS) and X-ray absorption K-edge spectroscopy. Further characterization of the (Cu,Zn)-pMMO was provided by pMMO-activity assays as well as low-temperature electron paramagnetic resonance (EPR) spectroscopy following reductive titration and incubation in air or air/propylene mixtures. The pMMO-activity assays indicated that the (Cu,Zn)-pMMO was no longer capable of supporting catalytic turnover of hydrocarbon substrates. However, the EPR studies revealed that the catalytic cluster (C-cluster) copper ions in the (Cu,Zn)-pMMO were still capable of supporting the activation of dioxygen when reduced, and that the 14N-superhyperfine features associated with one of the type 2 Cu(II) centers in the hydroxylation C-cluster remained unperturbed. The replacement of the E-cluster copper ions by Zn ions did compromise the ability of the protein to mediate the transfer of reducing equivalents from exogenous reductants to the C-clusters. These observations provide strong support for the electron transfer and catalytic roles for the E-cluster and C-cluster copper ions, respectively.

  6. Polarization Aberrations

    NASA Technical Reports Server (NTRS)

    Mcguire, James P., Jr.; Chipman, Russell A.

    1990-01-01

    The analysis of the polarization characteristics displayed by optical systems can be divided into two categories: geometrical and physical. Geometrical analysis calculates the change in polarization of a wavefront between pupils in an optical instrument. Physical analysis propagates the polarized fields wherever the geometrical analysis is not valid, i.e., near the edges of stops, near images, in anisotropic media, etc. Polarization aberration theory provides a starting point for geometrical design and facilitates subsequent optimization. The polarization aberrations described arise from differences in the transmitted (or reflected) amplitudes and phases at interfaces. The polarization aberration matrix (PAM) is calculated for isotropic rotationally symmetric systems through fourth order and includes the interface phase, amplitude, linear diattenuation, and linear retardance aberrations. The exponential form of Jones matrices used are discussed. The PAM in Jones matrix is introduced. The exact calculation of polarization aberrations through polarization ray tracing is described. The report is divided into three sections: I. Rotationally Symmetric Optical Systems; II. Tilted and Decentered Optical Systems; and Polarization Analysis of LIDARs.

  7. Polarization-dependent DANES study on vertically-aligned ZnO nanorods

    SciTech Connect

    Sun, Chengjun; Park, Chang-In; Jin, Zhenlan; Hwang, In-Hui; Heald, Steve M.; Han, Sang-Wook

    2016-01-01

    The local structural and local density of states of vertically-aligned ZnO nanorods were examined by using a polarization-dependent diffraction anomalous near edge structure (DANES) measurements from c-oriented ZnO nanorods at the Zn K edge with the incident x-ray electric field parallel and perpendicular to the x-ray momentum transfer direction. Orientation-dependent local structures determined by DANES were comparable with polarization-dependent EXAFS results. Unlike other techniques, polarization-dependent DANES can uniquely describe the orientation-dependent local structural properties and the local density of states of a selected element in selected-phased crystals of compounds or mixed-phased structures.

  8. Polar Bear

    USGS Publications Warehouse

    Amstrup, S.D.; ,; Lentfer, J.W.

    1988-01-01

    Polar bears are long-lived, late-maturing carnivores that have relatively low rates of reproduction and natural mortality. Their populations are susceptible to disturbance from human activities, such as the exploration and development of mineral resources or hunting. Polar bear populations have been an important renewable resource available to coastal communities throughout the Arctic for thousands of years.

  9. Macrophage Polarization.

    PubMed

    Murray, Peter J

    2017-02-10

    Macrophage polarization refers to how macrophages have been activated at a given point in space and time. Polarization is not fixed, as macrophages are sufficiently plastic to integrate multiple signals, such as those from microbes, damaged tissues, and the normal tissue environment. Three broad pathways control polarization: epigenetic and cell survival pathways that prolong or shorten macrophage development and viability, the tissue microenvironment, and extrinsic factors, such as microbial products and cytokines released in inflammation. A plethora of advances have provided a framework for rationally purifying, describing, and manipulating macrophage polarization. Here, I assess the current state of knowledge about macrophage polarization and enumerate the major questions about how activated macrophages regulate the physiology of normal and damaged tissues.

  10. Local structure investigation of (Co, Cu) co-doped ZnO nanocrystals and its correlation with magnetic properties

    NASA Astrophysics Data System (ADS)

    Tiwari, N.; Doke, S.; Lohar, A.; Mahamuni, Shailaja; Kamal, C.; Chakrabarti, Aparna; Choudhary, R. J.; Mondal, P.; Jha, S. N.; Bhattacharyya, D.

    2016-03-01

    Pure, Co doped and (Co, Cu) co-doped ZnO nanocrystals have been prepared by wet chemical route at room temperature to investigate the effect of Cu doping in Co doped ZnO nanocrystals . The nanocrystals have initially been characterized by X-ray diffraction, FTIR, Raman, optical absorption and EPR spectroscopy and the results were corroborated with DFT based electronic structure calculations. Magnetic properties of the samples have been investigated by studying their magnetic hysteresis behavior and temperature dependence of susceptibilities. Finally the local structure at the host and dopant sites of the nanocrystals have been investigated by Zn, Co and Cu K edges EXAFS measurements with synchrotron radiation to explain their experimentally observed magnetic properties.

  11. -Interface effects on the magnetic moment of Co and Cu in CoCu granular alloys

    SciTech Connect

    Garcia Prieto, A.; Fdez-Gubieda, M.L.; Chaboy, J.; Laguna-Marco, M.A.; Muro, T.; Nakamura, T.

    2005-12-01

    We report on x-ray magnetic circular dichroism experiments performed on Co{sub 5}Cu{sub 95} annealed granular alloys with giant magnetoresistance. Results on the Co-L{sub 2,3} edge evidence a direct correlation between the Co orbital and spin magnetic moment and the Co clusters interfacial roughness. On the other hand, we have found dichroism on the Cu-L{sub 2,3} edge, revealing an induced magnetic polarization of the Cu interfacial atoms. The magnetic moment of the Cu atoms is mainly of spin character and is ferromagnetically coupled with the Co magnetic moment.

  12. Pd/Cu site interchange in UCu{sub 5-x}Pd{sub x}

    SciTech Connect

    Booth, C.H.; Bauer, E.D.; Maple, M.B.; Chau, R.; Kwei, G.H.

    2001-07-11

    Although Pd/Cu site interchange in the non-Fermi liquid (NFL) material UCu{sub 4}Pd has been observed, the relationship between this disorder and the NFL behavior remains unclear. In order to better compare to the UCu{sub 5-x}Pd{sub x} phase diagram, they report results from Pd K edge x-ray absorption fine structure (XAFS) experiments on this series (x = 0.3-1.5) that determine the fraction of Pd atoms on the nominally Cu (16e) sites, s. They find that for these unannealed samples, s is at least 17% for all the samples measured, even for x < 1.0, although it does climb monotonically beyond its minimum at x = 0.7. These data are compared to changes in the lattice parameter as a function of x.

  13. Polar Bears

    USGS Publications Warehouse

    Amstrup, Steven C.; Douglas, David C.; Reynolds, Patricia E.; Rhode, E.B.

    2002-01-01

    Polar bears (Ursus maritimus) are hunted throughout most of their range. In addition to hunting polar bears of the Beaufort Sea region are exposed to mineral and petroleum extraction and related human activities such as shipping road-building, and seismic testing (Stirling 1990).Little was known at the start of this project about how polar bears move about in their environment, and although it was understood that many bears travel across political borders, the boundaries of populations had not been delineated (Amstrup 1986, Amstrup et al. 1986, Amstrup and DeMaster 1988, Garner et al. 1994, Amstrup 1995, Amstrup et al. 1995, Amstrup 2000).As human populations increase and demands for polar bears and other arctic resources escalate, managers must know the sizes and distributions of the polar bear populations. Resource managers also need reliable estimates of breeding rates, reproductive intervals, litter sizes, and survival of young and adults.Our objectives for this research were 1) to determine the seasonal and annual movements of polar bears in the Beaufort Sea, 2) to define the boundaries of the population(s) using this region, 3) to determine the size and status of the Beaufort Sea polar bear population, and 4) to establish reproduction and survival rates (Amstrup 2000).

  14. Polar Glaciology

    NASA Technical Reports Server (NTRS)

    Robin, G. D.

    1984-01-01

    Two fields of research on polar ice sheets are likely to be of dominant interest during the 1990s. These are: the role of polar ice sheets in the hydrological cycle ocean-atmosphere-ice sheets-oceans, especially in relation to climate change; and the study and interpretation of material in deep ice cores to provide improved knowledge of past climates and of the varying levels of atmospheric constituents such as CO2, NOx, SO2, aerosols, etc., over the past 200,000 years. Both topics require a better knowledge of ice dynamics. Many of the studies that should be undertaken in polar regions by Earth Observing System require similar instruments and techniques to those used elsewhere over oceans and inland surfaces. However to study polar regions two special requirements need to be met: Earth Observing System satellite(s) need to be in a sufficiently high inclination orbit to cover most of the polar regions. Instruments must also be adapted, often by relatively limited changes, to give satisfactory data over polar ice. The observational requirements for polar ice sheets in the 1990s are summarized.

  15. Characterization of Binary Ag-Cu Ion Mixtures in Zeolites: Their Reduction Products and Stability to Air Oxidation

    SciTech Connect

    Fiddy, Steven; Petranovskii, Vitalii; Ogden, Steve; Iznaga, Inocente Rodriguez

    2007-02-02

    A series of Ag+-Cu2+ binary mixtures with different Ag/Cu ratios were supported on mordenite with different Si/Al ratios and were subsequently reduced under hydrogen in the temperature range 323K - 473K. Ag and Cu K-edge X-ray Absorption Spectroscopy (XAS) was conducted on these systems in-situ to monitor the reduction species formed and the kinetics of their reduction. In-situ XANES clearly demonstrates that the formation of silver particles is severely impeded by the addition of copper and that the copper is converted from Cu(II) to Cu(I) during reduction and completely reverts back to Cu(II) during cooling. There are no indications at any stage of the formation of bimetallic Ag-Cu clusters. Interestingly, the Ag/Cu ratio appears to have no influence of the reduction kinetics and reduction products formed with only the highest Si/Al ratio (MR = 128) investigated during this study having an influence on the reduction and stability to air oxidation.

  16. Copper position in type-I Ba 8Cu 4Si 42 clathrate

    NASA Astrophysics Data System (ADS)

    Yang, L.; Wang, Y.; Liu, T.; Hu, T. D.; Li, B. X.; Ståhl, K.; Chen, S. Y.; Li, M. Y.; Shen, P.; Lu, G. L.; Wang, Y. W.; Jiang, J. Z.

    2005-06-01

    Local structure of Cu in a type-I Ba 8Cu 4Si 42 clathrate has been investigated by synchrotron X-ray powder diffraction, Cu K-edge extended X-ray absorption fine spectroscopy, X-ray absorption near edge spectroscopy (XANES) and theoretical calculation. It is found that XANES spectra cannot be explained by the substitution of Cu atoms at Si16 i, and Si24 k positions. Our calculations show that the binding energies of the Si atom in Si16 i, Si24 k and Si6 c positions are 9.000, 9.495 and 8.911 eV, respectively. Both experimental and theoretical results support that Cu atoms in the type-I Ba 8Cu 4Si 42 clathrate, as a doped element, prefer to occupy the least-binding Si, i.e., the Si6 c sites. No structural change between 112 and 300 K was observed and the (100)-faceted cubic crystal has negligible distortion/ordering according to transmission electron microscopy.

  17. Corrosion behavior of Au and Ag modified Cu-Ni-Mn alloys.

    PubMed

    Wright, S R; Cocks, F H; Gettleman, L

    1980-04-01

    The linear electrochemical polarization method was used to provide quantitative in vitro measurements of corrosion rates as a function of exposure time for Cu-Ni-Mn, Cu-Ni-Mn-Au, Cu-Ni-Mn-Ag, and Cu-Ni-Mn-Au-Ag alloys in artificial saliva. Both Au and Ag additives to dental-cast Cu-Ni-Mn alloys lowered the corrosion rate significantly.

  18. Polar Plumage

    NASA Image and Video Library

    2006-05-08

    This Mars MOC image shows dunes in the north polar region of Mars covered by a layer of carbon dioxide frost that accumulated during the winter in 2005. Dark spots indicate areas where frost has begun to sublime away

  19. Polar Dunes

    NASA Image and Video Library

    2010-09-27

    By high summer, the extensive dune fields of the north polar region are completely defrosted and the number and variety of dunes are readily visible. This image was captured by NASA Mars Odyssey on August 31, 2010.

  20. Polar Cone

    NASA Image and Video Library

    2006-07-10

    This MOC image shows a cone-shaped hill, perhaps a remnant of a material that was once more laterally extensive across the area, on a textured plain in the Hyperboreus Labyrinthus region in the north polar region of Mars

  1. Polarizing cues.

    PubMed

    Nicholson, Stephen P

    2012-01-01

    People categorize themselves and others, creating ingroup and outgroup distinctions. In American politics, parties constitute the in- and outgroups, and party leaders hold sway in articulating party positions. A party leader's endorsement of a policy can be persuasive, inducing co-partisans to take the same position. In contrast, a party leader's endorsement may polarize opinion, inducing out-party identifiers to take a contrary position. Using survey experiments from the 2008 presidential election, I examine whether in- and out-party candidate cues—John McCain and Barack Obama—affected partisan opinion. The results indicate that in-party leader cues do not persuade but that out-party leader cues polarize. This finding holds in an experiment featuring President Bush in which his endorsement did not persuade Republicans but it polarized Democrats. Lastly, I compare the effect of party leader cues to party label cues. The results suggest that politicians, not parties, function as polarizing cues.

  2. Polar Clouds

    NASA Image and Video Library

    2012-02-27

    With the changing of seasons comes changes in weather. This image from NASA 2001 Mars Odyssey spacecraft shows clouds in the north polar region. The surface is just barely visible in part of the image.

  3. Hepatocyte Polarity

    PubMed Central

    Treyer, Aleksandr; Müsch, Anne

    2013-01-01

    Hepatocytes, like other epithelia, are situated at the interface between the organism’s exterior and the underlying internal milieu and organize the vectorial exchange of macromolecules between these two spaces. To mediate this function, epithelial cells, including hepatocytes, are polarized with distinct luminal domains that are separated by tight junctions from lateral domains engaged in cell-cell adhesion and from basal domains that interact with the underlying extracellular matrix. Despite these universal principles, hepatocytes distinguish themselves from other nonstriated epithelia by their multipolar organization. Each hepatocyte participates in multiple, narrow lumina, the bile canaliculi, and has multiple basal surfaces that face the endothelial lining. Hepatocytes also differ in the mechanism of luminal protein trafficking from other epithelia studied. They lack polarized protein secretion to the luminal domain and target single-spanning and glycosylphosphatidylinositol-anchored bile canalicular membrane proteins via transcytosis from the basolateral domain. We compare this unique hepatic polarity phenotype with that of the more common columnar epithelial organization and review our current knowledge of the signaling mechanisms and the organization of polarized protein trafficking that govern the establishment and maintenance of hepatic polarity. The serine/threonine kinase LKB1, which is activated by the bile acid taurocholate and, in turn, activates adenosine monophosphate kinase-related kinases including AMPK1/2 and Par1 paralogues has emerged as a key determinant of hepatic polarity. We propose that the absence of a hepatocyte basal lamina and differences in cell-cell adhesion signaling that determine the positioning of tight junctions are two crucial determinants for the distinct hepatic and columnar polarity phenotypes. PMID:23720287

  4. Vibrations on Cu surfaces covered with Ni monolayer

    NASA Astrophysics Data System (ADS)

    Sklyadneva, I. Yu.; Rusina, G. G.; Chulkov, E. V.

    1999-08-01

    Vibrational modes on the Cu(100) and Cu(111) surfaces covered with a Ni monolayer have been calculated using the embedded-atom method. A detailed discussion of the dispersion relations and polarizations of adsorbate modes and surface phonons is presented. The dispersion of the Rayleigh phonon is in good agreement with the experimental EELS data. The changes in interatomic force constants are discussed.

  5. Growth control, structure, chemical state, and photoresponse of CuO-CdS core-shell heterostructure nanowires.

    PubMed

    El Mel, A A; Buffière, M; Bouts, N; Gautron, E; Tessier, P Y; Henzler, K; Guttmann, P; Konstantinidis, S; Bittencourt, C; Snyders, R

    2013-07-05

    The growth of single-crystal CuO nanowires by thermal annealing of copper thin films in air is studied. We show that the density, length, and diameter of the nanowires can be controlled by tuning the morphology and structure of the copper thin films deposited by DC magnetron sputtering. After identifying the optimal conditions for the growth of CuO nanowires, chemical bath deposition is employed to coat the CuO nanowires with CdS in order to form p-n nanojunction arrays. As revealed by high-resolution TEM analysis, the thickness of the polycrystalline CdS shell increases when decreasing the diameter of the CuO core for a given time of CdS deposition. Near-edge x-ray absorption fine-structure spectroscopy combined with transmission x-ray microscopy allows the chemical analysis of isolated nanowires. The absence of modification in the spectra at the Cu L and O K edges after the deposition of CdS on the CuO nanowires indicates that neither Cd nor S diffuse into the CuO phase. We further demonstrate that the core-shell nanowires exhibit the I-V characteristic of a resistor instead of a diode. The electrical behavior of the device was found to be photosensitive, since increasing the incident light intensity induces an increase in the collected electrical current.

  6. Quantifying point defects in Cu2ZnSn(S,Se)4 thin films using resonant x-ray diffraction

    DOE PAGES

    Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.; ...

    2016-10-17

    Cu2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu2ZnSnS4 (8.6% efficiency) and Cu2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level of CuZn and ZnCumore » defects on the 2c and 2d Wyckoff positions. Furthermore, we observe a significantly lower concentration of ZnSn defects and Cu or Zn vacancies.« less

  7. Local Structure Studies of As-Made Cu2ZnSnS4 Nanoparticles

    NASA Astrophysics Data System (ADS)

    Jewell, Leila; Rocco, Sophia; Bridges, Frank; Carter, Sue A.

    2017-06-01

    Though Cu2ZnSnS4 (CZTS) is a promising material for thin-film solar cells, a significant challenge remains in understanding the structures being formed, particularly in nonstoichiometric materials. We use the extended x-ray absorption fine-structure technique to study the local structure and stoichiometry of as-made, Cu-deficient CZTS nanoparticles and present K -edge data and fits for each of the cations (Cu, Zn, and Sn). The data show that all of the metal-S (M -S ) pairs have the bond lengths of the kesterite structure within 0.02 Å, and the pair distribution function is very narrow (σ ˜0.07 Å ). These results preclude significant fractions of other phases with different M -S bond lengths. The data also reveal some Sn second neighbors around Sn, whereas there are none in the stoichiometric kesterite (or stannite) structure. Consequently, Sn antisite defects must be present on Cu or Zn sites; this is not surprising since there is some excess of Sn. More importantly, the second-neighbor Sn-Sn distance is significantly longer than other M -M distances, and the antisite Sn defects must therefore introduce significant disorder within the Cu and Zn sublattices. The largest distortions are found around Cu and are modeled using a strongly broadened (or split) peak distribution for the Cu -Cu /Zn pairs. We also find that excess Zn does not occupy Cu sites but instead, goes onto Sn sites. The samples are best described as a kesterite structure with significant antisite disorder.

  8. Three-dimensional local structure of photoexcited Cu diimine complex refined by quantitative XANES analysis.

    SciTech Connect

    Smolentsev, G.; Soldatov, A. V.; Chen, L. X.; Chemical Sciences and Engineering Division; Southern Federal Univ.; Northwestern Univ.

    2008-05-28

    The structural details of [Cu(dmp){sub 2}]{sup +} (dmp = 2,9-dimethyl-1,10-phenanthroline) at its metal-to-ligand charge-transfer (MLCT) excited-state in acetonitrile were extracted using quantitative analysis of Cu K-edge X-ray adsorption near edge structure (XANES). The study combines two techniques: fitting experimental XANES spectra with a multidimensional interpolation approximation, and calculating theoretical XANES spectra with molecular potentials beyond the muffin-tin approximation. The results of the study show that the best fit of the experimental XANES data must include a solvent molecule binding to the Cu with a short Cu-N distance of 2.00 {angstrom}. This confirms that the formation of an exciplex is responsible for the excited-state quenching in coordinating solvents, such as acetonitrile. Moreover, the calculations suggest that the formation of this exciplex state is accompanied by significant rocking distortions of the dmp ligands resulting in a 108{sup o} angle between the N(solvent)-Cu bond and the C{sub 2} symmetry axis of the dmp ligand. This combined approach allows us to extract molecular configurations that would otherwise be missed in a conventional qualitative XANES analysis.

  9. Full Polarization Analysis of Resonant Superlattice and Forbidden x-ray Reflections in Magnetite

    SciTech Connect

    Wilkins, S.B.; Bland, S.R.; Detlefs, B.; Beale, T.A.W.; Mazzoli, C.; Joly, Y.; Hatton, P.D.; Lorenzo, J.E.; Brabers, V.A.M.

    2009-12-02

    Despite being one of the oldest known magnetic materials, and the classic mixed valence compound, thought to be charge ordered, the structure of magnetite below the Verwey transition is complex and the presence and role of charge order is still being debated. Here, we present resonant x-ray diffraction data at the iron K-edge on forbidden (0, 0, 2n+1){sub C} and superlattice (0, 0, 2n+1/2)C reflections. Full linear polarization analysis of the incident and scattered light was conducted in order to explore the origins of the reflections. Through simulation of the resonant spectra we have confirmed that a degree of charge ordering takes place, while the anisotropic tensor of susceptibility scattering is responsible for the superlattice reflections below the Verwey transition. We also report the surprising result of the conversion of a significant proportion of the scattered light from linear to nonlinear polarization.

  10. Cu-Induced Dielectric Breakdown of Porous Low-Dielectric-Constant Film

    NASA Astrophysics Data System (ADS)

    Cheng, Yi-Lung; Lee, Chih-Yen; Huang, Yao-Liang; Sun, Chung-Ren; Lee, Wen-Hsi; Chen, Giin-Shan; Fang, Jau-Shiung; Phan, Bach Thang

    2017-02-01

    Dielectric breakdown induced by Cu ion migration in porous low-k dielectric films has been investigated in alternating-polarity bias conditions using a metal-insulator-metal capacitor with Cu top metal electrode. The experimental results indicated that Cu ions migrated into the dielectric film under stress with positive polarity, leading to weaker dielectric strength and shorter time to failure (TTF). In the alternating-polarity test, the measured TTFs increased with decreasing stressing frequency, implying backward migration of Cu ions during reverse-bias stress. Additionally, compared with a direct-current stress condition, the measured TTFs were higher as the frequency was decreased to 10-2 Hz. The electric-field acceleration factor for porous low-k dielectric film breakdown in the alternating-polarity test was also found to increase. This Cu backward migration effect is effective when the stressing time under negative polarity is longer than 0.1 s.

  11. Cu-Induced Dielectric Breakdown of Porous Low-Dielectric-Constant Film

    NASA Astrophysics Data System (ADS)

    Cheng, Yi-Lung; Lee, Chih-Yen; Huang, Yao-Liang; Sun, Chung-Ren; Lee, Wen-Hsi; Chen, Giin-Shan; Fang, Jau-Shiung; Phan, Bach Thang

    2017-06-01

    Dielectric breakdown induced by Cu ion migration in porous low- k dielectric films has been investigated in alternating-polarity bias conditions using a metal-insulator-metal capacitor with Cu top metal electrode. The experimental results indicated that Cu ions migrated into the dielectric film under stress with positive polarity, leading to weaker dielectric strength and shorter time to failure (TTF). In the alternating-polarity test, the measured TTFs increased with decreasing stressing frequency, implying backward migration of Cu ions during reverse-bias stress. Additionally, compared with a direct-current stress condition, the measured TTFs were higher as the frequency was decreased to 10-2 Hz. The electric-field acceleration factor for porous low- k dielectric film breakdown in the alternating-polarity test was also found to increase. This Cu backward migration effect is effective when the stressing time under negative polarity is longer than 0.1 s.

  12. Polarized Campuses.

    ERIC Educational Resources Information Center

    Parr, Susan Resneck

    1991-01-01

    On college campuses, the climate is polarized because of intolerance and discrimination, censorship, factionalism, and anger among students and faculty. As a result, the campus is in danger of becoming dominated by political issues and discouraging the exchange of ideas characteristic of a true liberal arts education. (MSE)

  13. Polar Stratigraphy

    NASA Technical Reports Server (NTRS)

    1999-01-01

    These three images were taken on three different orbits over the north polar cap in April 1999. Each shows a different part of the same ice-free trough. The left and right images are separated by a distance of more than 100 kilometers (62 miles). Note the similar layers in each image.

  14. Polar Dune

    NASA Image and Video Library

    2009-07-01

    A large sand sheet with surface dune forms is located on the floor of this crater near the south pole. The polar cap rests against the southern part of the sand sheet. The dune appears bright in this daytime 2001 Mars Odyssey THEMIS IR image.

  15. Magnetic interactions in CuII-LnIII cyclic tetranuclear complexes: is it possible to explain the occurrence of SMM behavior in CuII-TbIII and CuII-DyIII complexes?

    PubMed

    Hamamatsu, Takefumi; Yabe, Kazuya; Towatari, Masaaki; Osa, Shutaro; Matsumoto, Naohide; Re, Nazzareno; Pochaba, Andrzej; Mrozinski, Jerzy; Gallani, Jean-Louis; Barla, Alessandro; Imperia, Paolo; Paulsen, Carley; Kappler, Jean-Paul

    2007-05-28

    An extensive series of tetranuclear CuII2LnIII2 complexes [CuIILLnIII(hfac)2]2 (with LnIII being all lanthanide(III) ions except for the radioactive PmIII) has been prepared in order to investigate the nature of the CuII-LnIII magnetic interactions and to try to answer the following question: What makes the CuII2TbIII2 and CuII2DyIII2 complexes single molecule magnets while the other complexes are not? All the complexes within this series possess a similar cyclic tetranuclear structure, in which the CuII and LnIII ions are arrayed alternately via bridges of ligand complex (CuIIL). Regular SQUID magnetometry measurements have been performed on the series. The temperature-dependent magnetic susceptibilities from 2 to 300 K and the field-dependent magnetizations from 0 to 5 T at 2 K have been measured for the CuII2LnIII2 and NiII2LnIII2 complexes, with the NiII2LnIII2 complex containing diamagnetic NiII ions being used as a reference for the evaluation of the CuII-LnIII magnetic interactions. These measurements have revealed that the interactions between CuII and LnIII ions are very weakly antiferromagnetic if Ln=Ce, Nd, Sm, Yb, ferromagnetic if Ln=Gd, Tb, Dy, Ho, Er, Tm, and negligible if Ln=La, Eu, Pr, Lu. With the same goal of better understanding the evolution of the intramolecular magnetic interactions, X-ray magnetic circular dichroism (XMCD) has also been measured on CuII2TbIII2, CuII2DyIII2, and NiII2TbIII2 complexes, either at the L- and M-edges of the metal ions or at the K-edge of the N and O atoms. Last, the CuII2TbIII2 complex exhibiting SMM behavior has received a closer examination of its low temperature magnetic properties down to 0.1 K. These particular measurements have revealed the unusual very slow setting-up of a 3D order below 0.6 K.

  16. Phase transition from fcc to bcc structure of the Cu-clusters during nanocrystallization of Fe85.2Si1B9P4Cu0.8 soft magnetic alloy

    NASA Astrophysics Data System (ADS)

    Nishijima, Masahiko; Matsuura, Makoto; Takenaka, Kana; Takeuchi, Akira; Ofuchi, Hironori; Makino, Akihiro

    2014-05-01

    A role of Cu on the nanocrystallization of an Fe85.2Si1B9P4Cu0.8 alloy was investigated by X-ray absorption fine structure (XAFS) and transmission electron microscopy (TEM). The Cu K-edge XAFS results show that local structure around Cu is disordered for the as-quenched sample whereas it changes to fcc-like structure at 613 K. The fcc Cu-clusters are, however, thermodynamically unstable and begin to transform into bcc structure at 638 K. An explicit bcc structure is observed for the sample annealed at 693 K for 600 s in which TEM observation shows that precipitated bcc-Fe crystallites with ˜12 nm are homogeneously distributed. The bcc structure of the Cu-clusters transforms into the fcc-type again at 973 K, which can be explained by the TEM observations; Cu segregates at grain boundaries between bcc-Fe crystallites and Fe3(B,P) compounds. Combining the XAFS results with the TEM observations, the structure transition of the Cu-clusters from fcc to bcc is highly correlated with the preliminary precipitation of the bcc-Fe which takes place prior to the onset of the first crystallization temperature, Tx1 = 707 K. Thermodynamic analysis suggests that an interfacial energy density γ between an fcc-Cu cluster and bcc-Fe matrix dominates at a certain case over the structural energy between fcc and bcc Cu, ΔGfcc - bcc, which causes phase transition of the Cu clusters from fcc to bcc structure.

  17. Electronic excitations around the substituted atom in La2Cu1 -yNiyO4 as seen via resonantinelastic x-ray scattering

    SciTech Connect

    Ishii K.; Cai Y.; Tsutsui, K.; Ikeuchi, K.; Jarrige, I.; Mizuki, J.; Hiraka, H.; Yamada, K.; Tohyama, T.; Maekawa, S.; Endoh, Y.; Ishii, H.

    2012-03-14

    We perform a resonant inelastic x-ray scattering (RIXS) study of Ni-substituted La{sub 2}CuO{sub 4} and Cu-substituted La{sub 2}NiO{sub 4}. Resonantly enhanced charge-transfer excitations are successfully observed by tuning the incident photon energy to the K edge of the substituted element. These excitations display a very weak momentum dependence, evidencing their local character. We find a shift in the energy of the onset edge of these features compared with the nonsubstituted compounds La{sub 2}CuO{sub 4} and La{sub 2}NiO{sub 4}. This shift is quantitatively reproduced by exact diagonalization calculations of the RIXS spectra. RIXS is shown to be a powerful tool to probe the electronic states of substituted elements and to understand their interaction with surrounding atoms.

  18. Calculated Performance Of The Variable-Polarization Undulator Upgrade To The Daresbury SRS Soft X-Ray Undulator Beamline

    SciTech Connect

    Roper, Mark D.; Bird, Daniel T.

    2004-05-12

    The soft x-ray beamline 5U1 on the Daresbury Laboratory SRS currently uses a planar undulator, producing linearly polarized radiation in the range 100 to 1000 eV. The undulator is soon to be replaced by a variable-polarization device of the Apple II design. The aim is to produce circularly polarized light in the energy range 265 to 1000 eV, covering the K-edges of C, N and O, and the first row transition element L-edges. This will greatly enhance the provision of circularly polarized soft-x-rays on the SRS and open up new opportunities for experimenters. The device will also produce linear polarization with a selectable angle of polarization with respect to the orbit plane, which is currently unavailable on the SRS. In order to provide the coverage over this energy range, we are exploiting the relatively large emittance of the SRS to allow us to use the second and third harmonics even in circular polarization mode. This paper presents the expected beamline output in various polarization modes and the predicted degree of polarization.

  19. A quantitative description of the ground-state wave function of Cu(A) by X-ray absorption spectroscopy: comparison to plastocyanin and relevance to electron transfer.

    PubMed

    DeBeer George, S; Metz, M; Szilagyi, R K; Wang, H; Cramer, S P; Lu, Y; Tolman, W B; Hedman, B; Hodgson, K O; Solomon, E I

    2001-06-20

    To evaluate the importance of the electronic structure of Cu(A) to its electron-transfer (ET) function, a quantitative description of the ground-state wave function of the mixed-valence (MV) binuclear Cu(A) center engineered into Pseudomonas aeruginosa azurin has been developed, using a combination of S K-edge and Cu L-edge X-ray absorption spectroscopies (XAS). Parallel descriptions have been developed for a binuclear thiolate-bridged MV reference model complex ([(L(i)(PrdacoS)Cu)(2)](+)) and a homovalent (II,II) analogue ([L(i)(Pr2tacnS)Cu)(2)](2+), where L(i)(PrdacoS) and L(i)(Pr2tacnS) are macrocyclic ligands with attached thiolates that bridge the Cu ions. Previous studies have qualitatively defined the ground-state wave function of Cu(A) in terms of ligand field effects on the orbital orientation and the presence of a metal--metal bond. The studies presented here provide further evidence for a direct Cu--Cu interaction and, importantly, experimentally quantify the covalency of the ground-state wave function. The experimental results are further supported by DFT calculations. The nature of the ground-state wave function of Cu(A) is compared to that of the well-defined blue copper site in plastocyanin, and the importance of this wave function to the lower reorganization energy and ET function of Cu(A) is discussed. This wave function incorporates anisotropic covalency into the intra- and intermolecular ET pathways in cytochrome c oxidase. Thus, the high covalency of the Cys--Cu bond allows a path through this ligand to become competitive with a shorter His path in the intramolecular ET from Cu(A) to heme a and is particularly important for activating the intermolecular ET path from heme c to Cu(A).

  20. Micro-Raman Study of Orientation Effects of CuxSe-Crystallites on Cu-rich CuGaSe2 Thin Films

    NASA Astrophysics Data System (ADS)

    Xue, C.; Papadimitriou, D.; Raptis, Y. S.; Richter, W.; Esser, N.; Siebentritt, S.; Lux-Steiner, M. Ch.

    2004-08-01

    The structural properties of copper selenide (CuxSe), formed as a secondary phase on the surface of CuGaSe2 films grown under Cu-rich conditions on GaAs (100) substrates, were studied by micro-Raman spectroscopy. Raman bands at 45 and 263cm-1, observed on crystallites dispersed on the CuGaSe2 film, are in agreement with the Raman modes of CuSe and Cu2Se. Polarization- and angular-dependent micro-Raman measurements reveal that the CuxSe-crystallites are grown with a preferential orientation on the CuGaSe2 surface.

  1. EXAFS spectra using synchrotron radiation of Cu (II) complexes

    NASA Astrophysics Data System (ADS)

    Ninama, Samrath; Mishra, A.

    2016-10-01

    EXAFS analysis of Cu (II) complex as a ligand of 2-methyl-3-[(bis-aniline(R) phenyl]- 3H-1, 5 benzodiazepine. Extended X-ray absorption fine structure (EXAFS) spectra have been recorded at the K-edge of Cu (II) using the energy dispersive EXAFS beam line at 2.5GeV Indus - 2 synchrotron source at RRCAT, Indore, India. A theoretical EXAFS data analysis is also carried out by Fourier analysis of experimental EXAFS data of the copper (II) complexes. This analysis includes details of the Fourier transform of the data and the extraction of metal-ligand bond length. Bond lengths determined from data analysis methods are compared with the bond lengths obtained from several other known techniques, namely, Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. These data have also been calibrated by derivative method and bond lengths have also been obtained from Fourier transformation method and the results have been compared with the each other. The EXAFS data have been analyzed using the computer software Athena.

  2. Quasi-zero dimensional CuB2O4: a resonant inelastic X-ray scattering case study

    SciTech Connect

    Hancock, J.N.

    2010-04-29

    We explore the general phenomenology of resonant inelastic scattering (RIXS) using CuB{sub 2}O{sub 4}, a network of CuO{sub 4} plaquettes electronically isolated by B{sup +3} ions. Spectra show a small number of well-separated features, and we exploit the simple electronic structure to explore RIXS phenomenology by developing a calculation which allows for intermediate-state effects ignored in standard approaches. These effects are found to be non-negligible and good correspondence between our model and experiment leads to a simple picture of such phenomenology as the genesis of d {yields} d excitations at the K edge and intermediate-state interference effects.

  3. Influence of ligands on the electronic and magnetic properties of Fe porphyrin in gas phase and on Cu(001)

    SciTech Connect

    Brena, Barbara; Herper, Heike C.

    2015-05-07

    A study of the adsorption of different axial ligands on Fe porphyrin (FeP), both isolated and adsorbed on Cu(001), was performed by means of Density Functional Theory. The electronic and magnetic properties of the adsorbed FeP resulted to be strongly influenced by the axial ligands considered, Cl and O. Cl induces an enhancement of the overall molecular magnetic moment of 3.0 μ{sub B} while O or O{sub 2} leave the spin state of the molecule unchanged. The influence of the Cl in the electronic states was moreover studied by means of theoretical NEXAFS N K-edge, where the spectra of isolated FeP and FeP with Cl ligand were calculated. The adsorption of the FeP molecules on Cu(001) leads in case of Cl to a further increase of the magnetic moment due to strong deformation of the Fe-N bond.

  4. Structural study of an amorphous CuTi alloy produced by mechanical alloying using XRD, EXAFS and RMC simulations

    NASA Astrophysics Data System (ADS)

    Machado, K. D.; Maciel, G. A.; Sanchez, D. F.; de Lima, J. C.; Jóvári, P.

    2010-09-01

    The structure of an amorphous Cu 64Ti 36 alloy produced by mechanical alloying was studied by X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy techniques and modeled through reverse Monte Carlo simulations using the total structure factor S(K) and the EXAFS χ(k) oscillations on Cu K edge as input data. From the simulations the partial pair distribution functions g(r) and the bond-angle distribution functions Θ(cosθ) were determined and, from these functions, average coordination numbers and average interatomic distances for the first neighbors were calculated. We also obtained information about the three-dimensional structures present in the alloy.

  5. How the local geometry of the Cu-binding site determines the thermal stability of blue copper proteins.

    PubMed

    Chaboy, Jesús; Díaz-Moreno, Sofía; Díaz-Moreno, I; De la Rosa, Miguel A; Díaz-Quintana, Antonio

    2011-01-28

    Identifying the factors that govern the thermal resistance of cupredoxins is essential for understanding their folding and stability, and for improving our ability to design highly stable enzymes with potential biotechnological applications. Here, we show that the thermal unfolding of plastocyanins from two cyanobacteria--the mesophilic Synechocystis and the thermophilic Phormidium--is closely related to the short-range structure around the copper center. Cu K-edge X-ray absorption spectroscopy shows that the bond length between Cu and the S atom from the cysteine ligand is a key structural factor that correlates with the thermal stability of the cupredoxins in both oxidized and reduced states. These findings were confirmed by an additional study of a site-directed mutant of Phormidium plastocyanin showing a reverse effect of the redox state on the thermal stability of the protein.

  6. Photoinduced ferrimagnetic systems in Prussian blue analogues C(I)xCo4[Fe(CN)6]y (C(I) = alkali cation). 4. Characterization of the ferrimagnetism of the photoinduced metastable state in Rb1.8Co4[Fe(CN)6]3.3-13H2O by K edges X-ray magnetic circular dichroism.

    PubMed

    Champion, G; Escax, V; Cartier Dit Moulin, C; Bleuzen, A; Villain, F; Baudelet, F; Dartyge, E; Verdaguer, M

    2001-12-19

    In Part 2 of this work, the electronic and local structure of the photoinduced metastable magnetic state of the Prussian blue analogue Rb1.8Co4[Fe(CN)6]3.3-13H2O were characterized. To determine directly the relative orientation of the magnetic moments of Co(II) and Fe(III) ions in the metastable state, and the nature of the exchange interaction between them, we performed X-ray magnetic circular dichroism (XMCD) experiments at the cobalt and iron K edges. We present the first direct experimental evidence of the antiferromagnetic interaction between the cobalt and the iron ions, leading to the ferrimagnetism of the photoinduced metastable state.

  7. Persistent multiferroicity without magnetoelectric effects in CuO

    NASA Astrophysics Data System (ADS)

    Wang, Fen; Zou, Tao; Liu, Yi; Yan, Li-Qin; Sun, Young

    2011-09-01

    Multiferroicity and magnetoelectric effects in CuO have been investigated by measurements of magnetization, dielectric constant, and electric polarization with and without magnetic fields. Dielectric anomalies which indicate ferroelectric transitions were observed at two magnetic transition temperatures. Ferroelectric polarization was well detected in the incommensurate spiral phase. However, both dielectric constant and polarization have little changes in a 7 T magnetic field. Our study suggests that although with a high multiferroic temperature, the spiral spin structure in CuO is very stable and the induced ferroelectricity sustains even in a high magnetic field, which results in little magnetoelectric effects.

  8. Cell polarity

    PubMed Central

    Romereim, Sarah M

    2011-01-01

    Despite extensive genetic analysis of the dynamic multi-phase process that transforms a small population of lateral plate mesoderm into the mature limb skeleton, the mechanisms by which signaling pathways regulate cellular behaviors to generate morphogenetic forces are not known. Recently, a series of papers have offered the intriguing possibility that regulated cell polarity fine-tunes the morphogenetic process via orienting cell axes, division planes and cell movements. Wnt5a-mediated non-canonical signaling, which may include planar cell polarity, has emerged as a common thread in the otherwise distinct signaling networks that regulate morphogenesis in each phase of limb development. These findings position the limb as a key model to elucidate how global tissue patterning pathways direct local differences in cell behavior that, in turn, generate growth and form. PMID:22064549

  9. Polar Diving

    NASA Technical Reports Server (NTRS)

    2006-01-01

    3 July 2006 This Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) image shows layers exposed by erosion in a trough within the north polar residual cap of Mars, diving beneath a younger covering of polar materials. The layers have, since the Mariner 9 mission in 1972, been interpreted to be composed of a combination of dust and ice in unknown proportions. In this scene, a layer of solid carbon dioxide, which was deposited during the previous autumn and winter, blankets the trough as well as the adjacent terrain. Throughout northern spring, the carbon dioxide will be removed; by summer, the layers will be frost-free.

    Location near: 81.4oN, 352.2oW Image width: 3 km (1.9 mi) Illumination from: lower left Season: Northern Spring

  10. Polar Diving

    NASA Technical Reports Server (NTRS)

    2006-01-01

    3 July 2006 This Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) image shows layers exposed by erosion in a trough within the north polar residual cap of Mars, diving beneath a younger covering of polar materials. The layers have, since the Mariner 9 mission in 1972, been interpreted to be composed of a combination of dust and ice in unknown proportions. In this scene, a layer of solid carbon dioxide, which was deposited during the previous autumn and winter, blankets the trough as well as the adjacent terrain. Throughout northern spring, the carbon dioxide will be removed; by summer, the layers will be frost-free.

    Location near: 81.4oN, 352.2oW Image width: 3 km (1.9 mi) Illumination from: lower left Season: Northern Spring

  11. Polar Textures

    NASA Image and Video Library

    2017-06-08

    This VIS image of the south pole was taken at the end of summer. Frost will soon start to form as the season transitions into fall. Fall in the southern hemisphere means spring in the northern, so the north polar cap is just starting to thaw. Orbit Number: 67893 Latitude: -87.0251 Longitude: 275.679 Instrument: VIS Captured: 2017-04-04 06:19 https://photojournal.jpl.nasa.gov/catalog/PIA21679

  12. High-T(c) Superconductivity at the Interface between the CaCuO2 and SrTiO3 Insulating Oxides.

    PubMed

    Di Castro, D; Cantoni, C; Ridolfi, F; Aruta, C; Tebano, A; Yang, N; Balestrino, G

    2015-10-02

    At interfaces between complex oxides it is possible to generate electronic systems with unusual electronic properties, which are not present in the isolated oxides. One important example is the appearance of superconductivity at the interface between insulating oxides, although, until now, with very low T(c). We report the occurrence of high T(c) superconductivity in the bilayer CaCuO(2)/SrTiO(3), where both the constituent oxides are insulating. In order to obtain a superconducting state, the CaCuO(2)/SrTiO(3) interface must be realized between the Ca plane of CaCuO(2) and the TiO(2) plane of SrTiO(3). Only in this case can oxygen ions be incorporated in the interface Ca plane, acting as apical oxygen for Cu and providing holes to the CuO(2) planes. A detailed hole doping spatial profile can be obtained by scanning transmission electron microscopy and electron-energy-loss spectroscopy at the O K edge, clearly showing that the (super)conductivity is confined to about 1-2 CaCuO(2) unit cells close to the interface with SrTiO(3). The results obtained for the CaCuO(2)/SrTiO(3) interface can be extended to multilayered high T(c) cuprates, contributing to explaining the dependence of T(c) on the number of CuO(2) planes in these systems.

  13. High-Tc superconductivity at the interface between the CaCuO2 and SrTiO3 insulating oxides

    DOE PAGES

    Di Castro, D.; Cantoni, C.; Ridolfi, F.; ...

    2015-09-28

    At interfaces between complex oxides it is possible to generate electronic systems with unusual electronic properties, which are not present in the isolated oxides. One important example is the appearance of superconductivity at the interface between insulating oxides, although, until now, with very low Tc. We report the occurrence of high Tc superconductivity in the bilayer CaCuO2/SrTiO3, where both the constituent oxides are insulating. In order to obtain a superconducting state, the CaCuO2/SrTiO3 interface must be realized between the Ca plane of CaCuO2 and the TiO2 plane of SrTiO3. Only in this case can oxygen ions be incorporated in themore » interface Ca plane, acting as apical oxygen for Cu and providing holes to the CuO2 planes. In addition, a detailed hole doping spatial profile can be obtained by scanning transmission electron microscopy and electron-energy-loss spectroscopy at the O K edge, clearly showing that the (super)conductivity is confined to about 1–2 CaCuO2 unit cells close to the interface with SrTiO3. The results obtained for the CaCuO2/SrTiO3 interface can be extended to multilayered high Tc cuprates, contributing to explaining the dependence of Tc on the number of CuO2 planes in these systems.« less

  14. Evidence for Weakly Correlated Oxygen Holes in the Highest-Tc Cuprate Superconductor HgBa2 Ca2 Cu3 O8 +δ

    NASA Astrophysics Data System (ADS)

    Chainani, A.; Sicot, M.; Fagot-Revurat, Y.; Vasseur, G.; Granet, J.; Kierren, B.; Moreau, L.; Oura, M.; Yamamoto, A.; Tokura, Y.; Malterre, D.

    2017-08-01

    We study the electronic structure of HgBa2 Ca2 Cu3 O8 +δ (Hg1223; Tc=134 K ) using photoemission spectroscopy (PES) and x -ray absorption spectroscopy (XAS). Resonant valence band PES across the O K edge and Cu L edge identifies correlation satellites originating in O 2 p and Cu 3 d two-hole final states, respectively. Analyses using the experimental O 2 p and Cu 3 d partial density of states show quantitatively different on-site Coulomb energy for the Cu site (Ud d=6.5 ±0.5 eV ) and O site (Up p=1.0 ±0.5 eV ). Cu2 O7 -cluster calculations with nonlocal screening explain the Cu 2 p core level PES and Cu L -edge XAS spectra, confirm the Ud d and Up p values, and provide evidence for the Zhang-Rice singlet state in Hg1223. In contrast to other hole-doped cuprates and 3 d -transition metal oxides, the present results indicate weakly correlated oxygen holes in Hg1223.

  15. Inducing electric polarization in ultrathin insulating layers

    NASA Astrophysics Data System (ADS)

    Martinez-Castro, Jose; Piantek, Marten; Persson, Mats; Serrate, David; Hirjibehedin, Cyrus F.

    Studies of ultrathin polar oxide films have attracted the interest of researchers for a long time due to their different properties compared to bulk materials. However they present several challenges such as the difficulty in the stabilization of the polar surfaces and the limited success in tailoring their properties. Moreover, recently developed Van der Waals materials have shown that the stacking of 2D-layers trigger new collective states thanks to the interaction between layers. Similarly, interface phenomena emerge in polar oxides, like induced ferroelectricity. This represents a promising way for the creation of new materials with customized properties that differ from those of the isolated layers. Here we present a new approach for the fabrication and study of atomically thin insulating films. We show that the properties of insulating polar layers of sodium chloride (NaCl) can be engineered when they are placed on top of a charge modulated template of copper nitride (Cu2N). STM studies carried out in ultra-high vacuum and at low temperatures over NaCl/Cu2N/Cu(001) show that we are able to build up and stabilize interfaces of polar surface at the limit of one atomic layer showing new properties not present before at the atomic scale.

  16. Probing absolute spin polarization at the nanoscale.

    PubMed

    Eltschka, Matthias; Jäck, Berthold; Assig, Maximilian; Kondrashov, Oleg V; Skvortsov, Mikhail A; Etzkorn, Markus; Ast, Christian R; Kern, Klaus

    2014-12-10

    Probing absolute values of spin polarization at the nanoscale offers insight into the fundamental mechanisms of spin-dependent transport. Employing the Zeeman splitting in superconducting tips (Meservey-Tedrow-Fulde effect), we introduce a novel spin-polarized scanning tunneling microscopy that combines the probing capability of the absolute values of spin polarization with precise control at the atomic scale. We utilize our novel approach to measure the locally resolved spin polarization of magnetic Co nanoislands on Cu(111). We find that the spin polarization is enhanced by 65% when increasing the width of the tunnel barrier by only 2.3 Å due to the different decay of the electron orbitals into vacuum.

  17. Continuous control of spin polarization using a magnetic field

    SciTech Connect

    Gifford, J. A.; Zhao, G. J.; Li, B. C.; Tracy, Brian D.; Zhang, J.; Kim, D. R.; Smith, David J.; Chen, T. Y.

    2016-05-23

    The giant magnetoresistance (GMR) of a point contact between a Co/Cu multilayer and a superconductor tip varies for different bias voltage. Direct measurement of spin polarization by Andreev reflection spectroscopy reveals that the GMR change is due to a change in spin polarization. This work demonstrates that the GMR structure can be utilized as a spin source and that the spin polarization can be continuously controlled by using an external magnetic field.

  18. CuSbS2 as a negative electrode material for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Marino, C.; Block, T.; Pöttgen, R.; Villevieille, C.

    2017-02-01

    CuSbS2 was tested as a negative electrode material for sodium-ion batteries. The material synthesized by ball milling offers a specific charge of 730 mAh g-1, close to the theoretical value (751 mAh g-1), over a few cycles. The reaction mechanism was investigated by means of operando X-ray diffraction, 121Sb Mössbauer spectroscopy, and Cu K-edge X-ray absorption spectroscopy. These studies reveal a sodiation mechanism that involves an original conversion reaction in two steps, through the formation of a ternary phase, CuSb(1-x)S(2-y), as well as a NaxS alloy and Sb, followed by an alloying reaction involving the previously formed Sb. The desodiation process ends with the reformation of the ternary phase, CuSb(1-x‧)S(2-y‧), deficient in Sb and S; this phase is responsible for the good reversibility observed upon cycling.

  19. Cluster-seeded synthesis of doped CdSe:Cu4 quantum dots.

    PubMed

    Jawaid, Ali M; Chattopadhyay, Soma; Wink, Donald J; Page, Leah E; Snee, Preston T

    2013-04-23

    We report here a method for synthesizing CdSe quantum dots (QDs) containing copper such that each QD is doped with four copper ions. The synthesis is a derivative of the cluster-seed method, whereby organometallic clusters act as nucleation centers for quantum dots. The method is tolerant of the chemical identity of the seed; as such, we have doped four copper ions into CdSe QDs using [Na(H2O)3]2[Cu4(SPh)6] as a cluster seed. The controlled doping allows us to monitor the photophysical properties of guest ions with X-ray spectroscopy, specifically XANES and EXAFS at the copper K-edge. These data reveal that copper can capture both electrons and holes from photoexcited CdSe QDs. When the dopant is oxidized, photoluminescence is quenched and the copper ions translocate within the CdSe matrix, which slows the return to an emissive state.

  20. Polar Landforms

    NASA Technical Reports Server (NTRS)

    2005-01-01

    10 August 2005 This Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) image shows eroded remnants of carbon dioxide ice in the south polar residual cap of Mars. The scarps that outline each small mesa have retreated about 3 meters (10 feet) per Mars year since MGS began orbiting the red planet in 1997.

    Location near: 87.0oS, 31.9oW Image width: width: 3 km (1.9 mi) Illumination from: upper left Season: Southern Spring

  1. Polar ozone

    NASA Technical Reports Server (NTRS)

    Solomon, S.; Grose, W. L.; Jones, R. L.; Mccormick, M. P.; Molina, Mario J.; Oneill, A.; Poole, L. R.; Shine, K. P.; Plumb, R. A.; Pope, V.

    1990-01-01

    The observation and interpretation of a large, unexpected ozone depletion over Antarctica has changed the international scientific view of stratospheric chemistry. The observations which show the veracity, seasonal nature, and vertical structure of the Antarctic ozone hole are presented. Evidence for Arctic and midlatitude ozone loss is also discussed. The chemical theory for Antarctic ozone depletion centers around the occurrence of polar stratospheric clouds (PSCs) in Antarctic winter and spring; the climatology and radiative properties of these clouds are presented. Lab studies of the physical properties of PSCs and the chemical processes that subsequently influence ozone depletion are discussed. Observations and interpretation of the chemical composition of the Antarctic stratosphere are described. It is shown that the observed, greatly enhanced abundances of chlorine monoxide in the lower stratosphere are sufficient to explain much if not all of the ozone decrease. The dynamic meteorology of both polar regions is given, interannual and interhemispheric variations in dynamical processes are outlined, and their likely roles in ozone loss are discussed.

  2. Polar Terrains

    NASA Technical Reports Server (NTRS)

    2005-01-01

    [figure removed for brevity, see original site] Context image for PIA03577 Polar Terrains

    The region surrounding the South Polar Cap contains many different terrain types. This image shows both etched terrain and a region of 'mounds'.

    Image information: VIS instrument. Latitude 75S, Longitude 286.5E. 17 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  3. Polar Textures

    NASA Technical Reports Server (NTRS)

    2005-01-01

    [figure removed for brevity, see original site] Context image for PIA03638 Polar Textures

    This image illustrates the variety of textures that appear in the south polar region during late summer.

    Image information: VIS instrument. Latitude 80.5S, Longitude 57.9E. 17 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  4. Behavior of CuP and OFHC Cu anodes under electrodeposition conditions

    SciTech Connect

    Frankel, G.S.; Schrott, A.G.; Horkans, J.; Andricacos, P.C.; Isaacs, H.S.

    1992-08-01

    Films formed on CuP (with 0.05 wt % P) and OFHC Cu anodes in electroplating solutions were studied by X-ray Photoelectron Spectroscopy, X-ray Absorption Spectroscopy, electrochemical methods, and a newly developed gravimetric technique. The black film formed on CuP in Cl-containing solutions was found to resemble a porous sponge composed of CuCl but laden/with concentrated CuSO{sub 4} solution. The difference between the buoyancy-corrected measured mass change and the charge-equivalent mass change was found to have two components: a reversible part that comes and goes as the current is turned on and off, and an irreversible part that remains on the surface and increase in mass with time. The irreversible part results from the anodic film, which increases linearly with charge density but independent of current density. The reversible part of the mass change arises from the weight of the diffusion layer. In contrast to CuP, OFHC Cu releases much more Cu{sup +1} during anodic polarization and forms a poorly-adherent anodic film that is considerably heavier than the black film for a given charge density.

  5. Behavior of CuP and OFHC Cu anodes under electrodeposition conditions

    SciTech Connect

    Frankel, G.S.; Schrott, A.G.; Horkans, J.; Andricacos, P.C. . Thomas J. Watson Research Center); Isaacs, H.S. )

    1992-01-01

    Films formed on CuP (with 0.05 wt % P) and OFHC Cu anodes in electroplating solutions were studied by X-ray Photoelectron Spectroscopy, X-ray Absorption Spectroscopy, electrochemical methods, and a newly developed gravimetric technique. The black film formed on CuP in Cl-containing solutions was found to resemble a porous sponge composed of CuCl but laden/with concentrated CuSO{sub 4} solution. The difference between the buoyancy-corrected measured mass change and the charge-equivalent mass change was found to have two components: a reversible part that comes and goes as the current is turned on and off, and an irreversible part that remains on the surface and increase in mass with time. The irreversible part results from the anodic film, which increases linearly with charge density but independent of current density. The reversible part of the mass change arises from the weight of the diffusion layer. In contrast to CuP, OFHC Cu releases much more Cu{sup +1} during anodic polarization and forms a poorly-adherent anodic film that is considerably heavier than the black film for a given charge density.

  6. Magnetoelectric effects in the spiral magnets CuCl2 and CuBr2

    NASA Astrophysics Data System (ADS)

    Tolédano, P.; Ayala, A. P.; Furtado Filho, A. F. G.; do Nascimento, J. P. C.; Silva, M. A. S.; Sombra, A. S. B.

    2017-01-01

    The nature and symmetry of transition mechanisms in the spin-spiral copper halides CuCl2 and CuBr2 are analyzed theoretically. The magnetoelectric effects observed in the two multiferroic compounds are described and their phase diagram at zero and applied magnetic fields are worked out. The emergence of the electric polarization at zero field below the paramagnetic phase is shown to result from the coupling of two distinct spin-density waves and to be only partly related to the Dzialoshinskii-Moriya interactions. Applying a magnetic field along the two-fold monoclinic axis of CuCl2 yields a decoupling of the spin-density waves modifying the symmetry of the phase and the spin-spiral orientation. The remarkable periodic dependences of the magnetic susceptibility and polarization, on rotating the field in the monoclinic plane, are described theoretically.

  7. Magnetoelectric effects in the spiral magnets CuCl2 and CuBr2.

    PubMed

    Tolédano, P; Ayala, A P; Furtado Filho, A F G; do Nascimento, J P C; Silva, M A S; Sombra, A S B

    2017-01-25

    The nature and symmetry of transition mechanisms in the spin-spiral copper halides CuCl2 and CuBr2 are analyzed theoretically. The magnetoelectric effects observed in the two multiferroic compounds are described and their phase diagram at zero and applied magnetic fields are worked out. The emergence of the electric polarization at zero field below the paramagnetic phase is shown to result from the coupling of two distinct spin-density waves and to be only partly related to the Dzialoshinskii-Moriya interactions. Applying a magnetic field along the two-fold monoclinic axis of CuCl2 yields a decoupling of the spin-density waves modifying the symmetry of the phase and the spin-spiral orientation. The remarkable periodic dependences of the magnetic susceptibility and polarization, on rotating the field in the monoclinic plane, are described theoretically.

  8. Synthesis of Cu-doped Li2O and its cathode properties for lithium-ion batteries based on oxide/peroxide redox reactions

    NASA Astrophysics Data System (ADS)

    Kobayashi, Hiroaki; Hibino, Mitsuhiro; Makimoto, Tetsuya; Ogasawara, Yoshiyuki; Yamaguchi, Kazuya; Kudo, Tetsuichi; Okuoka, Shin-ichi; Ono, Hironobu; Yonehara, Koji; Sumida, Yasutaka; Mizuno, Noritaka

    2017-02-01

    Cu-doped Li2O, synthesized by mechanochemical reactions between Li2O and CuO, is demonstrated as a cathode material for lithium-ion batteries. The X-ray diffraction and absorption analyses suggest that in the Cu-doped Li2O, Cu2+ ions are located at 48g sites less symmetrical than 8c sites for Li+ ions, distorting the arrangement of surrounding O2- ions slightly from tetrahedral to square-planar, while the Cu2+ ions are doped in an antifluorite-type Li2O. The Cu-doped Li2O cathode has a charge capacity of 360 mAh g-1 without an irreversible O2 gas evolution reaction and exhibits a reversible capacity of 300 mAh g-1. Cu K-edge XANES spectroscopy and quantitative analysis of peroxide species reveal that redox of copper ions, formation/neutralization of O 2p electron holes, and generation/annihilation of peroxide species take place during charge/discharge.

  9. Anisotropic electric surface resistance of Cu(110)

    SciTech Connect

    Otto, A.; Lilie, P.; Dumas, P.; Hirschmugl, C.; Pilling, M.; Williams, Gwyn P.

    2007-08-01

    The electric surface resistance is measured without contacts by grazing incidence of p-polarized infrared (IR) radiation for the adsorbates CO and C{sub 2}H{sub 4}, which settle on top of the close packed atomic ridges of Cu(110) in the <1, -1, 0> direction. Surface resistance has only been observed for the IR electric currents in this direction. This can be explained by the assumption that IR induced currents in the <001> direction can only flow in the second and deeper layers of Cu(110). Therefore, in this direction, there is no friction with the adsorbates and hence no surface resistance.

  10. Understanding temperature and magnetic-field actuated magnetization polarity reversal in the Prussian blue analogue Cu0.73Mn0.77[Fe(CN)6].zH2O, using XMCD

    SciTech Connect

    Lahiri, Debdutta; Choi, Yongseong; Kumar, Amit; Ramanan, Nitya; Chattopadhyay, Soma; Sharma, Surinder; Haskel, Daniel; Yusuf, S. M.

    2016-03-01

    We have investigated the microscopic origin of temperature and magnetic-field actuated magnetization reversal in Cu0.73Mn0.77[Fe(CN)(6)]center dot zH(2)O, using XMCD. Our results show a fair deviation from the mean-field-theory in the form of different ordering temperatures of Fe and Mn sublattices. A preferential sign reversal of Mn spin under magnetic field and different spin cant angles for the two sublattices have also been observed. An antiferromagnetic coupling between the Fe and Mn sublattices along with different ordering temperatures (sublattice decoupling) for these sublattices explain the temperature-dependent magnetization reversal. Whereas, Mn spin reversal alone (under external magnetic field) is responsible for the observed field-dependent magnetization reversal. The dissimilar magnetic behavior of Fe and Mn sublattices in this cubic 3d-orbital system has been understood by invoking disparity and competition among inter-sublattice magnetic control parameters, viz. magnetic Zeeman energy, exchange coupling constant and magnetic anisotropy constant. Our results have significant design implications for future magnetic switches, by optimizing the competition among these magnetic control parameters.

  11. Polar Barchans

    NASA Technical Reports Server (NTRS)

    2004-01-01

    20 July 2004 This Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) image shows dark, barchan sand dunes of the north polar region of Mars. Barchan dunes are simple, rounded forms with two horns that extend downwind. Inequalities in local wind patterns may result in one horn being extended farther than the other, as is the case for several dunes in this image. The image also shows several barchans may merge to form a long dune ridge. The horns and attendant slip faces on these dunes indicate wind transport of sand from the upper left toward the lower right. The image is located near 77.6oN, 103.6oW. The picture covers an area about 3 km (1.9 mi) wide; sunlight illuminates the scene from the lower left.

  12. Polar Layers

    NASA Technical Reports Server (NTRS)

    2005-01-01

    [figure removed for brevity, see original site] Context image for PIA03581 Polar Layers

    This image shows just one example of the bright and dark markings that appear during summer time. The marks are related to the polar layers. If you happen to see a wild-eyed guy sticking his tongue out at you, you'll know why this image qualifies for the old 'art' category of THEMIS releases.

    Image information: VIS instrument. Latitude 80.6S, Longitude 34.1E. 17 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  13. Adsorption of Cu(II) to ferrihydrite and ferrihydrite-bacteria composites: Importance of the carboxyl group for Cu mobility in natural environments

    NASA Astrophysics Data System (ADS)

    Moon, Ellen M.; Peacock, Caroline L.

    2012-09-01

    Bacterially associated iron (hydr)oxide composites are widespread in natural environments, and by analogy with isolated iron (hydr)oxides and bacteria, are important scavengers of dissolved trace-metals. We precipitated ferrihydrite via rapid Fe(III) hydrolysis in the absence and presence of the non-Fe metabolising, Gram-positive bacterium Bacillus subtilis, commonly found in natural waters, soils and sediments. We combined XRD, SEM, BET and Fe K-edge EXAFS to examine the mineralogy, morphology and crystallinity of the ferrihydrite composites. We find that the mineral fraction of the composites is unaltered in primary mineralogy, morphology and crystallinity compared to pure ferrihydrite. We then measured the adsorption of Cu to ferrihydrite and the ferrihydrite-B. subtilis composites as a function of pH and the ferrihydrite:bacteria mass ratio of the composites, and used EXAFS to determine the molecular mechanisms of Cu adsorption. We determine directly for the first time that Cu uptake by ferrihydrite-B. subtilis composites is the result of adsorption to both the ferrihydrite and B. subtilis fractions. Adsorption of Cu by the B. subtilis fraction results in significant Cu uptake in the low pH regime (pH ˜4, ˜20% of [Cu]total) and significantly enhanced Cu uptake in the mid pH regime. This composite sorption behaviour is in stark contrast to pure ferrihydrite, where Cu adsorption is negligible at low pH. Overall, for composites dominated by either ferrihydrite or B. subtilis, the bacterial fraction is exclusively responsible for Cu adsorption at low pH while the ferrihydrite fraction is predominantly responsible for adsorption at high pH. Furthermore, with an increased mass ratio of bacteria, the dominance of Cu adsorption to the bacterial fraction persists into the mid pH regime and extends significantly into the upper pH region. As such, the distribution of the total adsorbed Cu between the composite fractions is a function of both pH and the ferrihydrite

  14. Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl 6 2– (M = Ti, Zr, Hf, U) and UOCl 5 Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory

    SciTech Connect

    Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Clark, David L.; Conradson, Steven D.; Kozimor, Stosh A.; Martin, Richard L.; Schwarz, Daniel E.; Shuh, David K.; Wagner, Gregory L.; Wilkerson, Marianne P.; Wolfsberg, Laura E.; Yang, Ping

    2012-03-28

    Chlorine K-edge X-ray absorption spectroscopy (XAS) and ground-state and time-dependent hybrid density functional theory (DFT) were used to probe electronic structure for O{sub h}-MCl{sub 6}{sup 2-}(M = Ti, Zr, Hf, U) and C{sub 4v}-UOCl{sub 5}{sup -}, and to determine the relative contributions of valence 3d, 4d, 5d, 6d, and 5f orbitals in M-Cl bonding. Spectral interpretations were guided by time-dependent DFT calculated transition energies and oscillator strengths, which agree well with the experimental XAS spectra. The data provide new spectroscopic evidence for the involvement of both 5f and 6d orbitals in actinide-ligand bonding in UCl{sub 6}{sup 2-}. For the MCl{sub 6}{sup 2-}, where transitions into d orbitals of t{sub 2g} symmetry are spectroscopically resolved for all four complexes, the experimentally determined Cl 3p character per M-Cl bond increases from 8.3(4)% (TiCl{sub 6}{sup 2-}) to 10.3(5)% (ZrCl{sub 6}{sup 2-}), 12(1)% (HfCl{sub 6}{sup 2-}), and 26 18(1)% (UCl{sub 6}{sup 2-}). Chlorine K-edge XAS spectra of UOCl{sub 5}{sup -} provide additional insights into the transition assignments by 27 lowering the symmetry to C{sub 4v}, where five pre-edge transitions into both 5f and 6d orbitals are observed. For UCl{sub 6}{sup 2-}, the XAS data 28 suggest that orbital mixing associated with the U 5f orbitals is considerably lower than that of the U 6d orbitals. For both UCl{sub 6}{sup 2-}29 and UOCl{sub 5}{sup -}, the ground-state DFT calculations predict a larger 5f contribution to bonding than is determined experimentally. 30 These findings are discussed in the context of conventional theories of covalent bonding for d- and f-block metal complexes.

  15. Local structure and polarization resistance of Ce doped SrMnO{sub 3} using extended x-ray fine structure analysis

    SciTech Connect

    Ryu, Jiseung; Lee, Heesoo

    2014-09-15

    Changes to the local structure of Sr and Mn atoms in Sr{sub 1−x}Ce{sub x}MnO{sub 3} (SCM) according to increasing Ce content and the effect of the structural change on the polarization resistance of SCM were investigated. The reduction of manganese was confirmed by the absorption edge shift of the Mn K-edge toward lower energies. The noise of oscillation in extended X-ray absorption fine structure k{sup 3}χ data at Mn K-edge reveals the distortion of the local structure of Mn atoms, and the peak that indicates the bonding length of Mn-O, Sr/Ce, and -Mn decreased with the addition of Ce content in Fourier transformations of the Mn K-edge. The distortion of the local structure at Mn atoms was affected by the reduced manganese ions having larger ionic radii than Mn{sup 4+}. Meanwhile, few distortions of local atomic structures of Sr atoms occurred, and the average nearest neighboring distances of Sr-O and Sr-Mn are ∼2.13 Å and ∼2.95 Å, respectively. The average bonding lengths of the Ce-O and Ce-Mn increased because the ionic radius of substituted Ce ion with 12 coordination number is smaller than that of Sr ion, which leads the reduction of Mn ions and the distortion of local structure at the substituted A-site. Therefore, we reasoned that the distortion of the local atomic structure at Mn atoms in MnO{sub 6} and Ce atoms in A-site is one of the causes for interrupting oxygen ion transfers as a geometric factor, which results in an increase in the polarization resistance of SCM within the Ce composition range from 10 mol. % to 30 mol. %.

  16. Polarization-dependent infrared reflectivity study of Sr2.5Ca11.5Cu24O41 under pressure: Charge dynamics, charge distribution, and anisotropy

    SciTech Connect

    Frank, S.; Huber, A.; Ammerahl, U.; Hücker, M.; Kuntscher, C. A.

    2014-12-18

    We present a polarization-dependent infrared reflectivity study of the spin-ladder compound Sr₂̣₅Ca₁₁̣₅Cu₂₄O₄₁ under pressure. The optical response is strongly anisotropic, with the highest reflectivity along the ladders/chains (E∥c) revealing a metallic character. For the polarization direction perpendicular to the ladder plane, an insulating behavior is observed. With increasing pressure the optical conductivity for E∥c shows a strong increase, which is most pronounced below 2000cm⁻¹. According to the spectral weight analysis of the E∥c optical conductivity the hole concentration in the ladders increases with increasing pressure and tends to saturate at high pressure. At ~7.5 GPa the number of holes per Cu atom in the ladders has increased by Δδ=0.09(±0.01), and the Cu valence in the ladders has reached the value +2.33. Thus, the optical data suggest that Sr₂̣₅Ca₁₁̣₅Cu₂₄O₄₁ remains electronically highly anisotropic up to high pressure, also at low temperatures.

  17. Electrochemical Corrosion Behavior of TiN-Coated Biomedical Ti-Cu Alloy Foam in Fluoride Containing Artificial Saliva

    NASA Astrophysics Data System (ADS)

    Mutlu, Ilven

    2014-07-01

    Highly porous Ti-Cu alloy foams were produced by powder metallurgy method for implant applications. Ti-Cu alloys were prepared with 3, 5, 7, and 10 wt pct Cu contents in order to determine optimum Cu addition. Cu addition enhances sinterability, and the Ti-Cu compacts were sintered at lower temperatures and times than pure Ti. Specimens were coated with a TiN film to enhance wear and corrosion resistance. Sintered specimens were precipitation hardened (aged) in order to increase mechanical properties. Corrosion properties of foams were examined by electrochemical techniques, such as potentiodynamic polarization, cyclic polarization, Tafel extrapolation, linear polarization resistance, and open-circuit potential measurement. Effect of Cu content, TiN coating, pH, and fluoride content of artificial saliva on electrochemical corrosion behavior of specimens was investigated.

  18. OPERATIONS AND PERFORMANCE OF RHIC AS A CU-CU COLLIDER.

    SciTech Connect

    PILAT, R.; AHRENS, L.; BAI, M.; BARTON, D.S.; ET AL.

    2005-05-16

    The 5th year of RHIC operations, started in November 2004 and expected to last till June 2005, consists of a physics run with Cu-Cu collisions at 100 GeV/u followed by one with polarized protons (pp) at 100 GeV [l]. We will address here the overall performance of the RHIC complex used for the first time as a Cu-Cu collider, and compare it with previous operational experience with Au, PP and asymmetric d-Au collisions. We will also discuss operational improvements, such as a {beta}* squeeze to 85cm in the high luminosity interaction regions from the design value of 1m, system improvements, machine performance and limitations, and address reliability and uptime issues.

  19. Sequence and symmetry of hole injection in YBa 2Cu 3O 6+x in situ and ex situ experiments on powders and single crystals using X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Tolentino, H.; Baudelet, F.; Fontaine, A.; Gourieux, T.; Krill, G.; Henry, J. Y.; Rossat-Mignod, J.

    1992-03-01

    Very accurate XAS in situ and ex situ measurements at the Cu K-edge on powders and single crystals of YBa 2Cu 3O 6+ x have been carried out using the time-resolved dispersive spectrometer at LURE-DCI. The whole range of oxygen content has been investigated and the x-dependence of the amount of Cu(I) has been evaluated at room and at high temperatures (from 400 to 750°C). Owing to the balance of charges, we derived the amount of the oxygen 2p holes. The sequence of injection was separated into steps, associated with three oxygen bands of distinct symmetries and with the well-known steps in the superconducting behavior.

  20. Inelastic scattering at the B K edge of hexagonal BN

    SciTech Connect

    Jia, J.J.; Callcott, T.A.; Zhou, L.

    1997-04-01

    Many recent soft x-ray fluorescence (SXF) studies have shown that inelastic scattering processes make important contributions to the observed spectra for excitation near the x-ray threshold. These effects are all attributed to a process, usually called an electronic Raman scattering (ERS) process, in which energy is lost to an electronic excitation. The theory has been described using second order perturbation theory by Tulkki and Aberg. In different materials, the detailed nature of the electronic excitation producing the energy loss may be very different. In crystalline Si, diamond and graphite, changes in spectral shape and dispersion of spectral features with variation of the excitation energy are observed, which are attributed to k conservation between the photoelectron generated in the excitation process and the valence hole remaining after the coupled emission process. Hence the process is strongly localized in k-space. In haxagonal boron nitride, which has a lattice and band structure very similar to graphite, inelastic scattering produces very different effects on the observed spectra. Here, the inelastic losses are coupled to a strong resonant elastic scattering process, in which the intermediate state is a localized core exciton and the final state is a localized valence exciton, so that the electronic excitation is strongly localized in real rather than reciprocal space.

  1. Carbon K-Edge XANES Spectromicroscopy of Natural Graphite

    SciTech Connect

    Brandes,J.; Cody, G.; Rumble, D.; Haberstroh, P.; Wirick, S.; Gelinas, Y.; Morais-Cabral, J.

    2008-01-01

    The black carbon continuum is composed of a series of carbon-rich components derived from combustion or metamorphism and characterized by contrasting environmental behavior and susceptibility to oxidation. In this work, we present a micro-scale density fractionation method that allows isolating the small quantities of soot-like and graphitic material usually found in natural samples. Organic carbon and {delta}{sup 13}C mass balance calculations were used to quantify the relative contributions of the two fractions to thermally-stable organic matter from a series of aquatic sediments. Varying proportions of soot-like and graphitic material were found in these samples, with large variations in {delta}{sup 13}C signatures suggesting important differences in their origin and/or dynamics in the environment.

  2. Cyclic-Anodic Polarization Studies of a Zr41.2Ti13.8Ni10Cu12.5Be22.5 Bulk Metallic Glass

    SciTech Connect

    Morrison, M. L.; Buchanan, R. A.; Peker, A.; Peter, William H; Horton Jr, Joe A; Liaw, Peter K

    2004-01-01

    Cyclic-anodic-polarization tests were conducted on a Zr-based bulk metallic glass (BMG) with a chemical composition of Zr{sub 41.2}Ti{sub 13.8}Ni{sub 10}Cu{sub 12.5}Be{sub 22.5}. Samples were compared in two different electrolytes at two different temperatures. Tests were conducted at 22 and 37 C in both, an aerated 0.6 M NaCl electrolyte and a phosphate-buffered saline (PBS) electrolyte with a physiologically relevant dissolved oxygen content. For all tested conditions, the alloy demonstrated passive behavior at the open-circuit potential with low corrosion rates. However, a susceptibility to localized pitting corrosion was observed in all of the tested conditions. At both temperatures, statistical analyses revealed that the LM-001 BMG exhibited comparable or improved values for every corrosion parameter in the PBS electrolyte, as compared to the NaCl electrolyte. The mean differences between the protection potentials and the open-circuit corrosion potentials were determined to be positive values with greater magnitudes for the PBS electrolyte. Thus, the material may undergo pitting corrosion at surface flaws or after incubation-time periods, depending on the local and bulk environments, with lower probabilities for the PBS electrolyte.

  3. The polarization properties of a tilted polarizer.

    PubMed

    Korger, Jan; Kolb, Tobias; Banzer, Peter; Aiello, Andrea; Wittmann, Christoffer; Marquardt, Christoph; Leuchs, Gerd

    2013-11-04

    Polarizers are key components in optical science and technology. Thus, understanding the action of a polarizer beyond oversimplifying approximations is crucial. In this work, we study the interaction of a polarizing interface with an obliquely incident wave experimentally. To this end, a set of Mueller matrices is acquired employing a novel procedure robust against experimental imperfections. We connect our observation to a geometric model, useful to predict the effect of polarizers on complex light fields.

  4. 3D Epitaxy of Graphene nanostructures in the Matrix of Ag, Al and Cu

    NASA Astrophysics Data System (ADS)

    Salamanca-Riba, Lourdes; Isaacs, Romaine; Wuttig, Manfred; Lemieux, Melburne; Hu, Liangbing; Iftekhar, Jaim; Rashkeev, Sergey; Kukla, Maija; Rabin, Oded; Mansour, Azzam

    2015-03-01

    Graphene nanostructures in the form ribbons were embedded in the lattice of metals such as Ag, Cu, and Al in concentrations up to 36.4 at.%, 21.8 at% and 10.5 at.%, respectively. These materials are called covetics. Raman scattering from Ag and Al covetics indicate variations in the intensity of peaks at ~ 1,300 cm-1 and 1,600 cm-1 with position on the sample. These peaks are associated with the D (defects) and G (graphite E2g mode) peaks of graphitic carbon with sp2 bonding and reveal various degrees of imperfections in the graphene layers. First principles calculations of the dynamic matrix of Ag and Al covetics show bonding between C and the metal. EELS mapping of the C-K edge and high resolution lattice images show that the graphene-like regions form ribbons with epitaxial orientation with the metal lattice of Ag and Al. The temperature dependences of the resistivites of Ag and Cu covetics are similar to those of the pure metals with only slight increase in resistivity. Films of Cu covetic deposited by e-beam evaporation and PLD show higher transmittance and resistance to oxidation than pure metal films of the same thickness indicating that copper covetic films can be used for transparent electrodes. Funded by DARPA/ARL Grant No. W911NF-13-1-0058, and ONR Award No N000141410042.

  5. Polarization in Scattering

    DTIC Science & Technology

    2010-09-01

    we refer to the linear polarization as parallel if the polarization vector is in the scattering plane or perpendicular if the polarization vector is...obvious that the different polarization states can all be represented as linear combinations of any of the independent pairs of polarization states...J.C. (1976) “Improvement of underwater visibility by reduction of backscatter with a circular polarization technique, Applied Optics, 6, 321-330

  6. Polarized internal target apparatus

    DOEpatents

    Holt, R.J.

    1984-10-10

    A polarized internal target apparatus with a polarized gas target of improved polarization and density (achieved by mixing target gas atoms with a small amount of alkali metal gas atoms, and passing a high intensity polarized light source into the mixture to cause the alkali metal gas atoms to become polarized which interact in spin exchange collisions with target gas atoms yielding polarized target gas atoms) is described.

  7. Polarized internal target apparatus

    DOEpatents

    Holt, Roy J.

    1986-01-01

    A polarized internal target apparatus with a polarized gas target of improved polarization and density achieved by mixing target gas atoms with a small amount of alkali metal gas atoms, and passing a high intensity polarized light source into the mixture to cause the alkali metal gas atoms to become polarized which interact in spin exchange collisions with target gas atoms yielding polarized target gas atoms.

  8. Soft X-ray Observation of electronic contribution to ferroelectric polarization

    NASA Astrophysics Data System (ADS)

    Wilkins, Stuart

    2012-02-01

    Multiferroic materials open up new interesting possibilities for devices by enabling the switching of an electric state by magnetic field or vice-versa. In addition to this functionality, multiferroics are intriguing from a fundamental physics perspective, raising interesting questions concerning coupling of the electric and magnetic order parameters. To date, most coupling mechanisms are understood to occur due to distortions in the crystal lattice. Here we present experimental evidence that in the multiferroics RMn2O5 (where R is a rare earth) there exists a new, purely electronic contribution to the ferroelectric polarization, which can exist in the absence of any lattice distortions. This contribution arises due to spin-dependent hybridization of O 2p and Mn 3d states and was observed through soft x-ray resonant scattering, which has proved to be a very useful tool in the study of the magnetic structure of multiferroics[1]. Through resonant x-ray scattering at the oxygen K-edge, we find that such spin dependent hybridization occurs in both TbMn2O5[2] and YMn2O5[3]. Remarkably, in YMn2O5 we find that the temperature dependence of the integrated intensity of the signal at the oxygen K-edge closely follows the macroscopic electric polarization [3], and hence is proportional to the ferroelectric order parameter. This is in contrast with the temperature dependence observed at the Mn L3 edge, which reflects the Mn magnetic order parameter. Work performed at BNL was supported by the US Department of Energy, Division of Materials Science, under contract No. DE-AC02-98CH10886. [4pt] [1] S.B. Wilkins et al., Phys. Rev. Lett. 103, 207602 (2009)[0pt] [2] T.A.W. Beale, S. B. Wilkins et al., Phys. Rev. Lett. 105, 087203 (2010)[0pt] [3] S. Partzsch, S. B. Wilkins et al., Phys. Rev. Lett. 107, 057201 (2011)

  9. Cu+ -ATPases brake system.

    PubMed

    Argüello, José M; González-Guerrero, Manuel

    2008-06-01

    Copper (Cu+) transport ATPases are characterized by cytoplasmic metal-binding repeats. Using cryo-electron microscopy (cryo-EM) of functionally intact Cu+-ATPases and high-resolution structures of isolated domains, Wu et al. (2008) produced a model that explains how Cu+ binding to cytoplasmic sites controls the enzyme transport rate.

  10. Broadband graphene polarizer

    NASA Astrophysics Data System (ADS)

    Bao, Qiaoliang; Zhang, Han; Wang, Bing; Ni, Zhenhua; Lim, Candy Haley Yi Xuan; Wang, Yu; Tang, Ding Yuan; Loh, Kian Ping

    2011-07-01

    Conventional polarizers can be classified into three main modes of operation: sheet polarizer using anisotropic absorption media, prism polarizer by refraction and Brewster-angle polarizer by reflection. These polarizing components are not easily integrated with photonic circuits. The in-line fibre polarizer, which relies on polarization-selective coupling between the evanescent field and birefringent crystal or metal, is a promising alternative because of its compatibility with most fibre-optic systems. Here, we demonstrate the operation of a broadband fibre polarizer based on graphene, an ultrathin two-dimensional carbon material. The out-coupled light in the telecommunication band shows a strong s-polarization effect with an extinction ratio of 27 dB. Unlike polarizers made from thin metal film, a graphene polarizer can support transverse-electric-mode surface wave propagation due to its linear dispersion of Dirac electrons.

  11. Polar Color

    NASA Technical Reports Server (NTRS)

    2004-01-01

    [figure removed for brevity, see original site]

    Released 3 May 2004 This nighttime visible color image was collected on January 1, 2003 during the Northern Summer season near the North Polar Troughs.

    This daytime visible color image was collected on September 4, 2002 during the Northern Spring season in Vastitas Borealis. The THEMIS VIS camera is capable of capturing color images of the martian surface using its five different color filters. In this mode of operation, the spatial resolution and coverage of the image must be reduced to accommodate the additional data volume produced from the use of multiple filters. To make a color image, three of the five filter images (each in grayscale) are selected. Each is contrast enhanced and then converted to a red, green, or blue intensity image. These three images are then combined to produce a full color, single image. Because the THEMIS color filters don't span the full range of colors seen by the human eye, a color THEMIS image does not represent true color. Also, because each single-filter image is contrast enhanced before inclusion in the three-color image, the apparent color variation of the scene is exaggerated. Nevertheless, the color variation that does appear is representative of some change in color, however subtle, in the actual scene. Note that the long edges of THEMIS color images typically contain color artifacts that do not represent surface variation.

    Image information: VIS instrument. Latitude 79, Longitude 346 East (14 West). 19 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with

  12. Phase transition from fcc to bcc structure of the Cu-clusters during nanocrystallization of Fe{sub 85.2}Si{sub 1}B{sub 9}P{sub 4}Cu{sub 0.8} soft magnetic alloy

    SciTech Connect

    Nishijima, Masahiko; Matsuura, Makoto; Takenaka, Kana; Takeuchi, Akira; Makino, Akihiro; Ofuchi, Hironori

    2014-05-15

    A role of Cu on the nanocrystallization of an Fe{sub 85.2}Si{sub 1}B{sub 9}P{sub 4}Cu{sub 0.8} alloy was investigated by X-ray absorption fine structure (XAFS) and transmission electron microscopy (TEM). The Cu K-edge XAFS results show that local structure around Cu is disordered for the as-quenched sample whereas it changes to fcc-like structure at 613 K. The fcc Cu-clusters are, however, thermodynamically unstable and begin to transform into bcc structure at 638 K. An explicit bcc structure is observed for the sample annealed at 693 K for 600 s in which TEM observation shows that precipitated bcc-Fe crystallites with ∼12 nm are homogeneously distributed. The bcc structure of the Cu-clusters transforms into the fcc-type again at 973 K, which can be explained by the TEM observations; Cu segregates at grain boundaries between bcc-Fe crystallites and Fe{sub 3}(B,P) compounds. Combining the XAFS results with the TEM observations, the structure transition of the Cu-clusters from fcc to bcc is highly correlated with the preliminary precipitation of the bcc-Fe which takes place prior to the onset of the first crystallization temperature, T{sub x1} = 707 K. Thermodynamic analysis suggests that an interfacial energy density γ between an fcc-Cu cluster and bcc-Fe matrix dominates at a certain case over the structural energy between fcc and bcc Cu, ΔG{sub fcc} {sub −} {sub bcc}, which causes phase transition of the Cu clusters from fcc to bcc structure.

  13. Skeletal Ru/Cu catalysts prepared from crystalline and quasicrystalline ternary alloy precursors: characterization by X-ray absorption spectroscopy and CO oxidation.

    PubMed

    Highfield, James; Liu, Tao; Loo, Yook Si; Grushko, Benjamin; Borgna, Armando

    2009-02-28

    The Ru/Cu system is of historical significance in catalysis. The early development and application of X-ray absorption spectroscopy (XAS) led to the original 'bimetallic cluster" concept for highly-immiscible systems. This work explores alkali leaching of Al-based ternary crystalline and quasicrystalline precursors as a potential route to bulk Ru/Cu alloys. Single-phase ternary alloys at 3 trial compositions; Al(71)Ru(22)Cu(7), Al(70.5)Ru(17)Cu(12.5), and Al(70)Ru(10)Cu(20), were prepared by arc melting of the pure metal components. After leaching, the bimetallic residues were characterized principally by transmission XAS, "as-leached" and after annealing in H(2) (and passivation) in a thermobalance. XRD and BET revealed a nanocrystalline product with a native structure of hexagonal Ru. XPS surface analysis of Ru(22)Cu(7) and Ru(17)Cu(12.5) found only slight enrichment by Cu in the as-leached forms, with little change upon annealing. Ru(10)Cu(20) was highly segregated as-leached. XANES data showed preferential oxidation of Cu in Ru(22)Cu(7), implying that it exists as an encapsulating layer. TG data supports this view since it does not show the distinct two-stage O(2) uptake characteristic of skeletal Ru. Cu K-edge EXAFS data for Ru(22)Cu(7) were unique in showing a high proportion of Ru neighbours. The spacing, d(CuRu) = 2.65 A, was that expected from a hypothetical (ideal) solid solution at this composition, but this is unlikely in such a bulk-immiscible system and Ru K-edge EXAFS failed to confirm bulk alloying. Furthermore its invariance under annealing was more indicative of an interfacial bond between bulk components, although partial alloying with retention of local order cannot entirely be ruled out. The XAS and XPS data were reconciled in a model involving surface and bulk segregation, Cu being present at both the grain exterior and in ultra-fine internal pores. This structure can be considered as the 3-dimensional analogue of the classical type

  14. Studies on structural, optical and magnetic properties of Mg- and Li-doped Cu:ZnO films

    NASA Astrophysics Data System (ADS)

    Vachhani, P. S.; Rawal, Amit H.; Bhatnagar, A. K.; Choudhary, R. J.; Phase, D. M.; Rajput, Parasmani; Jha, S. N.; Bhattacharyya, D.

    2017-07-01

    Structural, optical and magnetic properties of Zn0.96Li0.02Cu0.02O and Zn0.98-x Mg x Cu0.02O (x  =  0.00, 0.02, 0.08) films grown by pulsed laser deposition (PLD) on a glass substrate coated with indium tin oxide (ITO) are presented in this paper. X-ray diffraction (XRD) measurements confirmed good structural quality without any impurity. No E 2(high) mode is observed in Raman spectra, possibly due to the breaking of translational symmetry caused by the intrinsic defects or by the dopant. Optical measurements show an increase in the bandgap of Mg- and Li-doped Cu:ZnO films with respect to that of Cu:ZnO film. Extended x-ray absorption fine structure spectroscopy (EXAFS) measurements at the Zn K-edge show some change in the coordination number, but no significant change was observed in the bond distances of the first and the second shells. The mean square relative displacement σ 2 increases with doping, indicating higher disorder in films caused by Mg and Li doping. No evidence of ferromagnetism is found in these films at 300 K.

  15. In operando evidence of deoxygenation in ionic liquid gating of YBa2Cu3O7-X

    PubMed Central

    Perez-Muñoz, Ana M.; Schio, Pedro; Poloni, Roberta; Fernandez-Martinez, Alejandro; Rivera-Calzada, Alberto; Salas-Colera, Eduardo; Kinney, Joseph; Leon, Carlos; Santamaria, Jacobo; Garcia-Barriocanal, Javier; Goldman, Allen M.

    2017-01-01

    Field-effect experiments on cuprates using ionic liquids have enabled the exploration of their rich phase diagrams [Leng X, et al. (2011) Phys Rev Lett 107(2):027001]. Conventional understanding of the electrostatic doping is in terms of modifications of the charge density to screen the electric field generated at the double layer. However, it has been recently reported that the suppression of the metal to insulator transition induced in VO2 by ionic liquid gating is due to oxygen vacancy formation rather than to electrostatic doping [Jeong J, et al. (2013) Science 339(6126):1402–1405]. These results underscore the debate on the true nature, electrostatic vs. electrochemical, of the doping of cuprates with ionic liquids. Here, we address the doping mechanism of the high-temperature superconductor YBa2Cu3O7-X (YBCO) by simultaneous ionic liquid gating and X-ray absorption experiments. Pronounced spectral changes are observed at the Cu K-edge concomitant with the superconductor-to-insulator transition, evidencing modification of the Cu coordination resulting from the deoxygenation of the CuO chains, as confirmed by first-principles density functional theory (DFT) simulations. Beyond providing evidence of the importance of chemical doping in electric double-layer (EDL) gating experiments with superconducting cuprates, our work shows that interfacing correlated oxides with ionic liquids enables a delicate control of oxygen content, paving the way to novel electrochemical concepts in future oxide electronics. PMID:28028236

  16. In operando evidence of deoxygenation in ionic liquid gating of YBa2Cu3O7-X.

    PubMed

    Perez-Muñoz, Ana M; Schio, Pedro; Poloni, Roberta; Fernandez-Martinez, Alejandro; Rivera-Calzada, Alberto; Cezar, Julio C; Salas-Colera, Eduardo; Castro, German R; Kinney, Joseph; Leon, Carlos; Santamaria, Jacobo; Garcia-Barriocanal, Javier; Goldman, Allen M

    2017-01-10

    Field-effect experiments on cuprates using ionic liquids have enabled the exploration of their rich phase diagrams [Leng X, et al. (2011) Phys Rev Lett 107(2):027001]. Conventional understanding of the electrostatic doping is in terms of modifications of the charge density to screen the electric field generated at the double layer. However, it has been recently reported that the suppression of the metal to insulator transition induced in VO2 by ionic liquid gating is due to oxygen vacancy formation rather than to electrostatic doping [Jeong J, et al. (2013) Science 339(6126):1402-1405]. These results underscore the debate on the true nature, electrostatic vs. electrochemical, of the doping of cuprates with ionic liquids. Here, we address the doping mechanism of the high-temperature superconductor YBa2Cu3O7-X (YBCO) by simultaneous ionic liquid gating and X-ray absorption experiments. Pronounced spectral changes are observed at the Cu K-edge concomitant with the superconductor-to-insulator transition, evidencing modification of the Cu coordination resulting from the deoxygenation of the CuO chains, as confirmed by first-principles density functional theory (DFT) simulations. Beyond providing evidence of the importance of chemical doping in electric double-layer (EDL) gating experiments with superconducting cuprates, our work shows that interfacing correlated oxides with ionic liquids enables a delicate control of oxygen content, paving the way to novel electrochemical concepts in future oxide electronics.

  17. by Cu Deficiencies

    NASA Astrophysics Data System (ADS)

    Wei, Tian-Ran; Li, Fu; Li, Jing-Feng

    2014-06-01

    This work revealed that the Cu-deficient ternary compounds Cu3- x SbSe4 free of Te and Pb exhibit enhanced thermoelectric performance. Cu3- x SbSe4 ( x = 0, 0.025, 0.050, 0.075) polycrystalline materials with high phase purity were fabricated by a facile method combining mechanical alloying and spark plasma sintering. Effects of Cu deficiencies on crystal structures, microstructures, element chemical states, and thermoelectric properties were systematically studied. High carrier concentration was obtained for the compositions Cu2.95SbSe4 and Cu2.925SbSe4 due to additional Cu vacancies, contributing to a remarkable increase in electrical conductivity. Together with a satisfactorily large Seebeck coefficient above 300 μV/K, a high power factor of about 890 μW/m-K2 at 523 K was achieved for Cu2.95SbSe4 and Cu2.925SbSe4, almost 60% larger than that of the stoichiometric sample with x = 0. The maximum ZT value was increased to 0.50 at 673 K in the Cu2.925SbSe4 sample sintered at a high temperature (703 K); this is the highest value reported so far for the undoped Cu3SbSe4 system.

  18. Perpendicularly magnetized spin filtering Cu/Ni multilayers

    SciTech Connect

    Shirahata, Yasuhiro; Wada, Eiji; Itoh, Mitsuru; Taniyama, Tomoyasu

    2014-01-20

    Spin filtering at perpendicular magnetized Cu/Ni multilayer/GaAs(001) interfaces is demonstrated at remanence using optical spin orientation method. [Cu(9 nm)/Ni(t{sub Ni} nm)]{sub n} multilayers are found to show a crossover from the in-plane to out-of-plane magnetic anisotropy at the Cu/Ni bilayer repetition n = 4 and the Ni layer thickness t{sub Ni} = 3. For a perpendicularly magnetized Cu/Ni multilayer/n-GaAs(001) interface, circular polarization dependent photocurrent shows a clear hysteretic behavior under optical spin orientation conditions as a function of magnetic field out-of-plane while the bias dependence exhibits a substantial peak at a forward bias, verifying that Cu/Ni multilayers work as an efficient spin filter in the remanent state.

  19. Spin-dependent Fabry-Pérot interference from a Cu thin film grown on fcc Co(001).

    PubMed

    Wu, Y Z; Schmid, A K; Altman, M S; Jin, X F; Qiu, Z Q

    2005-01-21

    Spin-dependent electron reflection from a Cu thin film grown on Co/Cu(001) was investigated using spin-polarized low-energy electron microscopy (SPLEEM). Fabry-Pe rot type interference was observed and is explained using the phase accumulation model. SPLEEM images of the Cu overlayer reveal magnetic domains in the Co underlayer, with the domain contrast oscillating with electron energy and Cu film thickness. This behavior is attributed to the spin-dependent electron reflectivity at the Cu/Co interface which leads to spin-dependent Fabry-Pe rot electron interference in the Cu film.

  20. Polarized Light in Astronomy.

    ERIC Educational Resources Information Center

    King, D. J.

    1983-01-01

    The application of very sensitive electronic detecting devices during the last decade has revolutionized and revitalized the study of polarization in celestial objects. The nature of polarization, how polaroids work, interstellar polarization, dichroic filters, polarization by scattering, and modern polarimetry are among the topics discussed. (JN)