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Sample records for absorption near-edge structure

  1. Hydrogen atom position in hydrated iodide anion from x-ray absorption near edge structure

    Hydrogen atom position in the hydrated iodide anion complex is determined from X-ray Absorption Near Edge Structure (XANES) of an aqueous iodide solution at both the K- and L-edges. The spectra are compared with the theoretical ones calculated by using the FEFF method for several model geometries having hydrogen atoms at different positions. Satisfactory agreements are obtained from models with an almost linear alignment of iodine-hydrogen-oxygen atoms, indicating the capability of the XANES analysis when it is combined with the multiple scattering calculations as a method to detect the positions of hydrogen atoms in the first coordination sphere. (author)

  2. Correction method for self-absorption effects of fluorescence x-ray absorption near-edge structure on multilayer samples

    It is well known that fluorescence x-ray absorption spectroscopy suffers from the self-absorption effects for thick and concentrated samples. In this study, a simple correction method is provided for correcting the self-absorption effects of fluorescence x-ray absorption near edge structure (XANES) spectrum for multilayer samples. This method is validated by application on fluorescence XANES spectra for a Cr/C multilayer measured at different incidence angles. The errors produced by the self-absorption effects for the measured fluorescence x-ray absorption spectra without corrections are also estimated and discussed. (paper)

  3. Single shot near edge x-ray absorption fine structure spectroscopy in the laboratory

    Mantouvalou, I.; Witte, K.; Martyanov, W.; Jonas, A.; Grötzsch, D.; Streeck, C.; Löchel, H.; Rudolph, I.; Erko, A.; Stiel, H.; Kanngießer, B.

    2016-05-01

    With the help of adapted off-axis reflection zone plates, near edge X-ray absorption fine structure spectra at the C and N K-absorption edge have been recorded using a single 1.2 ns long soft X-ray pulse. The transmission experiments were performed with a laser-produced plasma source in the laboratory rendering time resolved measurements feasible independent on large scale facilities. A resolving power of E/ΔE ˜ 950 at the respective edges could be demonstrated. A comparison of single shot spectra with those collected with longer measuring time proves that all features of the used reference samples (silicon nitrate and polyimide) can be resolved in 1.2 ns. Hence, investigations of radiation sensitive biological specimen become possible due to the high efficiency of the optical elements enabling low dose experiments.

  4. X-Ray Absorption Near Edge Structure Spectra as a basis for the speciation of lead

    For this study several inorganic lead (II) compounds were measured at the Pb-L3-(13035 eV), L1- (15860 eV) and M5- (2484 eV) edge using X-Ray Absorption Near Edge Structure Spectroscopy (XANES) to determine experimentally which edge is most sensitive to the coordination environment. Each edge probes a different electronic configuration because of the selection rules and has a different resolution because of life-time broadening. Pb-L1-XANES spectra are only sensitive to the first coordination shell. Pb-M5-XANES spectra show a better energy resolution which is due to decreased lifetime broadening, but the pure lead spectra are also sensitive only to the first coordination shell. Spectra at the Pb-L3-edge show the highest sensitivity: differences in coordination out to the third shell could be distinguished. Therefore, even though Pb-L1- and M5-edges have some advantages, because of physical conditions compared to the L3-edge, these advantages do not result in increased sensitivity.

  5. An energy and intensity monitor for X-ray absorption near-edge structure measurements

    Jonge, Martin D. de, E-mail: martin.dejonge@synchrotorn.org.a [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia); Paterson, David [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia); McNulty, Ian [Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439-4856 (United States); Rau, Christoph [Diamond Light Source Ltd, Didcot, Oxfordshire (United Kingdom); Brandes, Jay A. [Skidaway Institute of Oceanography, 10 Ocean Science Circle, Savannah, GA 31411 (United States); Ingall, Ellery [School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332-0340 (United States)

    2010-07-21

    An in-line X-ray beam energy and intensity monitor has been developed for use in focussed X-ray absorption near-edge spectroscopy (XANES) measurements. The monitor uses only the X-ray intensity that would otherwise bypass our zone-plate focussing optic and relies on a measurement of photoemission current. The monitor is inexpensive, easy to align, and provides valuable feedback about the X-ray energy. Operation of the monitor is demonstrated for measurements of phosphorus XANES. The precision of the energy determination is around 0.5 eV.

  6. An energy and intensity monitor for X-ray absorption near-edge structure measurements

    An in-line X-ray beam energy and intensity monitor has been developed for use in focussed X-ray absorption near-edge spectroscopy (XANES) measurements. The monitor uses only the X-ray intensity that would otherwise bypass our zone-plate focussing optic and relies on a measurement of photoemission current. The monitor is inexpensive, easy to align, and provides valuable feedback about the X-ray energy. Operation of the monitor is demonstrated for measurements of phosphorus XANES. The precision of the energy determination is around 0.5 eV.

  7. All-electron Bethe-Salpeter calculations for shallow-core x-ray absorption near-edge structures

    Olovsson, W.; Tanaka, I.; Mizoguchi, T.; Puschnig, P.; Ambrosch-Draxl, C.

    2009-01-01

    X-ray absorption near-edge structure spectra are calculated by fully solving the electron/core-hole Bethe-Salpeter equation (BSE) in an all-electron framework. We study transitions from shallow core states, including the Mg L2,3 edge in MgO, the Li K edge in the Li halides LiF, LiCl, LiBr, and LiI, as well as Li2O. We illustrate the advantage of the many-body approach over a core-hole supercell calculation. Both schemes lead to strongly bound excitons, but the nonlocal treatment of the electr...

  8. First-principles study of phonon effects in x-ray absorption near-edge structure spectroscopy

    Nemausat, R.; Brouder, Ch; Gervais, Ch; Cabaret, D.

    2016-05-01

    Usually first-principles x-ray absorption near-edge structure (XANES) calculations are performed in the Born-Oppenheimer approximation assuming a static lattice, whereas the nuclear motion undoubtedly impacts XANES spectra notably at the K pre-edge of light elements in oxides. Here, an efficient method based on density-functional theory to account for quantum thermal fluctuations of nuclei is developed and is successfully applied to the K edge of corundum for temperatures up to 930 K. The zero-point motion influence is estimated. Comparison is made with previous theoretical approaches also developed to account for vibrations in XANES.

  9. Reduced chromium in olivine grains from lunar basalt 15555: X-ray absorption near edge structure (XANES)

    The oxidation state of Cr in 200 μm regions within individual lunar olivine and pyroxene grains from lunar basalt 15555 was inferred using X-ray Absorption Near Edge Structure (XANES). Reference materials had previously been studied by optical absorption spectroscopy and included Cr-bearing borosilicate glasses synthesized under controlled oxygen fugacity and Cr-doped olivines. The energy dependence of XANES spectral features defined by these reference materials indicated that Cr is predominantly divalent in the lunar olivine and trivalent in the pyroxene. These results coupled with the apparent fo2-independence of partitioning coefficients for Cr into olivine imply that the source magma was dominated by divalent Cr at the time of olivine crystallization. 29 refs., 8 figs., 1 tab

  10. Influence of the local atomic structure in the X-ray absorption near edge spectroscopy of neptunium oxo ions

    Experimental L(III) X-ray absorption near edge structure (XANES) spectra of the distorted octahedral neptunium oxo ions NpO2(OH)42- NpO4(OH)23-, and NpO66- are interpreted using relativistic full multiple scattering calculations of the X-ray absorption process. In this series of compounds, the neptunium cation exhibits two different oxidation states, VI and VII, with coordination spheres from di- to tetra oxo for the first two compounds. The comparison between calculated XANES spectra using the feff code and experimental ones shows that the main features in the spectra are determined by the local coordination around the actinide metal center. Furthermore, the projected density of electronic states (DOS) calculated from the XANES simulations using the feff code are compared to calculations using ADF code. They are both discussed in terms of molecular orbitals and qualitative evolution of bonding within this series of compounds. (authors)

  11. Determining Orientational Structure of Diamondoid Thiols Attached to Silver Using Near Edge X-ray Absorption Fine Structure Spectroscopy

    Willey, T M; Lee, J I; Fabbri, J D; Wang, D; Nielsen, M; Randel, J C; Schreiner, P R; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J P; Carlson, R K; Terminello, L J; Melosh, N A; van Buuren, T

    2008-10-07

    Near-edge x-ray absorption fine structure spectroscopy (NEXAFS) is a powerful tool for determination of molecular orientation in self-assembled monolayers and other surface-attached molecules. A general framework for using NEXAFS to simultaneously determine molecular tilt and twist of rigid molecules attached to surfaces is presented. This framework is applied to self-assembled monolayers of higher diamondoid, hydrocarbon molecules with cubic-diamond-cage structures. Diamondoid monolayers chemisorbed on metal substrates are known to exhibit interesting electronic and surface properties. This work compares molecular orientation in monolayers prepared on silver substrates using two different thiol positional isomers of [121]tetramantane, and thiols derived from two different pentamantane structural isomers, [1212]pentamantane and [1(2,3)4]pentamantane. The observed differences in monolayer structure demonstrate the utility and limitations of NEXAFS spectroscopy and the framework. The results also demonstrate the ability to control diamondoid assembly, in particular the molecular orientational structure, providing a flexible platform for the modification of surface properties with this exciting new class of nanodiamond materials.

  12. Quantitative phase analysis of cubic boron nitride based composites by X-ray absorption near edge structure

    Piskorska, Edyta [Institute of Physics Polish Academy of Science, Al. Lotnikow 32/46, 02-668 Warsaw (Poland)], E-mail: pisko@ifpan.edu.pl; Lawniczak-Jablonska, Krystyna [Institute of Physics Polish Academy of Science, Al. Lotnikow 32/46, 02-668 Warsaw (Poland)], E-mail: jablo@ifpan.edu.pl; Minikayev, Roman [Institute of Physics Polish Academy of Science, Al. Lotnikow 32/46, 02-668 Warsaw (Poland)], E-mail: minik@ifpan.edu.pl; Wolska, Anna [Institute of Physics Polish Academy of Science, Al. Lotnikow 32/46, 02-668 Warsaw (Poland)], E-mail: wolska@ifpan.edu.pl; Paszkowicz, Wojciech [Institute of Physics Polish Academy of Science, Al. Lotnikow 32/46, 02-668 Warsaw (Poland)], E-mail: paszk@ifpan.edu.pl; Klimczyk, Piotr [Institute of Metal Cutting, Wroclawska 37A Str., 30-011 Cracow (Poland)], E-mail: Piotr.Klimczyk@ios.krakow.pl; Benko, Ewa [Institute of Metal Cutting, Wroclawska 37A Str., 30-011 Cracow (Poland)

    2007-05-15

    X-ray absorption near edge structure (XANES) spectra of Ti, Si, B and N K-edges were investigated to determine the phase composition of multicompounds cubic boron nitride (cBN) based composites formed by reaction of cBN with Ti{sub 3}SiC{sub 2} ceramics. Knowing that the shape of XANES spectra is a fingerprint of chemical bonding of the element in compound, a linear combination of XANES spectra of reference compounds (phases) was fitted to the spectra of the composites. This procedure permitted to determine the fraction of the componential phases in studied materials. X-ray Diffraction (XRD) analysis confirmed the presence of compounds detected by XANES analysis. The similarities and differences between XANES and XRD results are discussed. The combination of XANES and XRD techniques allowed to estimate the quantity of presented compounds within the limits of sensitivity of each method.

  13. 3D Imaging of Nickel Oxidation States using Full Field X-ray Absorption Near Edge Structure Nanotomography

    Nelson, George; Harris, William; Izzo, John; Grew, Kyle N. (Connecticut); (USARL)

    2012-01-20

    Reduction-oxidation (redox) cycling of the nickel electrocatalyst phase in the solid oxide fuel cell (SOFC) anode can lead to performance degradation and cell failure. A greater understanding of nickel redox mechanisms at the microstructural level is vital to future SOFC development. Transmission x-ray microscopy (TXM) provides several key techniques for exploring oxidation states within SOFC electrode microstructure. Specifically, x-ray nanotomography and x-ray absorption near edge structure (XANES) spectroscopy have been applied to study samples of varying nickel (Ni) and nickel oxide (NiO) compositions. The imaged samples are treated as mock SOFC anodes containing distinct regions of the materials in question. XANES spectra presented for the individual materials provide a basis for the further processing and analysis of mixed samples. Images of composite samples obtained are segmented, and the distinct nickel and nickel oxide phases are uniquely identified using full field XANES spectroscopy. Applications to SOFC analysis are discussed.

  14. Probing Warm Dense Matter electronic structure using X-ray absorption Near Edge Spectroscopy (XANES)

    Benuzzi Mounaix, Alessandra

    2011-06-01

    The behavior and physical properties of warm dense matter, fundamental for various branches of physics including planetology and Inertial Confinement Fusion, are non trivial to simulate either theoretically, numerically or experimentally. Despite important progress obtained in the last decade on macroscopic characterization (e.g. equations of state), microscopic studies are today necessary to investigate finely the WDM structure changes, the phase transitions and to test physical hypothesis and approximations commonly used in calculations. In this work, highly compressed aluminum has been investigated with the aim of bringing information on the evolution of its electronic structure by using K-edge shift and XANES. The experiment was performed at LULI laboratory where we used one long pulse (500 ps, IL ~ 8 1013 W/cm2) to create a uniform shock and a second ps beam (IL ~ 1017 W/cm2) to generate an ultra-short broadband X-ray source near the Al K-edge. The spectra were registered by using two conical KAP Bragg crystals. The main target was designed to probe the Aluminum in reshocked conditions allowing us to probe and to test theories in an extreme regime up to now unexplored (ρ ~ 3 ρ0 and T ~ 8 eV). The hydrodynamical Al conditions were measured by using VISARs interferometers and self-emission diagnostics. By increasing the delay between the two beams, we have been able to observe the modification of absorption spectra for unloading Al conditions (ρ >= 0.5 g/cc), and to put in evidence the relocalization of the 3p valence electrons occurring in the metal-non metal transition. All data have been compared to ab initio and dense plasma calculations.

  15. Aluminum incorporation in Ti1-xAlxN films studied by x-ray absorption near-edge structure

    The local bonding structure of titanium aluminum nitride (Ti1-xAlxN) films grown by dc magnetron cosputtering with different AlN molar fractions (x) has been studied by x-ray absorption near-edge structure (XANES) recorded in total electron yield mode. Grazing incidence x-ray diffraction (GIXRD) shows the formation of a ternary solid solution with cubic structure (c-Ti1-xAlxN) that shrinks with the incorporation of Al and that, above a solubility limit of x∼0.7, segregation of w-AlN and c-Ti1-xAlxN phases occurs. The Al incorporation in the cubic structure and lattice shrinkage can also be observed using XANES spectral features. However, contrary to GIXRD, direct evidence of w-AlN formation is not observed, suggesting a dominance and surface enrichment of cubic environments. For x>0.7, XANES shows the formation of Ti-Al bonds, which could be related to the segregation of w-AlN. This study shows the relevance of local-order information to assess the atomic structure of Ti1-xAlxN solutions.

  16. Influence of the local atomic structure in the X-ray absorption near edge spectroscopy of neptunium oxo ions

    Lozano, J.M.; Den Auwer, Ch.; Fillaux, C.; Guilaumont, D. [CEA Marcoule, DEN, DRCP, SCPS, F-30207 Bagnols Sur, (France); Lozano, J.M.; Mustre de Leon, J. [Cinvestav Merida, Dept Fis Aplicada, Merida 97310, Yuc, (Mexico); Clark, D.L. [Los Alamos Natl Lab, GT Seaborg Inst Transactinium Sci, Los Alamos, NM 87544 (United States); Conradson, S.D. [Los Alamos Natl Lab, Div Mat Sci and Technol, Los Alamos, NM 87544 (United States); Keogh, D.W.; Palmer, Ph. [Los Alamos Natl Lab, Div Chem, Los Alamos, NM 87544 (United States); Simoni, E. [Univ Paris 11, IPN Orsay, F-91405 Orsay, (France)

    2009-07-01

    Experimental L(III) X-ray absorption near edge structure (XANES) spectra of the distorted octahedral neptunium oxo ions NpO{sub 2}(OH){sub 4}{sup 2-} NpO{sub 4}(OH){sub 2}{sup 3-}, and NpO{sub 6}{sup 6-} are interpreted using relativistic full multiple scattering calculations of the X-ray absorption process. In this series of compounds, the neptunium cation exhibits two different oxidation states, VI and VII, with coordination spheres from di- to tetra oxo for the first two compounds. The comparison between calculated XANES spectra using the feff code and experimental ones shows that the main features in the spectra are determined by the local coordination around the actinide metal center. Furthermore, the projected density of electronic states (DOS) calculated from the XANES simulations using the feff code are compared to calculations using ADF code. They are both discussed in terms of molecular orbitals and qualitative evolution of bonding within this series of compounds. (authors)

  17. X-ray absorption near-edge structures of disordered Mg1-xZnxO solid solutions

    In order to examine x-ray absorption near-edge structures (XANES) of disordered solid solutions of metal oxides, a combined approach of a first principles supercell method and a cluster expansion method is developed. Zn-L3 edge XANES are measured on a series of Mg1-xZnxO with a rocksalt structure in the range of x=0.025-0.3 using synchrotron source. A first principles orthogonalized linear combinations of an atomic orbital method is employed to obtain a theoretical spectrum of a given model. A Zn-2p core hole is included in the calculation, and a set of 128 atom supercells is used. Theoretical XANES of disordered solid solutions are obtained as a weighted sum of theoretical spectra for four ordered structures, with the weighting factors determined by the cluster expansion method. The dependence of the spectral shape on the solute concentration is reproduced only when the averaged environment of solute atoms as determined by the solute concentration and the effect of the disordering is taken into account. The formation of the disordered Mg1-xZnxO solid solution is confirmed by the Monte Carlo calculations

  18. Near-edge X-ray absorption fine-structure spectroscopy of naphthalene diimide-thiophene co-polymers

    Gann, Eliot; McNeill, Christopher R., E-mail: christopher.mcneill@monash.edu [Department of Materials Engineering, Monash University, Wellington Road, Clayton, Victoria 3800 (Australia); Szumilo, Monika; Sirringhaus, Henning [Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE (United Kingdom); Sommer, Michael [Institute of Macromolecular Chemistry, University of Freiburg, Stefan-Meier-Str. 31, 79104 Freiburg (Germany); Maniam, Subashani; Langford, Steven J. [School of Chemistry, Monash University, Wellington Road, Clayton, Victoria 3800 (Australia); Thomsen, Lars [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia)

    2014-04-28

    Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy is an important tool for probing the structure of conjugated polymer films used in organic electronic devices. High-performance conjugated polymers are often donor-acceptor co-polymers which feature a repeat unit with multiple functional groups. To facilitate better application of NEXAFS spectroscopy to the study of such materials, improved understanding of the observed NEXAFS spectral features is required. In order to examine how the NEXAFS spectrum of a donor-acceptor co-polymer relates to the properties of the sub-units, a series of naphthalene diimide-thiophene-based co-polymers have been studied where the nature and length of the donor co-monomer has been systematically varied. The spectra of these materials are compared with that of a thiophene homopolymer and naphthalene diimide monomer enabling peak assignment and the influence of inter-unit electronic coupling to be assessed. We find that while it is possible to attribute peaks within the π* manifold as arising primarily due to the naphthalene diimide or thiophene sub-units, very similar dichroism of these peaks is observed indicating that it may not be possible to separately probe the molecular orientation of the separate sub-units with carbon K-edge NEXAFS spectroscopy.

  19. Water formation reaction on Pt(111): Near edge x-ray absorption fine structure experiments and kinetic Monte Carlo simulations

    The catalytic water formation reaction was investigated by the energy dispersive near-edge x-ray absorption fine structure (dispersive NEXAFS) spectroscopy. An oxygen covered Pt(111) surface with the (2x2) structure was exposed to gaseous hydrogen (5.0x10-9 Torr) at constant surface temperatures (120-140 K). O K-edge NEXAFS spectra were measured during the reaction with a time interval of 35 s. Quantitative analyses of the spectra provided the coverage changes of the adsorbed species (O, OH, and H2O). The reaction is composed of three steps, which are characterized by an induction period (I), fast increase in coverage of OH and H2O with consuming O (II), and slow conversion of OH to H2O after the complete consumption of O (III). It was also found that the maximum OH coverage becomes smaller at a higher temperature. The kinetic Monte Carlo simulation has reproduced the three characteristic reaction steps; in the first step OH domains are created through two-dimensional aggregation of H2O (I), after the nucleation process the second step sets in where the OH domains propagate by the autocatalytic cycle until they contact with each other (II), and finally the merged OH domains convert to H2O (III). The reaction diffusion method was also applied to this system. It explained the reaction behavior in a wide surface area

  20. Near Edge X-ray Absorption Fine Structure Spectroscopy Studies of Single-Crystalline V2O5 Nanowire Arrays

    Velazquez, J.; Jaye, C; Fischer, D; Banerjee, S

    2009-01-01

    Near edge X-ray absorption fine structure (NEXAFS) spectroscopy is used to precisely probe the alignment, uniformity in crystal growth direction, and electronic structure of single-crystalline V2O5 nanowire arrays prepared by a cobalt-catalyzed vapor transport process. The dipole selection rules operational for core-level electron spectroscopy enable angle-dependent NEXAFS spectroscopy to be used as a sensitive probe of the anisotropy of these systems and provides detailed insight into bond orientation and the symmetry of the frontier orbital states. The experimental spectra are matched to previous theoretical predictions and allow experimental verification of features such as the origin of the split-off conduction band responsible for the semiconducting properties of V2O5 and the strongly anisotropic nature of vanadyl-oxygen-derived (VO) states thought to be involved in catalysis. The strong anisotropy observed across thousands of nanowires in the NEXAFS measurements clearly demonstrates the uniformity of crystal growth direction in these nanowire arrays.

  1. Near-edge X-ray absorption fine-structure spectroscopy of naphthalene diimide-thiophene co-polymers

    Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy is an important tool for probing the structure of conjugated polymer films used in organic electronic devices. High-performance conjugated polymers are often donor-acceptor co-polymers which feature a repeat unit with multiple functional groups. To facilitate better application of NEXAFS spectroscopy to the study of such materials, improved understanding of the observed NEXAFS spectral features is required. In order to examine how the NEXAFS spectrum of a donor-acceptor co-polymer relates to the properties of the sub-units, a series of naphthalene diimide-thiophene-based co-polymers have been studied where the nature and length of the donor co-monomer has been systematically varied. The spectra of these materials are compared with that of a thiophene homopolymer and naphthalene diimide monomer enabling peak assignment and the influence of inter-unit electronic coupling to be assessed. We find that while it is possible to attribute peaks within the π* manifold as arising primarily due to the naphthalene diimide or thiophene sub-units, very similar dichroism of these peaks is observed indicating that it may not be possible to separately probe the molecular orientation of the separate sub-units with carbon K-edge NEXAFS spectroscopy

  2. Speciation of sulfur in humic and fulvic acids using X-ray absorption near-edge structure (XANES) spectroscopy

    Morra, Matthew J.; Fendorf, Scott E.; Brown, Paul D.

    1997-02-01

    Sulfur species in soils and sediments have previously been determined indirectly using destructive techniques. A direct and more accurate method for S speciation would improve our understanding of S biogeochemistry. X-ray absorption near edge structure (XANES) spectroscopy was performed on purified humic and fulvic acids from terrestrial and aquatic environments. This methodology allows direct determination of S species using the relationship that exists with the energy required for core electron transitions and in some cases, correlation with additional spectral features. Soil, peat, and aquatic humic acids were dominated by sulfonates with an oxidation state of +5, but also contained ester-bonded sulfates with an oxidation state of +6. Leonardite humic acid contained ester-bonded sulfate and an unidentified S compound with an oxidation state of +4.0. In contrast, high-valent S in soil, peat, and aquatic fulvic acids was exclusively in the form of sulfonic acids. Reduced S species were also present in both humic and fulvic acids. XANES is a valuable method for the speciation of S in humic materials and of potential use in S speciation of unfractionated soils.

  3. Speciation of sulfur in humic and fulvic acids using X-ray Absorption Near-Edge Structures (XANES) spectroscopy

    Morra, M.J.; Fendorf, S.E.; Brown, P.D. [Univ. of Idaho, Moscow, ID (United States)

    1997-02-01

    Sulfur species in soils and sediments have previously been determined indirectly using destructive techniques. A direct and more accurate method for S speciation would improve our understanding of S biogeochemistry. X-ray absorption near edge structure (XANES) spectroscopy was performed on purified humic and fulvic acids from terrestrial and aquatic environments. This methodology allows direct determination of S species using the relationship that exists with the energy required for core electron transitions and in some cases, correlation with additional spectral features. Soil, peat, and aquatic humic acids were dominated by sulfonates with an oxidation state of +5, but also contained ester-bonded sulfates with an oxidation state of +6. Leonardite humic acid contained ester-bonded sulfate and an unidentified S compound with an oxidation state of +4.0. In contrast, high-valent S in soil, peat, and aquatic fulvic acids was exclusively in the form of sulfonic acids. Reduced S species were also present in both humic and fulvic acids. XANES is a valuable method for the speciation of S in humic materials and of potential use in S speciation of unfractionated soils. 27 refs., 4 figs., 3 tabs.

  4. Investigation of copper(I) oxide quantum dots by near edge X-ray absorption fine structure spectroscopy

    Copper(I) oxide quantum dots (OQDs) were grown in various thicknesses on different SrTiO3(001) surfaces and were investigated by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The experimental growth conditions for the OQDs were optimized to obtain Cu2O as the major phase. The OQDs grown on clean SrTiO3(001) surfaces at 825 K and higher with p(O-2) of 9.0 x 10(-7) Torr or greater contain mostly CuO, contrasting to OQDs grown at 800 K with p(O-2) of similar to 7.0 x10(-7) Torr that contain primarily Cu2O. Furthermore, there is a strong interaction between the SrTiO3(001) surface and the first few monolayers of the OQDs, which induces the formation of Cu(II). However, this interaction is mitigated with increasing thickness of OQDs, resulting in the exclusive formation of Cu2O in the top most layers. The influence of the SrTiO3(001) substrate on the formation of OQDs can be minimized by modifying the substrate surface using chemical treatment and/or energetic Au2+ ion-beam irradiation. Examination of the photochemical properties of these OQDs shows that prolonged soft X-ray irradiation under vacuum reduces Cu(II), which is present as a minor impurity in the Cu(I)OQDs

  5. X-ray absorption near-edge structure micro-spectroscopy study of vanadium speciation in Phycomyces blakesleeanus mycelium.

    Žižić, Milan; Dučić, Tanja; Grolimund, Daniel; Bajuk-Bogdanović, Danica; Nikolic, Miroslav; Stanić, Marina; Križak, Strahinja; Zakrzewska, Joanna

    2015-09-01

    Vanadium speciation in the fungus Phycomyces blakesleeanus was examined by X-ray absorption near-edge structure (XANES) spectroscopy, enabling assessment of oxidation states and related molecular symmetries of this transition element in the fungus. The exposure of P. blakesleeanus to two physiologically important vanadium species (V(5+) and V(4+)) resulted in the accumulation of this metal in central compartments of 24 h old mycelia, most probably in vacuoles. Tetrahedral V(5+), octahedral V(4+), and proposed intracellular complexes of V(5+) were detected simultaneously after addition of a physiologically relevant concentration of V(5+) to the mycelium. A substantial fraction of the externally added V(4+) remained mostly in its original form. However, observable variations in the pre-edge-peak intensities in the XANES spectra indicated intracellular complexation and corresponding changes in the molecular coordination symmetry. Vanadate complexation was confirmed by (51)V NMR and Raman spectroscopy, and potential binding compounds including cell-wall constituents (chitosan and/or chitin), (poly)phosphates, DNA, and proteins are proposed. The evidenced vanadate complexation and reduction could also explain the resistance of P. blakesleeanus to high extracellular concentrations of vanadium. PMID:26253227

  6. Influence of the geometric structure on the V L3 near edge X-ray absorption fine structure from vanadium phosphorus oxide catalysts

    Hävecker, M.; Knop-Gericke, A.; Mayer, R; Fait, M.; Bluhm, H.; Schlögl, R.

    2002-01-01

    We present the V L3 near edge X-ray absorption fine structure (NEXAFS) of a vanadium phosphorus oxide (VPO) catalyst. The spectrum is related to the V3d-O2p hybridised unoccupied states. The overall peak position at the V L3-absorption edge is determined by the formal oxidation state of the absorbing vanadium atom. Details of the absorption fine structure are influenced by the geometric structure of the compound. Empirically we found a linear relationship between the energy position of severa...

  7. Influence of the geometric structure on the V L3 near edge X-ray absorption fine structure from vanadium phosphorus oxide catalysts

    Hävecker, Michael; Knop-Gericke, Axel; Mayer, Ralf W.; Fait, Martin; Bluhm, Hendrik; Schlögl, Robert

    2002-01-01

    We present the V L3 near edge X-ray absorption fine structure (NEXAFS) of a vanadium phosphorus oxide (VPO) catalyst. The spectrum is related to the V3d-O2p hybridised unoccupied states. The overall peak position at the V L3-absorption edge is determined by the formal oxidation state of the absorbing vanadium atom. Details of the absorption fine structure are influenced by the geometric structure of the compound. Empirically we found a linear relationship between the energy position of severa...

  8. Photoelectron Experiments and Studies of X-Ray Absorption Near Edge Structure in Alkaline-Earth and Rare - Fluorides.

    Gao, Yuan

    Alkaline-earth fluorides and rare-earth trifluorides possess technological importance for applications in multi -layer electronic device structures and opto-electronic devices. Interfaces between thin films of YbF _3 and Si(111) substrates were studied by photoelectron spectroscopy and x-ray absorption spectroscopy using synchrotron radiation. Results of YbF_3 /Si(111) were compared with those of TmF _3/Si(111). While electrons in the Si valence band are prevented from occupying the empty 4f levels in TmF_3 at the interface by the on -site Coulomb repulsion energy, the charge transfer from Si to YbF_3 is possible because the totally filled 4f states in Yb still lie below the Si valence band maximum. The theory of x-ray absorption near edge structure (XANES) is incomplete except for a few particularly simple special cases. A Bragg reflection model was developed to qualitatively explain the oscillations in XANES, in terms of the scattering of the photoelectron wave between families of lattice planes as set out by the Bragg condition for backscattering. The model was found to represent the data for systems with nearly free electron like conduction bands reasonably well. High resolution CaF_2 fluorine K edge XANES was used as a prototype to understand XANES in more depth on systems with strong core hole effects. Unlike previous work which involved multiple scattering cluster calculations that include only short range order effects, both the long range order and the symmetry breaking core holes are included in a new bandstructure approach in which the core hole is treated with a supercell technique. A first principles calculation with the use of pseudopotentials successfully reproduced all the main features of the first 15 eV of the fluorine K edge in CaF_2 which had not been explained with the cluster calculations. A comparison of the theoretical and experimental fluorine K edges in CaF_2 and BaF _2 was used to identify the structure related features. The possibility

  9. X-ray absorption near-edge structure of GaN with high Mn concentration grown on SiC

    Sancho-Juan, O; Cantarero, A; Garro, N; Cros, A [Materials Science Institute, University of Valencia, PO Box 22085, E46071 Valencia (Spain); Martinez-Criado, G; Salome, M; Susini, J [European Synchrotron Radiation Facility, 6 rue Jules Horowitz, 38043 Grenoble (France); Olguin, D [Dept. de Fisica, CINVESTAV-IPN, 07300 Mexico D F (Mexico); Dhar, S [Experimentalphysik, Universitaet Duisburg-Essen, Lotharstrasse 1, 47057 Duisburg (Germany)

    2009-07-22

    By means of x-ray absorption near-edge structure (XANES) several Ga{sub 1-x}Mn{sub x}N (0.03near-edge structure, we have performed ab initio calculations using the full potential linear augmented plane wave method as implemented in the Wien2k code. The calculations show the appearance of a Mn bonding t{sub 2}arrow up band localized in the gap region, and the corresponding anti-bonding state t{sub 2}arrow down, which seem to be responsible for the double structure which appears at the pre-edge absorption region. The shoulders and main absorption peak of the XANES spectra are attributed to transitions from the Mn(1s) band to the conduction bands, which are partially dipole allowed because of the Mn(4p) contribution to these bands.

  10. Experimental evidence of thermal fluctuations on the X-ray absorption near-edge structure at the aluminum K-edge

    Manuel, Damien; Cabaret, Delphine; Brouder, Christian; Sainctavit, Philippe; Bordage, Amélie; TRCERA, Nicolas

    2012-01-01

    After a review of temperature-dependent experimental x-ray absorption near-edge structure (XANES) and related theoretical developments, we present the Al K-edge XANES spectra of corundum and beryl for temperature ranging from 300K to 930K. These experimental results provide a first evidence of the role of thermal fluctuation in XANES at the Al K-edge especially in the pre-edge region. The study is carried out by polarized XANES measurements of single crystals. For any orientation of the sampl...

  11. Local environment analysis of Na ions in β-tricalcium phosphate by X-ray absorption near-edge structure measurements and first-principles calculations

    Na-incorporated β-tricalcium phosphate (β-TCP) was synthesized via the solid-state reaction method and a substitution mechanism for Na ions in the synthesized materials has been investigated by X-ray absorption near-edge structure (XANES) analysis. In addition, total electronic energy calculations within density functional theory were also carried out to obtain the most energetically favorable substitution site for Na ions in β-TCP. Both the spectroscopic and computational analysis indicate that substituted Na ions are likely to occupy Ca(4) site in β-TCP. (author)

  12. X-Ray Absorption Near-Edge Structure (XANES) Spectroscopy Study of the Interaction of Silver Ions with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli

    Bovenkamp, Gudrun Lisa; Zanzen, Ulrike; Krishna, Katla Sai; Hormes, Josef; Prange, Alexander

    2013-01-01

    Silver ions are widely used as antibacterial agents, but the basic molecular mechanism of this effect is still poorly understood. X-ray absorption near-edge structure (XANES) spectroscopy at the Ag LIII, S K, and P K edges reveals the chemical forms of silver in Staphylococcus aureus and Escherichia coli (Ag+ treated). The Ag LIII-edge XANES spectra of the bacteria are all slightly different and very different from the spectra of silver ions (silver nitrate and silver acetate), which confirms...

  13. X-ray absorption near edge structure studies of Pb{sub 1-x}Mn{sub x}Te(In, Ga) systems

    Radisavljevic, Ivana; Novakovic, Nikola; Medic, Mirjana; Paskas-Mamula, Bojana; Ivanovic, Nenad [Belgrade Univ. (Serbia). Vinca Institute of Nuclear Science; Mahnke, Heinz-Eberhard [Helmholtz-Zentrum Berlin fuer Materialien und Energie GmbH, Berlin (Germany); Romcevic, Nebojsa [Belgrade Univ. (Serbia). Inst. of Physics

    2013-03-15

    The X-ray absorption near edge structure technique was employed for studies of coordination environments and valence states of impurity atoms (Mn, In and Ga) in a series of narrow band gap PbTe-based semiconductors. Impurity atoms' absorption data were analysed with the help of the Real Space Full Multiple Scattering FEFF8.2 code. These results are complemented with band structure calculations using the full potential augmented plane waves method extended by local orbitals using WIEN2k code. Impurity atoms are found to be off-centred from the regular lattice positions each in a specific manner, which leads to formation of significantly different local structures from that expected in host PbTe. Observed structural modifications are accompanied by the change in the impurity atoms' valence states. These findings support and extend our previous results obtained with various techniques on this class of materials. (orig.)

  14. Composition analysis of a polymer electrolyte membrane fuel cell microporous layer using scanning transmission X-ray microscopy and near edge X-ray absorption fine structure analysis

    George, Michael G.; Wang, Jian; Banerjee, Rupak; Bazylak, Aimy

    2016-03-01

    The novel application of scanning transmission X-ray microscopy (STXM) to the microporous layer (MPL) of a polymer electrolyte membrane fuel cell is investigated. A spatially resolved chemical component distribution map is obtained for the MPL of a commercially available SGL 25 BC sample. This is achieved with near edge X-ray absorption fine structure spectroscopic analysis. Prior to analysis the sample is embedded in non-reactive epoxy and ultra-microtomed to a thickness of 100 nm. Polytetrafluoroethylene (PTFE), carbon particle agglomerates, and supporting epoxy resin distributions are identified and reconstructed for a scanning area of 6 μm × 6 μm. It is observed that the spatial distribution of PTFE is strongly correlated to the carbon particle agglomerations. Additionally, agglomerate structures of PTFE are identified, possibly indicating the presence of a unique mesostructure in the MPL. STXM analysis is presented as a useful technique for the investigation of chemical species distributions in the MPL.

  15. Inorganic iodine incorporation into soil organic matter: evidence from iodine K-edge X-ray absorption near-edge structure.

    Yamaguchi, Noriko; Nakano, Masashi; Takamatsu, Rieko; Tanida, Hajime

    2010-06-01

    The transformation of inorganic iodine (I(-) and IO(3)(-)) incubated in soils with varying amounts of organic matter (Andosols from the surface layer of an upland field and forest, as well as Acrisols from surface and subsurface layers of an upland field) was investigated by using the iodine K-edge X-ray absorption near-edge structure (XANES). After 60d of reaction, both I(-) and IO(3)(-) were transformed into organoiodine in surface soils containing sufficient amounts of organic matter, whereas IO(3)(-) remained unchanged in the subsurface soil of Acrisols with low organic matter contents. Transformation of IO(3)(-) into organoiodine was not retarded when the microbial activity in soil was reduced by gamma-ray irradiation, suggesting that microbial activity was not essential for the transformation of inorganic iodine into organoiodine. Soil organic matter has the ability to transform inorganic iodine into organoiodine. PMID:18640749

  16. Atheoretical study of the oxygen K-edge near-edge X-ray absorption fine structure of N2O/Ir(110)

    Wu Tai-Quan; Zhu Ping; Wang Xin-Yan; Luo Hong-Lei

    2012-01-01

    A multiple-scattering cluster method is employed to calculate the oxygen K-edge near-edge X-ray absorption fine structure of N2O/Ir(ll0) and its monolayer.Two peaks and one weak resonance appear in both cases.The selfconsistent field DV-Xα calculations of the peaks and resonance show that the physical origin of the pre-cdge peak x is different from those of the main peak 1 and the other weak resonance σl.This setup is intrinsic to the N2O monolayer,owing to the interaction between the neighbouring molecular chains in the monolayer and partly to the adsorbed atomic oxygen,according to both the theoretical and experimental data.

  17. 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

    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.

  18. Study of Synchrotron Radiation Near-Edge X-Ray Absorption Fine-Structure of Amorphous Hydrogenated Carbon Films at Various Thicknesses

    Sarayut Tunmee

    2015-01-01

    Full Text Available The compositions and bonding states of the amorphous hydrogenated carbon films at various thicknesses were evaluated via near-edge X-ray absorption fine-structure (NEXAFS and elastic recoil detection analysis combined with Rutherford backscattering spectrometry. The absolute carbon sp2 contents were determined to decrease to 65% from 73%, while the hydrogen contents increase from 26 to 33 at.% as the film thickness increases. In addition, as the film thickness increases, the π⁎ (C=C, σ⁎ (C–H, σ⁎ (C=C, and σ⁎ (C≡C bonding states were found to increase, whereas the π⁎ (C≡C and σ⁎ (C–C bonding states were observed to decrease in the NEXAFS spectra. Consequently, the film thickness is a key factor to evaluate the composition and bonding state of the films.

  19. Particle Formation from Pulsed Laser Irradiation of SootAggregates studied with scanning mobility particle sizer, transmissionelectron microscope and near-edge x-ray absorption fine structure.

    Michelsen, Hope A.; Tivanski, Alexei V.; Gilles, Mary K.; vanPoppel, Laura H.; Dansson, Mark A.; Buseck, Peter R.; Buseck, Peter R.

    2007-02-20

    We investigated the physical and chemical changes induced in soot aggregates exposed to laser radiation using a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope to perform near-edge x-ray absorption fine structure spectroscopy. Laser-induced nanoparticle production was observed at fluences above 0.12 J/cm(2) at 532 nm and 0.22 J/cm(2) at 1064 nm. Our results indicate that new particle formation proceeds via (1) vaporization of small carbon clusters by thermal or photolytic mechanisms, followed by homogeneous nucleation, (2) heterogeneous nucleation of vaporized carbon clusters onto material ablated from primary particles, or (3) both processes.

  20. Inorganic iodine incorporation into soil organic matter: evidence from iodine K-edge X-ray absorption near-edge structure

    The transformation of inorganic iodine (I- and IO3-) incubated in soils with varying amounts of organic matter (Andosols from the surface layer of an upland field and forest, as well as Acrisols from surface and subsurface layers of an upland field) was investigated by using the iodine K-edge X-ray absorption near-edge structure (XANES). After 60 d of reaction, both I- and IO3- were transformed into organoiodine in surface soils containing sufficient amounts of organic matter, whereas IO3- remained unchanged in the subsurface soil of Acrisols with low organic matter contents. Transformation of IO3- into organoiodine was not retarded when the microbial activity in soil was reduced by γ-ray irradiation, suggesting that microbial activity was not essential for the transformation of inorganic iodine into organoiodine. Soil organic matter has the ability to transform inorganic iodine into organoiodine.

  1. Liquid crystal alignment on ion-beam-treated polyimide with a long alkyl side chain: near edge X-ray absorption fine structure spectroscopy analysis.

    Seo, Joo-Hong; Hwang, Soo Won; Song, Dong Han; Shin, Jae Hoon; Yoon, Tae-Hoon; Kim, Jae Chang; Yi, Mi Hye

    2009-02-19

    Liquid crystal alignment on ion-beam-treated polyimides with a long alkyl side chain was investigated using near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The long alkyl side chains and the asymmetric distribution and orientational order of the pi-bonds of the polyimide surface can be determined by analyzing the angular dependent resonance intensities of the NEXAFS measurements. Herein, we demonstrate that the pretilt angle of the LC cell made by our method decreases as more long alkyl side chains are destroyed. Additionally, the tilt direction of the LC molecules can be determined from the asymmetric distribution of pi-bonds of the polyimide created by the ion beam irradiation. PMID:19161281

  2. Investigation of Pb species in soils, celery and duckweed by synchrotron radiation X-ray absorption near-edge structure spectrometry

    Luo, Liqiang; Shen, Yating; Liu, Jian; Zeng, Yuan

    2016-08-01

    The Pb species play a key role in its translocation in biogeochemical cycles. Soils, sediments and plants were collected from farmlands around Pb mines, and the Pb species in them was identified by X-ray absorption near-edge structure spectrometry. In soils, Pb5(PO4)3Cl and Pb3(PO4)2 were detected, and in sediments, Pb-fulvic acids (FAs) complex was identified. A Pb complex with FA fragments was also detected in celery samples. We found that (1) different Pb species were present in soils and sediments; (2) the Pb species in celery, which was grown in sediments, was different from the species present in duckweed, which grew in water; and (3) a Pb-FA-like compound was present in celery roots. The newly identified Pb species, the Pb-FA-like compound, may play a key role in Pb tolerance and translocation within plants.

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

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

    2014-08-01

    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.

  4. Multiple-Scattering of Near-Edge x-ray Absorption Fine Structure of Sulphur-Passivated InP(100) Surface

    曹松; 唐景昌; 沈少来; 陈更生; 马丹

    2003-01-01

    We use the multiple-scattering cluster method to calculate the sulphur 1s near-edge x-ray absorption fine structure (NEXAFS) of S-passivated InP(100) surface. The physical origins of the resonances in the NEXAFS have been unveiled. It is shown that the most important resonance is attributed to the photoelectron scattering between the central sulphur and the nearest indium atoms. The studies show that two S-S dimers with the bond lengths of 2.05 A and 3.05 A coexist in the surface, meanwhile the bridge and antibridge site adsorption of single S could not be ruled out. We support the scanning tunnelling microscopy result that the S-passivated InP(100) surface exhibits significant disorder.

  5. Identification of B-K near edge x-ray absorption fine structure peaks of boron nitride thin films prepared by sputtering deposition

    Four π* resonance peaks were observed in the B-K near edge x-ray absorption fine structure spectra of boron nitride thin films prepared by magnetron sputtering. In the past, these peaks have been explained as the K-absorption of boron atoms, which are present in environment containing nitrogen vacancies, the number of which is 1-3 corresponding to the three peaks at higher photon energy. However, the authors found that there was a strong correlation between the intensities of these three peaks and that of O-K absorption after wide range scanning and simultaneous measurement of nitrogen and oxygen K-absorptions of the BN films. Therefore, the authors conclude that these three peaks at the higher energy side correspond to boron atoms bound to one-to-three oxygen atoms instead of three nitrogen atoms surrounding the boron atom in the h-BN structure. The result of the first-principles calculation with a simple cluster model supported the validity of this explanation.

  6. Surface Structure and Chemical Switching of Thioctic Acid Adsorbed on Au(111) as Observed Using Near-Edge X-ray Absorption Fine Structure

    Meulenberg, R W; van Buuren, T; Vance, A L; Terminello, L J; Willey, T M; Bostedt, C; Fadley, C S

    2004-01-06

    Thioctic acid (alpha-lipoic acid) is a molecule with a large disulfide-containing base, a short alkyl-chain with four CH{sub 2} units, and a carboxyl termination. Self-assembled monolayer (SAM) films of thioctic acid adsorbed on Au(111) have been investigated with near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS) to determine film quality, bonding and morphology. Using standard preparation protocols for SAMs, that is, dissolving thioctic acid in ethanol and exposing gold to the solution, results in poor films. These films are highly disordered, contain a mixture of carboxyl and carboxylate terminations, have more than monolayer coverage, and exhibit unbound disulfide. Conversely, forming films by dissolving 1 mmol thioctic acid into 5% acetic acid in ethanol (as previously reported with carboxyl-terminated alkyl-thiols) forms ordered monolayers with small amounts of unbound sulfur. NEXAFS indicates tilted over endgroups with the carboxyl group normal on average 38{sup o} from the surface normal. Slight dichroism in other features indicates alkyl chains statistically more upright than prostrate on the surface. Reflection-absorption Fourier transform infrared (RA-FTIR) spectra indicate hydrogen bonding between neighboring molecules. In such well-formed monolayers, a stark reorientation occurs upon deprotonation of the endgroup by rinsing in a KOH solution. The carboxylate plane normal is now about 66{sup o} from sample normal, a much more upright orientation. Data indicate this reorientation may also cause a more upright orientation to the alkyl portion of the molecules.

  7. Near-edge X-ray absorption fine structure studies of Cr{sub 1−x}M{sub x}N coatings

    Mahbubur Rahman, M. [School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150 (Australia); Department of Physics, Jahangirnagar University, Savar, Dhaka 1342 (Bangladesh); Duan, Alex [School of Chemistry, The University of Melbourne, Parkville, VIC 3010 (Australia); Jiang, Zhong-Tao, E-mail: Z.Jiang@murdoch.edu.au [School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150 (Australia); Xie, Zonghan [School of Mechanical Engineering, University of Adelaide, SA 5005 (Australia); School of Engineering, Edith Cowan University, WA 6027 (Australia); Wu, Alex [School of Chemistry, The University of Melbourne, Parkville, VIC 3010 (Australia); Amri, Amun [Department of Chemical Engineering, Riau University, Pekanbaru (Indonesia); Cowie, Bruce [Australian Synchrotron, 800 Blackburn Rd., Clayton, VIC 3168 (Australia); Yin, Chun-Yang [Chemical and Analytical Sciences, Murdoch University, Murdoch, WA 6150 (Australia)

    2013-11-25

    Highlights: •Al or Si is doped on CrN and AlN coatings using magnetron sputtering system. •NEXAFS analysis is conducted to measure the Al and Si K-edges, and chromium L-edge. •Structural evolution of CrN matrix with addition of Al or Si element is investigated. -- Abstract: Cr{sub 1−x}M{sub x}N coatings, with doping concentrations (Si or Al) varying from 14.3 to 28.5 at.%, were prepared on AISI M2 tool steel substrates using a TEER UDP 650/4 closed field unbalanced magnetron sputtering system. Near-edge X-ray absorption fine structure (NEXAFS) characterization was carried out to measure the aluminum and silicon K-edges, as well as chromium L-edge, in the coatings. Two soft X-ray techniques, Auger electron yield (AEY) and total fluorescence yield (TFY), were employed to investigate the surface and inner structural properties of the materials in order to understand the structural evolution of CrN matrix with addition of Al (or Si) elements. Investigations on the local bonding states and grain boundaries of the coatings, using NEXAFS technique, provide significant information which facilitates understanding of the local electronic structure of the atoms and shed light on the origins of the high mechanical strength and oxidation resistance of these technologically important coatings.

  8. Iron speciation in human cancer cells by K-edge total reflection X-ray fluorescence-X-ray absorption near edge structure analysis

    Polgári, Zs.; Meirer, F.; Sasamori, S.; Ingerle, D.; Pepponi, G.; Streli, C.; Rickers, K.; Réti, A.; Budai, B.; Szoboszlai, N.; Záray, G.

    2011-03-01

    X-ray absorption near edge structure (XANES) analysis in combination with synchrotron radiation induced total reflection X-ray fluorescence (SR-TXRF) acquisition was used to determine the oxidation state of Fe in human cancer cells and simultaneously their elemental composition by applying a simple sample preparation procedure consisting of pipetting the cell suspension onto the quartz reflectors. XANES spectra of several inorganic and organic iron compounds were recorded and compared to that of different cell lines. The XANES spectra of cells, independently from the phase of cell growth and cell type were very similar to that of ferritin, the main Fe store within the cell. The spectra obtained after CoCl 2 or NiCl 2 treatment, which could mimic a hypoxic state of cells, did not differ noticeably from that of the ferritin standard. After 5-fluorouracil administration, which could also induce an oxidative-stress in cells, the absorption edge position was shifted toward higher energies representing a higher oxidation state of Fe. Intense treatment with antimycin A, which inhibits electron transfer in the respiratory chain, resulted in minor changes in the spectrum, resembling rather the N-donor Fe-α,α'-dipyridyl complex at the oxidation energy of Fe(III), than ferritin. The incorporation of Co and Ni in the cells was followed by SR-TXRF measurements.

  9. Iron speciation in human cancer cells by K-edge total reflection X-ray fluorescence-X-ray absorption near edge structure analysis

    X-ray absorption near edge structure (XANES) analysis in combination with synchrotron radiation induced total reflection X-ray fluorescence (SR-TXRF) acquisition was used to determine the oxidation state of Fe in human cancer cells and simultaneously their elemental composition by applying a simple sample preparation procedure consisting of pipetting the cell suspension onto the quartz reflectors. XANES spectra of several inorganic and organic iron compounds were recorded and compared to that of different cell lines. The XANES spectra of cells, independently from the phase of cell growth and cell type were very similar to that of ferritin, the main Fe store within the cell. The spectra obtained after CoCl2 or NiCl2 treatment, which could mimic a hypoxic state of cells, did not differ noticeably from that of the ferritin standard. After 5-fluorouracil administration, which could also induce an oxidative-stress in cells, the absorption edge position was shifted toward higher energies representing a higher oxidation state of Fe. Intense treatment with antimycin A, which inhibits electron transfer in the respiratory chain, resulted in minor changes in the spectrum, resembling rather the N-donor Fe-α,α'-dipyridyl complex at the oxidation energy of Fe(III), than ferritin. The incorporation of Co and Ni in the cells was followed by SR-TXRF measurements.

  10. Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure study on oxidative etching of diamond-like carbon films by hyperthermal atomic oxygen

    Surface structural changes of a hydrogenated diamond-like carbon (DLC) film exposed to a hyperthermal atomic oxygen beam were investigated by Rutherford backscattering spectroscopy (RBS), synchrotron radiation photoelectron spectroscopy (SR-PES), and near-edge X-ray absorption fine structure (NEXAFS). It was confirmed that the DLC surface was oxidized and etched by high-energy collisions of atomic oxygen. RBS and real-time mass-loss data showed a linear relationship between etching and atomic oxygen fluence. SR-PES data suggested that the oxide layer was restricted to the topmost surface of the DLC film. NEXAFS data were interpreted to mean that the sp2 structure at the DLC surface was selectively etched by collisions with hyperthermal atomic oxygen, and an sp3-rich region remained at the topmost DLC surface. The formation of an sp3-rich layer at the DLC surface led to surface roughening and a reduced erosion yield relative to the pristine DLC surface.

  11. Dynamic study of sub-micro sized LiFePO4 cathodes by in-situ tender X-ray absorption near edge structure

    Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong

    2016-01-01

    Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.

  12. X-ray absorption near-edge structure study on the configuration of Cu 2+ /histidine complexes at different pH values

    Mei-Juan, Yu; Yu, Wang; Wei, Xu

    2016-04-01

    The local configurations around metal ions in metalloproteins are of great significance for understanding their biological functions. Cu2+/histidine (His) is a typical complex existing in many metalloproteins and plays an important role in lots of physiological functions. The three-dimensional (3D) structural configurations of Cu2+/His complexes at different pH values (2.5, 6.5, and 8.5) are quantitatively determined by x-ray absorption near-edge structure (XANES). Generally Cu2+/His complex keeps an octahedral configuration consisting of oxygen atoms from water molecules and oxygen or nitrogen atoms from histidine molecules coordinated around Cu2+. It is proved in this work that the oxygen atoms from water molecules, when increasing the pH value from acid to basic value, are gradually substituted by the Ocarboxyl, Nam, and Nim from hisitidine molecules. Furthermore, the symmetries of Cu2+/His complexes at pH 6.5 and pH 8.5 are found to be lower than at pH 2.5. Project supported by the National Natural Science Foundation of China (Grant No. 11205186).

  13. Inorganic iodine incorporation into soil organic matter: evidence from iodine K-edge X-ray absorption near-edge structure

    Yamaguchi, Noriko, E-mail: nyamag@affrc.go.j [National Institute for Agro-Environmental Sciences, 3-1-3, Kan-non-dai, Tsukuba, Ibaraki, 305-8604 (Japan); Nakano, Masashi, E-mail: nakano27@vesta.ocn.ne.j [University of Tokyo, School of Agriculture and Life Science, 1-1-1, Yayoi, Tokyo 113-8657 (Japan); Takamatsu, Rieko, E-mail: takamats@vmas.kitasato-u.ac.j [School of Veterinary Medicine, Kitasato University, 35-1, Higashi-niju-sanban-cho, Towada, Aomori, 034-8628 (Japan); Tanida, Hajime, E-mail: tanida@spring8.or.j [SPring-8, Japan Synchrotron Radiation Research Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan)

    2010-06-15

    The transformation of inorganic iodine (I{sup -} and IO{sub 3}{sup -}) incubated in soils with varying amounts of organic matter (Andosols from the surface layer of an upland field and forest, as well as Acrisols from surface and subsurface layers of an upland field) was investigated by using the iodine K-edge X-ray absorption near-edge structure (XANES). After 60 d of reaction, both I{sup -} and IO{sub 3}{sup -} were transformed into organoiodine in surface soils containing sufficient amounts of organic matter, whereas IO{sub 3}{sup -} remained unchanged in the subsurface soil of Acrisols with low organic matter contents. Transformation of IO{sub 3}{sup -} into organoiodine was not retarded when the microbial activity in soil was reduced by gamma-ray irradiation, suggesting that microbial activity was not essential for the transformation of inorganic iodine into organoiodine. Soil organic matter has the ability to transform inorganic iodine into organoiodine.

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

    Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake; Ukai, Masatoshi [Department of Applied Physics, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184-8588 (Japan); Fujii, Kentaro; Yokoya, Akinari [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan); Fukuda, Yoshihiro; Saitoh, Yuji [Synchrotron Radiation Research Center, Japan Atomic Energy Agency, Sayo-gun, Hyougo 679-5148 (Japan)

    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.

  15. Near edge X-ray absorption fine structure study for optimization of hard diamond-like carbon film formation with Ar cluster ion beam

    Diamond-like carbon (DLC) film deposited using C60 vapor with simultaneous irradiation of an Ar cluster ion beam was characterized by a near edge X-ray absorption fine structure (NEXAFS), in order to optimize the hard DLC film deposition conditions. Contents of sp2 orbitals in the films, which were estimated from NEXAFS spectra, are 30% lower than that of a conventional DLC film deposited by a RF plasma method. Those contents were obtained under the flux ratio of the C60 molecules to the Ar cluster ions to range from 1 to 20, at 5keV of Ar cluster ion acceleration energy. Average hardness of the films was 50 GPa under these flux ratios. This hardness was three times higher than that of a conventional DLC film. Furthermore, the lowest sp2 content and above-mentioned high hardness were obtained at room temperature of the substrate when the depositions were performed in the range of the substrate temperature from room temperature to 250degC. (author)

  16. Sulfur species in source rock bitumen before and after hydrous pyrolysis determined by X-ray absorption near-edge structure

    Bolin, Trudy B.; Birdwell, Justin E.; Lewan, Michael; Hill, Ronald J.; Grayson, Michael B.; Mitra-Kirtley, Sudipa; Bake, Kyle D.; Craddock, Paul R.; Abdallah, Wael; Pomerantz, Andrew E.

    2016-01-01

    The sulfur speciation of source rock bitumen (chloroform-extractable organic matter in sedimentary rocks) was examined using sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy for a suite of 11 source rocks from around the world. Sulfur speciation was determined for both the native bitumen in thermally immature rocks and the bitumen produced by thermal maturation of kerogen via hydrous pyrolysis (360 °C for 72 h) and retained within the rock matrix. In this study, the immature bitumens had higher sulfur concentrations than those extracted from samples after hydrous pyrolysis. In addition, dramatic and systematic evolution of the bitumen sulfur moiety distributions following artificial thermal maturation was observed consistently for all samples. Specifically, sulfoxide sulfur (sulfur double bonded to oxygen) is abundant in all immature bitumen samples but decreases substantially following hydrous pyrolysis. The loss in sulfoxide sulfur is associated with a relative increase in the fraction of thiophene sulfur (sulfur bonded to aromatic carbon) to the extent that thiophene is the dominant sulfur form in all post-pyrolysis bitumen samples. This suggests that sulfur moiety distributions might be used for estimating thermal maturity in source rocks based on the character of the extractable organic matter.

  17. Assignment of near-edge x-ray absorption fine structure spectra of metalloporphyrins by means of time-dependent density-functional calculations

    Schmidt, Norman; Fink, Rainer; Hieringer, Wolfgang

    2010-08-01

    The C 1s and N 1s near-edge x-ray absorption fine structure (NEXAFS) spectra of three prototype tetraphenyl porphyrin (TPP) molecules are discussed in the framework of a combined experimental and theoretical study. We employ time-dependent density-functional theory (TDDFT) to compute the NEXAFS spectra of the open- and closed-shell metalloporphyrins CoTPP and ZnTPP as well as the free-base 2HTPP in realistic nonplanar conformations. Using Becke's well-known half-and-half hybrid functional, the computed core excitation spectra are mostly in good agreement with the experimental data in the low-energy region below the appropriate ionization threshold. To make these calculations feasible, we apply a new, simple scheme based on TDDFT using a modified single-particle input spectrum. This scheme is very easy to implement in standard codes and allows one to compute core excitation spectra at a similar cost as ordinary UV/vis spectra even for larger molecules. We employ these calculations for a detailed assignment of the NEXAFS spectra including subtle shifts in certain peaks of the N 1s spectra, which depend on the central coordination of the TPP ligand. We furthermore assign the observed NEXAFS resonances to the individual molecular subunits of the investigated TPP molecules.

  18. Near edge X-ray absorption fine structure study for optimization of hard diamond-like carbon film formation with Ar cluster ion beam

    Kitagawa, T; Kanda, K; Shimizugawa, Y; Toyoda, N; Matsui, S; Yamada, I; Tsubakino, H; Matsuo, J

    2003-01-01

    Diamond-like carbon (DLC) film deposited using C sub 6 sub 0 vapor with simultaneous irradiation of an Ar cluster ion beam was characterized by a near edge X-ray absorption fine structure (NEXAFS), in order to optimize the hard DLC film deposition conditions. Contents of sp sup 2 orbitals in the films, which were estimated from NEXAFS spectra, are 30% lower than that of a conventional DLC film deposited by a RF plasma method. Those contents were obtained under the flux ratio of the C sub 6 sub 0 molecules to the Ar cluster ions to range from 1 to 20, at 5keV of Ar cluster ion acceleration energy. Average hardness of the films was 50 GPa under these flux ratios. This hardness was three times higher than that of a conventional DLC film. Furthermore, the lowest sp sup 2 content and above-mentioned high hardness were obtained at room temperature of the substrate when the depositions were performed in the range of the substrate temperature from room temperature to 250degC. (author)

  19. X-ray absorption near-edge structure (XANES) spectroscopy study of the interaction of silver ions with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli.

    Bovenkamp, Gudrun Lisa; Zanzen, Ulrike; Krishna, Katla Sai; Hormes, Josef; Prange, Alexander

    2013-10-01

    Silver ions are widely used as antibacterial agents, but the basic molecular mechanism of this effect is still poorly understood. X-ray absorption near-edge structure (XANES) spectroscopy at the Ag LIII, S K, and P K edges reveals the chemical forms of silver in Staphylococcus aureus and Escherichia coli (Ag(+) treated). The Ag LIII-edge XANES spectra of the bacteria are all slightly different and very different from the spectra of silver ions (silver nitrate and silver acetate), which confirms that a reaction occurs. Death or inactivation of bacteria was observed by plate counting and light microscopy. Silver bonding to sulfhydryl groups (Ag-S) in cysteine and Ag-N or Ag-O bonding in histidine, alanine, and DL-aspartic acid was detected by using synthesized silver-amino acids. Significantly lower silver-cysteine content, coupled with higher silver-histidine content, in Gram-positive S. aureus and Listeria monocytogenes cells indicates that the peptidoglycan multilayer could be buffering the biocidal effect of silver on Gram-positive bacteria, at least in part. Bonding of silver to phosphate groups was not detected. Interaction with DNA or proteins can occur through Ag-N bonding. The formation of silver-cysteine can be confirmed for both bacterial cell types, which supports the hypothesis that enzyme-catalyzed reactions and the electron transport chain within the cell are disrupted. PMID:23934494

  20. Near-Edge X-Ray Absorption Fine Structure of Ultrananocrystalline Diamond/Hydrogenated Amorphous Carbon Films Prepared by Pulsed Laser Deposition

    Shinya Ohmagari

    2009-01-01

    Full Text Available The atomic bonding configuration of ultrananocrystalline diamond (UNCD/hydrogenated amorphous carbon (a-C:H films prepared by pulsed laser ablation of graphite in a hydrogen atmosphere was examined by near-edge X-ray absorption fine structure spectroscopy. The measured spectra were decomposed with simple component spectra, and they were analyzed in detail. As compared to the a-C:H films deposited at room substrate-temperature, the UNCD/a-C:H and nonhydrogenated amorphous carbon (a-C films deposited at a substrate-temperature of 550∘C exhibited enhanced π∗ and σ∗C≡C peaks. At the elevated substrate-temperature, the π∗ and σ∗C≡C bonds formation is enhanced while the σ∗C–H and σ∗C–C bonds formation is suppressed. The UNCD/a-C:H film showed a larger σ∗C–C peak than the a-C film deposited at the same elevated substrate-temperature in vacuum. We believe that the intense σ∗C–C peak is evidently responsible for UNCD crystallites existence in the film.

  1. Assessment of chemical species of lead accumulated in tidemarks of human articular cartilage by X-ray absorption near-edge structure analysis

    Meirer, Florian [Atominstitut, Vienna University of Technology, 1020 Wien (Austria); MiNALab, CMM-Irst, Fondazione Bruno Kessler, Via Sommarive 18, 38123 Trento (Italy); Pemmer, Bernhard, E-mail: bpemmer@ati.ac.at [Atominstitut, Vienna University of Technology, 1020 Wien (Austria); Pepponi, Giancarlo [MiNALab, CMM-Irst, Fondazione Bruno Kessler, Via Sommarive 18, 38123 Trento (Italy); Zoeger, Norbert; Wobrauschek, Peter [Atominstitut, Vienna University of Technology, 1020 Wien (Austria); Sprio, Simone; Tampieri, Anna [Istituto di Scienza e Tecnologia dei Materiali Ceramici CNR, Faenca (Italy); Goettlicher, Joerg; Steininger, Ralph; Mangold, Stefan [Institute for Synchrotron Radiation, Karlsruhe Institute of Technology, Campus South, 76344 Eggenstein-Leopoldshafen (Germany); Roschger, Paul [Ludwig Boltzmann Institute of Osteology, Hanusch Hospital of WGKK and AUVA Trauma Centre Meidling, 4th Medical Department, Hanusch Hospital, Vienna (Austria); Berzlanovich, Andrea [Department of Forensic Medicine, Medical University of Vienna, A-1090 Vienna (Austria); Hofstaetter, Jochen G. [Ludwig Boltzmann Institute of Osteology, Hanusch Hospital of WGKK and AUVA Trauma Centre Meidling, 4th Medical Department, Hanusch Hospital, Vienna (Austria); Department of Orthopaedics, Vienna General Hospital, Medical University of Vienna, A-1090 Vienna (Austria); Streli, Christina [Atominstitut, Vienna University of Technology, 1020 Wien (Austria)

    2011-03-01

    Lead is a toxic trace element that shows a highly specific accumulation in the transition zone between calcified and non-calcified articular cartilage, the so-called ‘tidemark’. Excellent agreement has been found between XANES spectra of synthetic Pb-doped carbonated hydroxyapatite and spectra obtained in the tidemark region and trabecular bone of normal human samples, confirming that in both tissues Pb is incorporated into the hydroxyapatite crystal structure of bone. During this study the µ-XANES set-up at the SUL-X beamline at ANKA was tested and has proven to be well suited for speciation of lead in human mineralized tissue samples. A highly specific accumulation of the toxic element lead was recently measured in the transition zone between non-calcified and calcified normal human articular cartilage. This transition zone, the so-called ‘tidemark’, is considered to be an active calcification front of great clinical importance. However, little is known about the mechanisms of accumulation and the chemical form of Pb in calcified cartilage and bone. Using spatially resolved X-ray absorption near-edge structure analysis (µ-XANES) at the Pb L{sub 3}-edge, the chemical state of Pb in the osteochondral region was investigated. The feasibility of the µ-XANES set-up at the SUL-X beamline (ANKA synchrotron light source) was tested and confirmed by comparing XANES spectra of bulk Pb-reference compounds recorded at both the XAS and the SUL-X beamline at ANKA. The µ-XANES set-up was then used to investigate the tidemark region of human bone (two patella samples and one femoral head sample). The spectra recorded at the tidemark and at the trabecular bone were found to be highly correlated with the spectra of synthetic Pb-doped carbonated hydroxyapatite, suggesting that in both of these very different tissues Pb is incorporated into the hydroxyapatite structure.

  2. Assessment of chemical species of lead accumulated in tidemarks of human articular cartilage by X-ray absorption near-edge structure analysis

    Lead is a toxic trace element that shows a highly specific accumulation in the transition zone between calcified and non-calcified articular cartilage, the so-called ‘tidemark’. Excellent agreement has been found between XANES spectra of synthetic Pb-doped carbonated hydroxyapatite and spectra obtained in the tidemark region and trabecular bone of normal human samples, confirming that in both tissues Pb is incorporated into the hydroxyapatite crystal structure of bone. During this study the µ-XANES set-up at the SUL-X beamline at ANKA was tested and has proven to be well suited for speciation of lead in human mineralized tissue samples. A highly specific accumulation of the toxic element lead was recently measured in the transition zone between non-calcified and calcified normal human articular cartilage. This transition zone, the so-called ‘tidemark’, is considered to be an active calcification front of great clinical importance. However, little is known about the mechanisms of accumulation and the chemical form of Pb in calcified cartilage and bone. Using spatially resolved X-ray absorption near-edge structure analysis (µ-XANES) at the Pb L3-edge, the chemical state of Pb in the osteochondral region was investigated. The feasibility of the µ-XANES set-up at the SUL-X beamline (ANKA synchrotron light source) was tested and confirmed by comparing XANES spectra of bulk Pb-reference compounds recorded at both the XAS and the SUL-X beamline at ANKA. The µ-XANES set-up was then used to investigate the tidemark region of human bone (two patella samples and one femoral head sample). The spectra recorded at the tidemark and at the trabecular bone were found to be highly correlated with the spectra of synthetic Pb-doped carbonated hydroxyapatite, suggesting that in both of these very different tissues Pb is incorporated into the hydroxyapatite structure

  3. Systematic Oxidation of Polystyrene by Ultraviolet-Ozone, Characterized by Near-Edge X-ray Absorption Fine Structure and Contact Angle

    Klein,R.; Fischer, D.; Lenhart, J.

    2008-01-01

    The process of implanting oxygen in polystyrene (PS) via exposure to ultraviolet-ozone (UV-O) was systematically investigated using the characterization technique of near-edge X-ray absorption fine structure (NEXAFS). Samples of PS exposed to UV-O for 10-300 s and washed with isopropanol were analyzed using the carbon and oxygen K-edge NEXAFS partial electron yields, using various retarding bias voltages to depth-profile the oxygen penetration into the surface. Evaluation of reference polymers provided a scale to quantify the oxygen concentration implanted by UV-O treatment. We find that ozone initially reacts with the double bonds on the phenyl rings, forming carbonyl groups, but within 1 min of exposure, the ratio of double to single oxygen bonds stabilizes at a lower value. Oxygen penetrates the film with relative ease, creating a fairly uniform distribution of oxygen within at least the first 4 nm (the effective depth probed by NEXAFS here). Before oxygen accumulates in large concentrations, however, it preferentially degrades the uppermost layer of the film by removing oxygenated low-molecular-weight oligomers. The failure to accumulate high concentrations of oxygen is seen in the nearly constant carbon edge jump, the low concentration of oxygen even at 5 min exposure (58% of that in poly(4-acetoxystyrene), the polymer with the most similarities to UV-O-treated PS), and the relatively high contact angles. At 5 min exposure the oxygen concentration contains ca. 7 atomic % oxygen. The oxygen species that are implanted consist predominantly of single O-C bonds and double OC bonds but also include a small fraction of O-H. UV-O treatment leads a plateau after 2 min exposure in the water contact angle hysteresis, at a value of 67 {+-} 2, due primarily to chemical heterogeneity. Annealing above Tg allows oxygenated species to move short distances away from the surface but not diffuse further than 1-2 nm.

  4. Characterization of Functionalized Self-Assembled Monolayers and Surface-Attached Interlocking Molecules Using Near-Edge X-ray Absorption Fine Structure Spectroscopy

    Willey, T; Willey, T

    2004-03-24

    Quantitative knowledge of the fundamental structure and substrate binding, as well as the direct measurement of conformational changes, are essential to the development of self-assembled monolayers (SAMs) and surface-attached interlocking molecules, catenanes and rotaxanes. These monolayers are vital to development of nano-mechanical, molecular electronic, and biological/chemical sensor applications. This dissertation investigates properties of functionalized SAMs in sulfur-gold based adsorbed molecular monolayers using quantitative spectroscopic techniques including near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy (XPS). The stability of the gold-thiolate interface is addressed. A simple model SAM consisting of dodecanethiol adsorbed on Au(111) degrades significantly in less than 24 hours under ambient laboratory air. S 2p and O 1s XPS show the gold-bound thiolates oxidize to sulfinates and sulfonates. A reduction of organic material on the surface and a decrease in order are observed as the layer degrades. The effect of the carboxyl vs. carboxylate functionalization on SAM structure is investigated. Carboxyl-terminated layers consisting of long alkyl-chain thiols vs. thioctic acid with short, sterically separated, alkyl groups are compared and contrasted. NEXAFS shows a conformational change, or chemical switchability, with carboxyl groups tilted over and carboxylate endgroups more upright. Surface-attached loops and simple surface-attached rotaxanes are quantitatively characterized, and preparation conditions that lead to desired films are outlined. A dithiol is often insufficient to form a molecular species bound at each end to the substrate, while a structurally related disulfide-containing polymer yields surface-attached loops. Similarly, spectroscopic techniques show the successful production of a simple, surface-attached rotaxane that requires a ''molecular riveting'' step to hold the

  5. Electronic structure and optical properties of CdS{sub x}Se{sub 1−x} solid solution nanostructures from X-ray absorption near edge structure, X-ray excited optical luminescence, and density functional theory investigations

    Murphy, M. W. [DESY (Deutsches Elektronen-Synchrotron), FS-PEX, Notkestrasse 85, 22607 Hamburg (Germany); Yiu, Y. M., E-mail: yyiu@uwo.ca; Sham, T. K. [Department of Chemistry, University of Western Ontario, London, ON N6A5B7 (Canada); Ward, M. J. [Cornell High Energy Synchrotron Source (CHESS), Cornell University, Ithaca, NY 14853 (United States); Liu, L. [Institute of Functional Nano and Soft Materials (FUNSOM) and Soochow University-Western University Center for Synchrotron Radiation Research, Soochow University, Suzhou, Jiangsu, 215123 (China); Hu, Y. [Canadian Light Source, University of Saskatchewan, Saskatoon, SK S7N2V3 (Canada); Zapien, J. A. [Center Of Super-Diamond and Advanced Films (COSDAF) and Department of Physics and Materials Science, City University of Hong Kong, Hong Kong SAR (China); Liu, Yingkai [Institute of Physics and Electronic Information, Yunnan Normal University, Kunming, Yunnan, 650500 (China)

    2014-11-21

    The electronic structure and optical properties of a series of iso-electronic and iso-structural CdS{sub x}Se{sub 1−x} solid solution nanostructures have been investigated using X-ray absorption near edge structure, extended X-ray absorption fine structure, and X-ray excited optical luminescence at various absorption edges of Cd, S, and Se. It is found that the system exhibits compositions, with variable local structure in-between that of CdS and CdSe accompanied by tunable optical band gap between that of CdS and CdSe. Theoretical calculation using density functional theory has been carried out to elucidate the observations. It is also found that luminescence induced by X-ray excitation shows new optical channels not observed previously with laser excitation. The implications of these observations are discussed.

  6. Intracellular nanoparticles mass quantification by near-edge absorption soft X-ray nanotomography

    Jose Javier Conesa; Joaquín Otón; Michele Chiappi; Jose María Carazo; Eva Pereiro; Francisco Javier Chichón; Carrascosa, José L.

    2016-01-01

    We used soft X-ray three-dimensional imaging to quantify the mass of superparamagnetic iron oxide nanoparticles (SPION) within whole cells, by exploiting the iron oxide differential absorption contrast. Near-edge absorption soft X-ray nanotomography (NEASXT) combines whole-cell 3D structure determination at 50 nm resolution, with 3D elemental mapping and high throughput. We detected three-dimensional distribution of SPIONs within cells with 0.3 g/cm3 sensitivity, sufficient for detecting the ...

  7. Intracellular nanoparticles mass quantification by near-edge absorption soft X-ray nanotomography

    Conesa, Jose Javier; Otón, Joaquín; Chiappi, Michele; Carazo, Jose María; Pereiro, Eva; Chichón, Francisco Javier; Carrascosa, José L.

    2016-01-01

    We used soft X-ray three-dimensional imaging to quantify the mass of superparamagnetic iron oxide nanoparticles (SPION) within whole cells, by exploiting the iron oxide differential absorption contrast. Near-edge absorption soft X-ray nanotomography (NEASXT) combines whole-cell 3D structure determination at 50 nm resolution, with 3D elemental mapping and high throughput. We detected three-dimensional distribution of SPIONs within cells with 0.3 g/cm3 sensitivity, sufficient for detecting the density corresponding to a single nanoparticle. PMID:26960695

  8. Structure analyses using X-ray photoelectron spectroscopy and X-ray absorption near edge structure for amorphous MS3 (M: Ti, Mo) electrodes in all-solid-state lithium batteries

    Matsuyama, Takuya; Deguchi, Minako; Mitsuhara, Kei; Ohta, Toshiaki; Mori, Takuya; Orikasa, Yuki; Uchimoto, Yoshiharu; Kowada, Yoshiyuki; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2016-05-01

    Electronic structure changes of sulfurs in amorphous TiS3 and MoS3 for positive electrodes of all-solid-state lithium batteries are examined by X-ray photoelectron spectroscopy (XPS) and the X-ray absorption near edge structure (XANES). The all-solid-state cell with amorphous TiS3 electrode shows the reversible capacity of about 510 mAh g-1 for 10 cycles with sulfur-redox in amorphous TiS3 during charge-discharge process. On the other hand, the cell with amorphous MoS3 shows the 1st reversible capacity of about 720 mAh g-1. The obtained capacity is based on the redox of both sulfur and molybdenum in amorphous MoS3. The irreversible capacity of about 50 mAh g-1 is observed at the 1st cycle, which is attributed to the irreversible electronic structure change of sulfur during the 1st cycle. The electronic structure of sulfur in amorphous MoS3 after the 10th charge is similar to that after the 1st charge. Therefore, the all-solid-state cell with amorphous MoS3 electrode shows relatively good cyclability after the 1st cycle.

  9. Characterization of local chemistry and disorder in synthetic and natural α-Al2O3 materials by X-ray absorption near edge structure spectroscopy

    X-ray absorption fine spectra at the Al K-edge were measured experimentally on and calculated theoretically via the multiple-scattering formalism for a chemically pure and physically perfect synthetic α-Al2O3 (α-alumina), a natural 'ruby/sapphire' (corundum) and a series of artificial 'corundum' produced for technical purposes and used as geochemical standards. The Al K-edge spectra differ despite of the identical coordination (short-range arrangement) assumed by O around Al, and vary slightly in relation to the slightly different chemistries of the materials (substitutional defects) as well as on account of the location taken by foreign atoms in the structural lattices (positional defects). A quantitative treatment of the observed changes is made in terms of short-range modification of the coordination polyhedron and of medium- to long-range modifications in the overall structure; both of them induced by substitutions. In some technical 'corundums', the impurities of admixed 'β-alumina', where Al is both in four- and six-fold coordination, produce another small but detectable effect on Al K-edges. Therefore, XAFS spectroscopy proves its potentials for both measuring a light element such as Al, and detecting minor coordination changes and substitutions (ca. 1∼3 wt.% as oxide) of the absorber by dilute other atoms, at least under favorable conditions as those occurring in this system are

  10. The iron-site structure of [Fe]-hydrogenase and model systems: an X-ray absorption near edge spectroscopy study†‡

    Salomone-Stagni, Marco; Stellato, Francesco; Whaley, C. Matthew; Vogt, Sonja; Morante, Silvia; Shima, Seigo; Rauchfuss, Thomas B.; Meyer-Klaucke, Wolfram

    2010-01-01

    The [Fe]-hydrogenase is an ideal system for studying the electronic properties of the low spin iron site that is common to the catalytic centres of all hydrogenases. Because they have no auxiliary iron-sulfur clusters and possess a cofactor containing a single iron centre, the [Fe]-hydrogenases are well suited for spectroscopic analysis of those factors required for the activation of molecular hydrogen. Specifically, in this study we shed light on the electronic and molecular structure of the...

  11. Quantitative investigation of two metallohydrolases by X-ray absorption spectroscopy near-edge spectroscopy

    The last several years have witnessed a tremendous increase in biological applications using X-ray absorption spectroscopy (BioXAS), thanks to continuous advancements in synchrotron radiation (SR) sources and detector technology. However, XAS applications in many biological systems have been limited by the intrinsic limitations of the Extended X-ray Absorption Fine Structure (EXAFS) technique e.g., the lack of sensitivity to bond angles. As a consequence, the application of the X-ray absorption near-edge structure (XANES) spectroscopy changed this scenario that is now continuously changing with the introduction of the first quantitative XANES packages such as Minut XANES (MXAN). Here we present and discuss the XANES code MXAN, a novel XANES-fitting package that allows a quantitative analysis of experimental data applied to Zn K-edge spectra of two metalloproteins: Leptospira interrogans Peptide deformylase (LiPDF) and acutolysin-C, a representative of snake venom metalloproteinases (SVMPs) from Agkistrodon acutus venom. The analysis on these two metallohydrolases reveals that proteolytic activities are correlated to subtle conformation changes around the zinc ion. In particular, this quantitative study clarifies the occurrence of the LiPDF catalytic mechanism via a two-water-molecules model, whereas in the acutolysin-C we have observed a different proteolytic activity correlated to structural changes around the zinc ion induced by pH variations

  12. Quantitative investigation of two metallohydrolases by X-ray absorption spectroscopy near-edge spectroscopy

    Zhao, W. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Chu, W.S.; Yang, F.F.; Yu, M.J.; Chen, D.L.; Guo, X.Y. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Zhou, D.W.; Shi, N. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy); Niu, L.W.; Teng, M.K. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Gong, W.M. [Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101 (China); Benfatto, M. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy); Wu, Z.Y. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy)], E-mail: wuzy@ihep.ac.cn

    2007-09-21

    The last several years have witnessed a tremendous increase in biological applications using X-ray absorption spectroscopy (BioXAS), thanks to continuous advancements in synchrotron radiation (SR) sources and detector technology. However, XAS applications in many biological systems have been limited by the intrinsic limitations of the Extended X-ray Absorption Fine Structure (EXAFS) technique e.g., the lack of sensitivity to bond angles. As a consequence, the application of the X-ray absorption near-edge structure (XANES) spectroscopy changed this scenario that is now continuously changing with the introduction of the first quantitative XANES packages such as Minut XANES (MXAN). Here we present and discuss the XANES code MXAN, a novel XANES-fitting package that allows a quantitative analysis of experimental data applied to Zn K-edge spectra of two metalloproteins: Leptospira interrogans Peptide deformylase (LiPDF) and acutolysin-C, a representative of snake venom metalloproteinases (SVMPs) from Agkistrodon acutus venom. The analysis on these two metallohydrolases reveals that proteolytic activities are correlated to subtle conformation changes around the zinc ion. In particular, this quantitative study clarifies the occurrence of the LiPDF catalytic mechanism via a two-water-molecules model, whereas in the acutolysin-C we have observed a different proteolytic activity correlated to structural changes around the zinc ion induced by pH variations.

  13. Order-disorder in olivine minerals by synchrotron X-ray absorption near-edge structure (Xane) spectroscopy at the Mg, Fe and Ca K edges

    In this paper, are presented new, high-resolution experimental spectra at the Mg and Fe K edges for the two Fe-Mg endmembers F o and F a, and for three other olivines. Two are the Ca endmembers of the family, namely monticellite (Mtc: CaMgSiO4) and kirschsteinite (Krs: CaFeSiO4). The main purpose of this work is to investigate the effects of Mg, Fe, and Ca partition in the Pbnm (or α) olivine structure on the electronic properties, as well as the relationships that exist between chemical substitutions and features occurring in Xanes spectra. One wants to explore the relationships that intervene between LRO, as determined by XRD, and SRO, as determined by Xanes, on the endmembers and on a well-known intermediate member as well, and deduce from it a model for the behavior of the entire olivine solid-solution system

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

    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

    2016-04-01

    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. PMID:26959687

  15. [Distribution and speciation of Pb in Arabidopsis thaliana shoot and rhizosphere soil by in situ synchrotron radiation micro X-ray fluorescence and X-ray absorption near edge structure].

    Shen, Ya-Ting

    2014-03-01

    In order to investigate plant reacting mechanism with heavy metal stress in organ and tissue level, synchrotron radiation micro X-ray fluorescence (micro-SRXRF) was used to determine element distribution characteristics of K, Ca, Mn, Fe, Cu, Zn, Pb in an Arabidopsis thaliana seedling grown in tailing dam soil taken from a lead-zinc mine exploration area. The results showed a regular distribution characters of K, Ca, Fe, Cu and Zn, while Pb appeared not only in root, but also in a leaf bud which was beyond previously understanding that Pb mainly appeared in plant root. Pb competed with Mn in the distribution of the whole seedling. Pb may cause the increase of oxidative stress in root and leaf bud, and restrict Mn absorption and utilization which explained the phenomenon of seedling death in this tailing damp soil. Speciation of Pb in Arabidopsis thaliana and tailing damp rhizosphere soil were also presented after using PbL3 micro X-ray absorption near edge structure (micro-XANES). By comparison of PbL3 XANES peak shape and peak position between standard samples and rhizosphere soil sample, it was demonstrated that the tailing damp soil was mainly formed by amorphous forms like PbO (64.2%), Pb (OH)2 (28.8%) and Pb3O4 (6.3%) rather than mineral or organic Pb speciations. The low plant bioavailability of Pb demonstrated a further research focusing on Pb absorption and speciation conversion is needed, especially the role of dissolve organic matter in soil which may enhance Pb bioavailability. PMID:25208420

  16. Neutralization of calcite in mineral aerosols by acidic sullur species collected in China and Japan studied by ca K-edge X-ray absorption near-edge structure.

    Takahashi, Yoshio; Miyoshi, Takuro; Higashi, Masayuki; Kamioka, Hikari; Kanai, Yutaka

    2009-09-01

    Calcium species in mineral aerosols collected simultaneously in Aksu (near the Taklimakan Desert), Qingdao (eastern China), and Tsukuba (Japan) during dust and nondust periods were determined using Ca K-edge X-ray absorption near-edge structure (XANES). From the fitting of XANES spectra, it was found that (i) calcite and gypsum were the main Ca species in the aerosol samples, and (ii) the gypsum fraction versus total Ca minerals [Gyp]/[Ca2+]t increased progressively in the order Aksu aerosols for all the samples except for that taken in Aksu during the dust period. The decrease of the [Gyp]/[Ca2+]t ratio with an increase in particle size showed that the neutralization effect proceeds from the particle surface. For the Aksu sample in the dust period, however, (i) the [Gyp]/[Ca2+]t ratios obtained by XANES measured in the fluorescence (FL; regarded as bulk analysis) and CEY modes were similar and (ii) size dependence was not found, showing that neutralization is not important for the sample because of the large supply of mineral aerosol with little neutralization effect in Aksu. It was also found that the pH of the aerosol and the ratio of (NH4)2SO4 to gypsum were positively and negatively correlated with the Ca (or calcite) content, respectively. The speciation of Ca by XANES revealed the neutralization processes of acidic sulfur species by calcite during the long-range transport of mineral aerosols. PMID:19764213

  17. A high resolution x-ray fluorescence spectrometer for near edge absorption studies

    A high resolution fluorescence spectrometer using a Johann geometry in a back scattering arrangement was developed. The spectrometer, with a resolution of 0.3 eV at 6.5 keV, combined with an incident beam, with a resolution of 0.7 eV, form the basis of a high resolution instrument for measuring x-ray absorption spectra. The advantages of the instrument are illustrated with the near edge absorption spectrum of dysprosium nitrate. 10 refs., 4 figs

  18. Arsenate reduction and methylation in the cells of Trichoderma asperellum SM-12F1, Penicillium janthinellum SM-12F4, and Fusarium oxysporum CZ-8F1 investigated with X-ray absorption near edge structure

    Su, S.M., E-mail: shimingsu@163.com [Institute of Environment and Sustainable Development in Agriculture, Chinese Academy of Agricultural Sciences/Key Laboratory of Agro-Environment, Ministry of Agriculture, Beijing (China); Zeng, X.B., E-mail: zengxb@ieda.org.cn [Institute of Environment and Sustainable Development in Agriculture, Chinese Academy of Agricultural Sciences/Key Laboratory of Agro-Environment, Ministry of Agriculture, Beijing (China); Li, L.F.; Duan, R.; Bai, L.Y. [Institute of Environment and Sustainable Development in Agriculture, Chinese Academy of Agricultural Sciences/Key Laboratory of Agro-Environment, Ministry of Agriculture, Beijing (China); Li, A.G.; Wang, J.; Jiang, S. [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai (China)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer Three fungal strains are capable of As(V) reduction and methylation. Black-Right-Pointing-Pointer As(V) reduction might be more easily processed than the methylation in fungal cells. Black-Right-Pointing-Pointer As sequestration and speciation transformation might be the detoxification processes. - Abstract: Synchrotron radiation-based X-ray absorption near edge structure (XANES) was introduced to directly analysis chemical species of arsenic (As) in the cells of Trichoderma asperellum SM-12F1, Penicillium janthinellum SM-12F4, and Fusarium oxysporum CZ-8F1 capable of As accumulation and volatilisation. After exposure to As(V) of 500 mg L{sup -1} for 15 days, a total of 60.5% and 65.3% of the accumulated As in the cells of T. asperellum SM-12F1 and P. janthinellum SM-12F4, respectively, was As(III), followed by 31.3% and 32.4% DMA (dimethylarsinic acid), 8.3% and 2.3% MMA (monomethylarsonic acid), respectively. However, for F. oxysporum CZ-8F1, 54.5% of the accumulated As was As(III), followed by 37.8% MMA and 7.7% As(V). The reduction and methylation of As(V) formed As(III), MMA, and DMA as the primacy products, and the reduction of As(V) might be more easily processed than the methylation. These results will help to understanding the mechanisms of As detoxification and its future application in bioremediation.

  19. Determination of forest soil organic nitrogen determination using technique of X-ray absorption near-edge structure%森林土壤有机氮的X光吸收近边结构光谱技术测定

    庄舜尧; 徐梦洁; 胡正义

    2006-01-01

    本研究通过采用氮的K边X光吸收近边结构(XANES)技术来了解森林土壤有机氮,以此深入研究土壤中有机氮种类与其转化的定量关系.土壤样品采自台湾中部的云杉、铁杉林与草地.结果表明,氮的XANES可以揭示样品中不同的氮的种类.在土壤腐植质、可溶性氮及本体土壤中胺态及吡咯氮占了主要的比率.然而不同处理及植被下的土壤样品氮的种类分布是不同的.云杉与铁杉土壤可溶性有机氮在402.3 eV能量处有显著的差异.在A层土壤中,吡啶类氮含量要显著高于O层土壤,说明氮在不同土层中的转化率存在极大的差异,这种变化对于氮在森林土壤中的循环将起重要作用.图3表1参8.%The forest soil organic N was investigated using N K-edge X-ray absorption near-edge structure (XANES) to gain an insight into the relationship between N speciation and its transformation in quantity. Soil samples were collected from spruce, hemlock and pine forests in central Taiwan. Results showed that various organic N types could be revealed by XANES spectra. Amide and pyrrolic N are the major parts of the composition in the humic substance, soluble organic nitrogen and original soils. The relative distribution of N speciation differed in treatments and vegetations samples. The spruce had a significant difference from the hemlock in soluble organic nitrogen (SON) spectra at 402.3 eV energy peak. In the A-horizon soils, the relative amount of pyridinic N was much higher than that in the O-horizon soils, indicating N transformation in quantity in the mineral horizon was different from that in the organic horizon, which might play an important role in N cycling of forest ecosystems.

  20. In situ time-resolved X-ray near-edge absorption spectroscopy of selenite reduction by siderite

    The reduction oxidation-reaction between aqueous selenite (SeO32-) and siderite (FeCO3(s)) was monitored by in situ, time-resolved X-ray absorption near-edge structure (XANES) spectroscopy at the selenium K edge in a controlled electrochemical environment. Spectral evolutions showed that more than 60% of selenite was reduced at the siderite surface after 20 h of experiment, at which time the reaction was still incomplete. Fitting of XANES spectra by linear combination of reference spectra showed that selenite reaction with siderite is essentially a two-step process, selenite ions being immobilized on siderite surface prior to their reduction. A kinetic model of the reduction step is proposed, allowing to identify the specific contribution of surface reduction. These results have strong implications for the retention of selenite by corrosion products in nuclear waste repositories and in a larger extent for the fate of selenium in the environment. (authors)

  1. Evaluation of iron-containing carbon nanotubes by near edge X-ray absorption technique

    The synthesis of carbon nanotubes (CNTs) via Chemical Vapor Deposition method with ferrocene results in CNTs filled with Fe-containing nanoparticles. The present work proposes a novel route to characterize the Fe phases in CNTs inherent to the synthesis process. CNTs were synthesized and, afterwards, the CNTs were heat treated at 1000 °C for 20 min in an inert atmosphere during a thermogravimetric experiment. X-Ray Absorption Spectroscopy (XAS) experiments were performed on the CNTs before and after the heat treatment and, also, during the heat treatment, e.g., in situ tests were performed while several Near-Edge X-Ray Absorption (XANES) spectra were collected during the heating of the samples. The XAS technique was successfully applied to evaluate the phases encapsulated by CNTs. Phase transformations of the Fe-based nanoparticles were also observed from iron carbide to metallic iron when the in situ experiments were performed. Results also indicated that the applied synthesis method guarantees that Fe phases are not oxidize. In addition, the results show that heat treatment under inert atmosphere can control which phase remains encapsulated by the CNTs. - Highlights: • CNTs filled with Fe-based nanoparticles were heat treated in inert atmosphere. • EXAFS analysis was performed on CNTs, and LCF and FT were obtained. • In situ XANES measurements were performed during the heating of the samples. • Fe-based particles change from Fe carbide to metallic Fe during the heat treatment. • The applied synthesis method guarantees that Fe phases are not oxidize

  2. X-ray absorption near-edge structures of LiMn2O4 and LiNi0.5Mn1.5O4 spinel oxides for lithium-ion batteries: the first-principles calculation study.

    Okumura, Toyoki; Yamaguchi, Yoichi; Kobayashi, Hironori

    2016-07-21

    Experimental Mn and Ni K-edge X-ray absorption near-edge structure (XANES) spectra were well reproduced for 5 V-class LixNi0.5Mn1.5O4 spinels as well as 4 V-class LixMn2O4 spinels using density functional theory. Local environmental changes around the Mn or Ni centres due to differences in the locations of Li ions and/or phase transitions in the spinel oxides were found to be very important contributors to the XANES shapes, in addition to the valence states of the metal ions. PMID:27333155

  3. Analysis of near edge fine structure and electronic populations in sapphire

    AlL and OK near edge fine structures in sapphire are studied using electron energy loss microspectroscopy in a transmission electron microscope; an analysis of the electronic populations of atoms Al and O, and a comparison between different partial cross sections are given. The authors consider the ionization of an atom in a homogeneous solid to interpret the elemental effects in the ionization region near edges. The chemical effects in the region near edge onset are interpreted by using extended Hueckel molecular orbital theory and Bloch's theorem including the effects of translation symmetry in crystals to calculate the electronic transitions from core-shell to unoccupied valence-shell. The authors also consider the additional chemical effects, which arise from the elastic backscattering of the atomic ionization waves by the atoms neighboring the exited atom, giving rise to the so-called extended fine structure in the ionization region. The agreement between the calculated results and the experimental energy loss spectra of sapphire from single-phase region is good

  4. X-ray Absorption Near Edge Structure (XANES) study of YBaCo4-xFexO7 (x = 0.2, 0.4, 0.5, 0.6, and 0.8) using synchrotron radiation

    YBaCo4O7 is an important material in the class of cobaltates which shows a high degree of magnetic frustration. The crystal structure of YBaCo4O7 is built up of Kagome sheets of CoO4 tetrahedra, linked by triangular layers of CoO4 tetrahedra. The ratio of Co ion numbers in the Kagome to triangular lattices is 3:1 and it shows mixed valency of Co consisting of Co2+ and Co3+ states. Here, we report the XANES measurements on Fe doped YBaCo4O7, i.e., YBaCo4-xFexO7 compounds using Synchrotron radiation. The shifts of the K-absorption edges of Co have been investigated for these samples as a function by Fe doping concentration. The measurements have been carried out at the recently commissioned Dispersive EXAFS beamline (BL-8) at INDUS-2 Synchrotron Radiation source at RRCAT, Indore. From the XANES spectra of the samples it is found that that Co K absorption edge (E0) of YBaCo4-xFexO7 samples is shifted gradually to the higher energy as the Fe concentration (x) in the samples is increased from 0.2 to 0.8

  5. Characterization of local chemistry and disorder in synthetic and natural {alpha}-Al{sub 2}O{sub 3} materials by X-ray absorption near edge structure spectroscopy

    Mottana, A. [Rome, Univ. `Roma Tre` (Italy). Dip. di Scienze Geologiche]|[INFN, Laboratori Nazionali di Frascati, Rome (Italy); Murata, T. [Kyoto, Univ. of Education (Japan). Dept. of Physics; Marcelli, A. [INFN, Laboratori Nazionali di Frascati, Rome (Italy)] [and others

    1997-11-01

    X-ray absorption fine spectra at the Al K-edge were measured experimentally on and calculated theoretically via the multiple-scattering formalism for a chemically pure and physically perfect synthetic {alpha}-Al{sub 2}O{sub 3} ({alpha}-alumina), a natural `ruby/sapphire` (corundum) and a series of artificial `corundum` produced for technical purposes and used as geochemical standards. The Al K-edge spectra differ despite of the identical coordination (short-range arrangement) assumed by O around Al, and vary slightly in relation to the slightly different chemistries of the materials (substitutional defects) as well as on account of the location taken by foreign atoms in the structural lattices (positional defects). A quantitative treatment of the observed changes is made in terms of short-range modification of the coordination polyhedron and of medium- to long-range modifications in the overall structure; both of them induced by substitutions. In some technical `corundums`, the impurities of admixed `{beta}-alumina`, where Al is both in four- and six-fold coordination, produce another small but detectable effect on Al K-edges. Therefore, XAFS spectroscopy proves its potentials for both measuring a light element such as Al, and detecting minor coordination changes and substitutions (ca. 1{approx}3 wt.% as oxide) of the absorber by dilute other atoms, at least under favorable conditions as those occurring in this system are.

  6. Electrosynthesis of ZnO nanorods and nanotowers: Morphology and X-ray Absorption Near Edge Spectroscopy studies

    Sigircik, Gokmen; Erken, Ozge; Tuken, Tunc; Gumus, Cebrail; Ozkendir, Osman M.; Ufuktepe, Yuksel

    2015-06-01

    Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. The resulting opto-electronic properties were interpreted extensively, using X-ray diffraction (XRD), X-ray Absorption Near Edge Spectroscopy (XANES), field emission scanning electron microscopy (FE-SEM), UV-Visible spectroscopy and four probe techniques. The ZnO deposition is mass transport controlled process and the interaction of chloride ions with the surface has great influence on diffusion kinetics, considering the substantial species (Zn2+ and OH-) involved in the construction of ZnO film. This effect does not change major lattice parameters, as shown with detailed analysis of XRD data. However, the texture coefficient (Tc) (0 0 2) value is higher in presence of chloride ions containing synthesis solution which gave vertically aligned, well defined and uniformly dispersed nanorods structure. The calculated Eg values are in the range 3.28-3.41 eV and 3.22-3.31 eV for ZnO nanorods and nanotowers synthesized at different deposition periods, respectively. Furthermore, the charge mobility values regarding the deposition periods were measured to be in the ranges from 130.4 to 449.2 cm2 V-1 s-1 and 126.2 to 204.7 cm2 V-1 s-1 for nanorods and nanotowers, respectively. From XANES results, it was shown that the Zn K-edge spectrum is dominated by the transition of Zn 1s core electrons into the unoccupied Zn 4p states of the conduction band. Comparing the rod and tower nano-structured ZnO thin films, the excitation behavior of valence band electrons is different. Moreover, the density states of Zn 4p are higher for ZnO nanorods.

  7. Double conical crystal x-ray spectrometer for high resolution ultrafast x-ray absorption near-edge spectroscopy of Al K edge

    Levy, A.; Dorchies, F.; Fourment, C.; Harmand, M.; Hulin, S.; Santos, J. J.; Descamps, D.; Petit, S.; Bouillaud, R. [Centre Lasers Intenses et Applications (CELIA), Universite de Bordeaux-CNRS-CEA, Talence F-33405 (France)

    2010-06-15

    An x-ray spectrometer devoted to dynamical studies of transient systems using the x-ray absorption fine spectroscopy technique is presented in this article. Using an ultrafast laser-induced x-ray source, this optical device based on a set of two potassium acid phthalate conical crystals allows the extraction of x-ray absorption near-edge spectroscopy structures following the Al absorption K edge. The proposed experimental protocol leads to a measurement of the absorption spectra free from any crystal reflectivity defaults and shot-to-shot x-ray spectral fluctuation. According to the detailed analysis of the experimental results, a spectral resolution of 0.7 eV rms and relative fluctuation lower than 1% rms are achieved, demonstrated to be limited by the statistics of photon counting on the x-ray detector.

  8. Preliminary optical design of a varied line-space spectrograph for the multi-channel detection of near-edge X-ray absorption fine structure (NEXAFS) spectra in the 280-550 eV energy range

    Wheeler, B.S.; McKinney, W.R.; Hussain, Z.; Padmore, H.

    1996-07-01

    The optical design of a varied line-space spectrograph for the multi-channel recording of NEXAFS spectra in a single {open_quotes}snapshot{close_quotes} is proposed. The spectrograph is to be used with a bending magnet source on beamline 7.3.2 at the Advanced Light Source (ALS). Approximately 20 volts of spectra are simultaneously imaged across a small square of material sample at each respective K absorption edge of carbon, nitrogen, and oxygen. Photoelectrons emitted from the material sample will be collected by an electron imaging microscope, the view field of which determines the sampling size. The sample also forms the exit slit of the optical system. This dispersive method of NEXAFS data acquisition is three to four orders of magnitude faster than the conventional method of taking data point-to-point using scanning of the grating. The proposed design is presented along with the design method and supporting SHADOW raytrace analysis.

  9. Electrosynthesis of ZnO nanorods and nanotowers: Morphology and X-ray Absorption Near Edge Spectroscopy studies

    Sigircik, Gokmen, E-mail: gsigircik@cu.edu.tr [Chemistry Department, University of Cukurova, 01330 Adana (Turkey); Erken, Ozge [Department of Physics, Faculty Science and Letters, Adiyaman University, 02040 Adiyaman (Turkey); Tuken, Tunc [Chemistry Department, University of Cukurova, 01330 Adana (Turkey); Gumus, Cebrail [Physics Department, University of Cukurova, 01330 Adana (Turkey); Ozkendir, Osman M. [Department of Energy Systems Engineering Tarsus Technology Faculty, Mersin University, 33400 Tarsus (Turkey); Ufuktepe, Yuksel [Physics Department, University of Cukurova, 01330 Adana (Turkey)

    2015-06-15

    Highlights: • Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. • Uniform and well-defined ZnO nano-towers and rods have been obtained via electrochemical deposition. • The presence of chloride ions altered the nucleation rate of ZnO particles on ITO substrates and resulting crystallographic properties. • Comparing the rod and tower nano-structured ZnO thin films, the excitation behavior of valance band electrons is different. - Abstract: Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. The resulting opto-electronic properties were interpreted extensively, using X-ray diffraction (XRD), X-ray Absorption Near Edge Spectroscopy (XANES), field emission scanning electron microscopy (FE-SEM), UV-Visible spectroscopy and four probe techniques. The ZnO deposition is mass transport controlled process and the interaction of chloride ions with the surface has great influence on diffusion kinetics, considering the substantial species (Zn{sup 2+} and OH{sup −}) involved in the construction of ZnO film. This effect does not change major lattice parameters, as shown with detailed analysis of XRD data. However, the texture coefficient (T{sub c}) (0 0 2) value is higher in presence of chloride ions containing synthesis solution which gave vertically aligned, well defined and uniformly dispersed nanorods structure. The calculated E{sub g} values are in the range 3.28–3.41 eV and 3.22–3.31 eV for ZnO nanorods and nanotowers synthesized at different deposition periods, respectively. Furthermore, the charge mobility values regarding the deposition periods were measured to be in the ranges from 130.4 to 449.2 cm{sup 2} V{sup −1} s{sup −1} and 126.2 to 204.7 cm{sup 2} V{sup −1} s{sup −1} for nanorods and nanotowers, respectively. From XANES results, it was shown that the Zn K

  10. Electrosynthesis of ZnO nanorods and nanotowers: Morphology and X-ray Absorption Near Edge Spectroscopy studies

    Highlights: • Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. • Uniform and well-defined ZnO nano-towers and rods have been obtained via electrochemical deposition. • The presence of chloride ions altered the nucleation rate of ZnO particles on ITO substrates and resulting crystallographic properties. • Comparing the rod and tower nano-structured ZnO thin films, the excitation behavior of valance band electrons is different. - Abstract: Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. The resulting opto-electronic properties were interpreted extensively, using X-ray diffraction (XRD), X-ray Absorption Near Edge Spectroscopy (XANES), field emission scanning electron microscopy (FE-SEM), UV-Visible spectroscopy and four probe techniques. The ZnO deposition is mass transport controlled process and the interaction of chloride ions with the surface has great influence on diffusion kinetics, considering the substantial species (Zn2+ and OH−) involved in the construction of ZnO film. This effect does not change major lattice parameters, as shown with detailed analysis of XRD data. However, the texture coefficient (Tc) (0 0 2) value is higher in presence of chloride ions containing synthesis solution which gave vertically aligned, well defined and uniformly dispersed nanorods structure. The calculated Eg values are in the range 3.28–3.41 eV and 3.22–3.31 eV for ZnO nanorods and nanotowers synthesized at different deposition periods, respectively. Furthermore, the charge mobility values regarding the deposition periods were measured to be in the ranges from 130.4 to 449.2 cm2 V−1 s−1 and 126.2 to 204.7 cm2 V−1 s−1 for nanorods and nanotowers, respectively. From XANES results, it was shown that the Zn K-edge spectrum is dominated by the transition of Zn 1s core electrons

  11. Experimental station for laser-based picosecond time-resolved x-ray absorption near-edge spectroscopy

    We present an experimental station designed for time-resolved X-ray Absorption Near-Edge Spectroscopy (XANES). It is based on ultrashort laser-plasma x-ray pulses generated from a table-top 100 mJ-class laser at 10 Hz repetition rate. A high transmission (10%–20%) x-ray beam line transport using polycapillary optics allows us to set the sample in an independent vacuum chamber, providing high flexibility over a wide spectral range from 0.5 up to 4 keV. Some XANES spectra are presented, demonstrating 1% noise level in only ∼1 mn and ∼100 cumulated laser shots. Time-resolved measurements are reported, indicating that the time resolution of the entire experimental station is 3.3 ± 0.6 ps rms

  12. Unraveling the Solid-Liquid-Vapor Phase Transition Dynamics at the Atomic Level with Ultrafast X-Ray Absorption Near-Edge Spectroscopy

    X-ray absorption near-edge spectroscopy (XANES) is a powerful probe of electronic and atomic structures in various media, ranging from molecules to condensed matter. We show how ultrafast time resolution opens new possibilities to investigate highly nonequilibrium states of matter including phase transitions. Based on a tabletop laser-plasma ultrafast x-ray source, we have performed a time-resolved (∼3 ps) XANES experiment that reveals the evolution of an aluminum foil at the atomic level, when undergoing ultrafast laser heating and ablation. X-ray absorption spectra highlight an ultrafast transition from the crystalline solid to the disordered liquid followed by a progressive transition of the delocalized valence electronic structure (metal) down to localized atomic orbitals (nonmetal--vapor), as the average distance between atoms increases.

  13. Biogeochemical reductive release of soil embedded arsenate around a crater area (Guandu) in northern Taiwan using X-ray absorption near-edge spectroscopy

    Kai-Ying Chiang; Tsan-Yao Chen; Chih-Hao Lee; Tsang-Lang Lin; Ming-Kuang Wang; Ling-Yun Jang; Jyh-Fu Lee

    2013-01-01

    This study investigates biogeochemical reductive release of arsenate from beudantite into solution in a crater area in northern Taiwan,using a combination of X-ray absorption near-edge structure (XANES) and atomic absorption spectrometry.Total arsenic (As)concentrations in the soil were more than 200 mg/kg.Over four months of laboratory experiments,less than 0.8% As was released into solution after reduction experiments.The 71% to 83% As was chemically reduced into arsenite (As(Ⅲ)) and partially weathering into the soluble phase.The kinetic dissolution and re-precipitation of As,Fe,Pb and sulfate in this area of paddy soils merits further study.

  14. A Study on Distribution and Chemical Speciation of Lead in Corn Seed Germination by Synchrotron Radiation X-ray Fluorescence and Absorption near Edge Structure Spectrometry%基于SRXRF和XANES研究Pb对玉米种子萌芽的影响及其分布和形态特征

    孙建伶; 罗立强

    2014-01-01

    Synchrotron radiation X-ray fluorescence analysis technology (SRXRF) can effectively reduce the detection limit for the determination of heavy metal elements, especially suitable for in situ nondestructive analysis of biological samples with low contents. By corn seed germination test, and combining with SRXRF technology, the effects of Pb on corn seed germination and Pb micro-distribution in the corn seed were studied. X-ray absorption near edge structure (XANES ) technique was used to analyze the Pb chemical speciation in different parts of corn seed. The above experiment was taken to understand the absorption and transformation mechanism of Pb by corn seeds. Results showed that germination rate, bud length and root length decreased with increased Pb contents. The analysis of variance showed that P-value of the germination rate, bud length and root elongation of corn seeds which were exposed to different concentration of Pb were 2. 0×10-3, 1. 4×10-4 and 2. 39×10-8, which were all less than 0. 01, therefore there were highly significant differences during these three indicators and the content of Pb. In addition, the inhibition effect on root growth was greater. SRXRF analysis results showed that Pb was mainly enriched in episperm and embryo, which would inhibit embryonic develop into bud and root. The Pb-LⅢ(13035 eV) XANES spectra of all samples include of root, shoot and the different part of seed were the same, they were the same speciation. Linear combination fitting results indicated that the lead phosphate chloride and lead stearate accounted for 74 . 3 %and 24. 2 % respectively, which suggested that the main Pb speciation of corn was lead phosphate chloride which deposited inside of corn, and a few combined with carboxylic to form the organic lead.%以受不同浓度Pb胁迫下的玉米种子萌芽试验为基础,结合SRXRF研究Pb对玉米种子萌芽的影响和Pb在玉米种子的微区分布特征,利用X射线吸收近边结构技术( XANES)对

  15. O K-energy loss near-edge structure change induced by tantalum impurity in monoclinic hafnium oxide

    The present paper reports the energy loss near-edge structure (ELNES) study of monoclinic HfO2 (m-HfO2) and tantalum doped m-HfO2 (Ta0.1Hf0.9O2) thin films prepared by radio frequency magnetron co-sputtering method. A change in the O K-ELNES spectra was observed as the amount of dopant increases. In order to precise the common features and the differences as a function of Ta defect nature (substitutional or interstitial) in HfO2, the O K-ELNES were commented with respect to density functional theory calculations implemented in Vienna ab initio simulation package code. The calculated Ta doped HfO2 band structure showed that substitutional tantalum is the dominant defect and the spectral differences between doped and non-doped HfO2 are mainly originated from the change in the local cation distribution around the oxygen atoms.

  16. In situ X-ray near-edge absorption spectroscopy investigation of the state of charge of all-vanadium redox flow batteries.

    Jia, Chuankun; Liu, Qi; Sun, Cheng-Jun; Yang, Fan; Ren, Yang; Heald, Steve M; Liu, Yadong; Li, Zhe-Fei; Lu, Wenquan; Xie, Jian

    2014-10-22

    Synchrotron-based in situ X-ray near-edge absorption spectroscopy (XANES) has been used to study the valence state evolution of the vanadium ion for both the catholyte and anolyte in all-vanadium redox flow batteries (VRB) under realistic cycling conditions. The results indicate that, when using the widely used charge-discharge profile during the first charge process (charging the VRB cell to 1.65 V under a constant current mode), the vanadium ion valence did not reach V(V) in the catholyte and did not reach V(II) in the anolyte. Consequently, the state of charge (SOC) for the VRB cell was only 82%, far below the desired 100% SOC. Thus, such incompletely charged mix electrolytes results in not only wasting the electrolytes but also decreasing the cell performance in the following cycles. On the basis of our study, we proposed a new charge-discharge profile (first charged at a constant current mode up to 1.65 V and then continuously charged at a constant voltage mode until the capacity was close to the theoretical value) for the first charge process that achieved 100% SOC after the initial charge process. Utilizing this new charge-discharge profile, the theoretical charge capacity and the full utilization of electrolytes has been achieved, thus having a significant impact on the cost reduction of the electrolytes in VRB. PMID:25191695

  17. Microbeam X-ray Absorption Near-Edge Spectroscopy study of the oxidation of Fe and Nb in zirconium alloy oxide layers

    Alloy optimization of zirconium based alloys used for nuclear fuel cladding is key to increasing corrosion resistance and reducing hydrogen pickup. The mechanism by which alloying elements influence these processes is investigated by focusing on the chemical state evolution of two alloying elements, Fe and Nb, when incorporated into the growing oxide layers of various production zirconium alloys – Zircaloy-4, ZIRLO® and Zr–2.5Nb – as well as a model alloy – Zr–0.4Fe–0.2Cr. X-ray Absorption Near-Edge Spectroscopy (XANES) measurements to determine the evolution of their oxidation states is performed using micro-beam synchrotron radiation on cross sectional oxide samples. A thin (∼12 μm) cross-sectional sample of Zircaloy-4 oxide was also designed and fabricated to differentiate the signal coming from the Fe in solid solution from the signal coming from the Fe in precipitates. The XANES spectra were fitted using a combination of standards, to determine the evolution of the oxidized fractions of Fe and Nb in the oxide as function of distance from the oxide/metal interface. The results show that the oxidation of Fe and Nb in the oxide layer is delayed relative to that of Zr. Both the second phase precipitates and solid solution Fe atoms were initially incorporated in metallic form into the oxide layer, although it appears that Fe in solid solution oxidizes first. It is shown that after a given distance from the metal/oxide interface (which is alloy dependent), the alloying elements start to oxidize. Qualitative TEM examinations of precipitates embedded in zirconium oxide layers correlate well with the quantitative XANES results. These results allow a discussion of a qualitative oxidation model of Fe and Nb in Zr alloys

  18. Debris of potassium–magnesium silicate glass generated by femtosecond laser-induced ablation in air: An analysis by near edge X-ray absorption spectroscopy, micro Raman and energy dispersive X-ray spectroscopy

    The redeposited material (debris) resulting from ablation of a potassium–magnesium silicate glass upon scanning femtosecond laser pulse irradiation (130 fs, 800 nm) in air environment is investigated by means of three complementary surface analytical methods. Changes in the electronic band structure of the glass constituent Magnesium (Mg) were identified by X-ray Absorption Near Edge Structure spectroscopy (XANES) using synchrotron radiation. An up-shift of ≈0.8 eV of a specific Magnesium K-edge absorption peak in the spectrum of the redeposited material along with a significant change in its leading edge position was detected. In contrast, the surface left after laser ablation exhibits a downshift of the peak position by ≈0.9 eV. Both observations may be related to a change of the Mg coordinative state of the laser modified/redeposited glass material. The presence of carbon in the debris is revealed by micro Raman spectroscopy (μ-RS) and was confirmed by energy dispersive X-ray spectroscopy (EDX). These observations are attributed to structural changes and chemical reactions taking place during the ablation process.

  19. Geometric and electronic structure effects in polarized V K-edge absorption near edge structure spectra

    Šipr, Ondřej; Šimůnek, Antonín; Bocharov, S.; Kirchner, T.; Dräger, G.

    1999-01-01

    Roč. 60, č. 20 (1999), s. 14115-14127. ISSN 0163-1829 R&D Projects: GA ČR GA202/97/0566; GA ČR GA203/99/0067 Grant ostatní: HASYLAB(DE) 00-95-67 Institutional research plan: CEZ:AV0Z1010914 Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.008, year: 1999

  20. 同步辐射软X射线近边吸收谱方法研究长期施肥对黑土有机氮官能团的影响%Effect of Long-Term Fertilization on Organic Nitrogen Functional Groups in Black Soil as Revealed by Synchrotron-Based X-Ray Absorption Near-Edge Structure Spectroscopy

    李辉; 高强; 王帅; 朱平; 张晋京; 赵屹东

    2015-01-01

    scientific basis for formulating the reasonable farmland management strategies .Synchrotron radiation soft X‐ray absorption near‐edge structure (N K‐edge XANES) spectroscopy is the most powerful tool to characterize in situ organic N functional groups compositions in soil .However ,to our most knowledge ,no studies have been conducted to examine the organic N functional groups compositions of soil using N K‐edge XANES spectroscopy under long‐term fertilization practices .Based on a long‐term field experiment (started in 1990) in a black soil (Gongzhuling ,Northeast China) ,we investigated the differences in organic N functional groups compositions in bulk soil and clay‐size soil fraction among fertilization patterns using synchrotron‐based N K‐edge XANES spectroscopy .Composite soil samples (0~20 cm) were collected in 2008 .The present study included six treat‐ments:farmland fallow (FALL ) ,no‐fertilization control (CK ) ,chemical nitrogen ,phosphorus ,and potassium fertilization (NPK) ,NPK in combination with organic manure (NPKM) ,1.5 times of NPKM (1.5 NPKM) ,and NPK in combination with maize straw (NPKS) .The results showed that N K‐edge XANES spectra of all the treatments under study exhibited characteris‐tic absorption peaks in the ranges of 401.2~401.6 and 402.7~403.1 eV ,which were assigned as amides/amine‐N and pyrrole‐N ,respectively .These characteristic absorption peaks were more obvious in clay‐size soil fraction than in bulk soil .The results obtained from the semi‐quantitative analysis of N K‐edge XANES spectra indicated that the relative proportion of amides/amine‐N was the highest in both bulk soil and clay‐size soil fraction ,and it was the most major forms in soil organic nitrogen functional groups .Compared with the FALL treatment ,the relative proportion of amide/amine‐N was lower whereas that of Pyrrole‐N was higher in the CK treatment .In the treatments with combined chemical fertilizers and organic manure

  1. Distribution and Speciation of Pb in Arabidopsis Thaliana Shoot and Rhizosphere Soil by In Situ Synchrotron Radiation Micro X-Ray Fluorescence and X-Ray Absorption Near Edge Structure%原位微区同步辐射X射线荧光和近边吸收谱研究拟南芥幼苗及根际土壤中铅分布与形态特征

    沈亚婷

    2014-01-01

    In order to investigate plant reacting mechanism with heavy metal stress in organ and tissue level ,synchrotron radia-tion micro X-ray fluorescence(μ-SRXRF) was used to determine element distribution characteristics of K ,Ca ,Mn ,Fe ,Cu ,Zn , Pb in an Arabidopsis thaliana seedling grown in tailing dam soil taken from a lead-zinc mine exploration area. The results showed a regular distribution characters of K ,Ca ,Fe ,Cu and Zn ,while Pb appeared not only in root ,but also in a leaf bud which was beyond previously understanding that Pb mainly appeared in plant root. Pb competed with Mn in the distribution of the whole seedling. Pb may cause the increase of oxidative stress in root and leaf bud ,and restrict Mn absorption and utilization which ex-plained the phenomenon of seedling death in this tailing damp soil. Speciation of Pb in Arabidopsis thaliana and tailing damp rhi-zosphere soil were also presented after using PbL3 micro X-ray absorption near edge structure(μ-XANES). By comparison of PbL3 XANES peak shape and peak position between standard samples and rhizosphere soil sample ,it was demonstrated that the tailing dampsoilwasmainlyformedbyamorphousformslikePbO(64.2% ),Pb(OH)2(28.8% )andPb3O4(6.3% )ratherthanmineral or organic Pb speciations. The low plant bioavailability of Pb demonstrated a further research focusing on Pb absorption and spe-ciation conversion is needed ,especially the role of dissolve organic matter in soil which may enhance Pb bioavailability.%为了从组织和器官水平研究植物在铅锌矿山开采区尾矿坝土壤中植物中毒和胁迫机制,使用同步辐射微束X射线荧光技术(μ-SRXRF)研究了K ,Ca ,Mn ,Fe ,Cu ,Zn ,Pb等元素在云南某铅锌矿区尾矿坝土壤中生长的拟南芥幼苗中的分布特征。发现Pb易富集于植物根部,也容易富集在植物顶端叶芽部位,这是很多研究没有发现的。整株幼苗中Pb都与M n形成明显的竞争分布特征。导致植株

  2. Examination of the site preference of metals in NiAl2−xGaxO4 spinel-type oxides by X-ray absorption near-edge spectroscopy

    Highlights: • Average coordination number of cations in NiAl2−xGaxO4 investigated by XANES. • Average Al and Ga coordination increases with increasing Ga concentration. • Al L2,3- and Ga K-edge XANES spectra are very sensitive to changes in coordination. - Abstract: Materials adopting the spinel-type structure have received considerable attention owing to the compositional diversity and the large number of potential applications for these materials. Although many studies of ternary spinel-type oxides have been completed, few studies have investigated quaternary materials. The NiAl2−xGaxO4 spinel-type system was investigated in this study by X-ray absorption near-edge spectroscopy (XANES) and powder X-ray diffraction to study how the metal-site preference changed depending on composition. The Al L2,3-edge XANES spectra showed that Al occupied the tetrahedral and octahedral sites when x in the chemical formula was low, and preferentially occupied the octahedral site as x increased. The Ga K-edge XANES spectra confirmed that Ga3+ has a strong preference for residing in the tetrahedral site and that this ion only partially occupied the octahedral sites when the concentration of Ga3+ in the system was sufficiently large. The Ni K-edge XANES spectra showed that Ni2+ has a strong preference for residing in the octahedral site, and that more Ni2+ was present in the tetrahedral site in NiAl2O4 vs. NiGa2O4. Rietveld refinement of powder X-ray diffraction patterns from the ternary end members were in general agreement with these results. This study has demonstrated the utility of using XANES to investigate the site preference of Al and Ga through the examination of Al L2,3- and Ga K-edge spectra, respectively

  3. Examination of the site preference of metals in NiAl{sub 2−x}Ga{sub x}O{sub 4} spinel-type oxides by X-ray absorption near-edge spectroscopy

    Walker, James D.S.; Hayes, John R.; Grosvenor, Andrew P., E-mail: andrew.grosvenor@usask.ca

    2014-08-15

    Highlights: • Average coordination number of cations in NiAl{sub 2−x}Ga{sub x}O{sub 4} investigated by XANES. • Average Al and Ga coordination increases with increasing Ga concentration. • Al L{sub 2,3}- and Ga K-edge XANES spectra are very sensitive to changes in coordination. - Abstract: Materials adopting the spinel-type structure have received considerable attention owing to the compositional diversity and the large number of potential applications for these materials. Although many studies of ternary spinel-type oxides have been completed, few studies have investigated quaternary materials. The NiAl{sub 2−x}Ga{sub x}O{sub 4} spinel-type system was investigated in this study by X-ray absorption near-edge spectroscopy (XANES) and powder X-ray diffraction to study how the metal-site preference changed depending on composition. The Al L{sub 2,3}-edge XANES spectra showed that Al occupied the tetrahedral and octahedral sites when x in the chemical formula was low, and preferentially occupied the octahedral site as x increased. The Ga K-edge XANES spectra confirmed that Ga{sup 3+} has a strong preference for residing in the tetrahedral site and that this ion only partially occupied the octahedral sites when the concentration of Ga{sup 3+} in the system was sufficiently large. The Ni K-edge XANES spectra showed that Ni{sup 2+} has a strong preference for residing in the octahedral site, and that more Ni{sup 2+} was present in the tetrahedral site in NiAl{sub 2}O{sub 4} vs. NiGa{sub 2}O{sub 4}. Rietveld refinement of powder X-ray diffraction patterns from the ternary end members were in general agreement with these results. This study has demonstrated the utility of using XANES to investigate the site preference of Al and Ga through the examination of Al L{sub 2,3}- and Ga K-edge spectra, respectively.

  4. Electron energy-loss spectroscopic profiling of thin film structures: 0.39 nm line resolution and 0.04 eV precision measurement of near-edge structure shifts at interfaces

    The method of energy-loss spectroscopic profiling of interfaces, planar defects and thin film structures in a transmission electron microscope with an imaging filter is introduced. Ways to calculate true chemical profiles with near-atomic line resolution are described. An application to the perovskite system (La,Ca)MnO3/SrTiO3 demonstrates that the technical merit of this method is the simultaneous achievement of high resolution (down to 0.39 nm line resolution), high chemical sensitivity (around 1 at% standard deviation) and very high precision in the measurement of shifts of edge onsets and energy-loss near-edge structure details (down to 0.04 eV). The combination of these characteristics makes the method a powerful tool for the quantification of diffusion and segregation of elements on the atomic scale in a variety of materials systems

  5. On the importance of nuclear quantum motions in near edge x-ray absorption fine structure (NEXAFS) spectroscopy of molecules

    Schwartz, Craig P.; Uejio, Janel S.; Saykally, Richard J.; Prendergast, David

    2009-02-26

    We report the effects of sampling nuclear quantum motion with path integral molecular dynamics (PIMD) on calculations of the nitrogen K-edge spectra of two isolated organic molecules. S-triazine, a prototypical aromatic molecule occupying primarily its vibrational ground state at room temperature, exhibits substantially improved spectral agreement when nuclear quantum effects are included via PIMD, as compared to the spectra obtained from either a single fixed-nuclei based calculation or from a series of configurations extracted from a classical molecular dynamics trajectory. Nuclear quantum dynamics can accurately explain the intrinsic broadening of certain features. Glycine, the simplest amino acid, is problematic due to large spectral variations associated with multiple energetically accessible conformations at the experimental temperature. This work highlights the sensitivity of NEXAFS to quantum nuclear motions in molecules, and the necessity of accurately sampling such quantum motion when simulating their NEXAFS spectra.

  6. Coupled-cluster response theory for near-edge x-ray-absorption fine structure of atoms and molecules

    Coriani, Sonia; Christiansen, Ove; Fransson, Thomas;

    2012-01-01

    Based on an asymmetric Lanczos-chain subspace algorithm, damped coupled cluster linear response functions have been implemented for the hierarchy of coupled cluster (CC) models including CC with single excitations (CCS), CC2, CC with single and double excitations (CCSD), and CCSD with noniterativ...... electronic relaxation and correlation that amount to 1–2 eV. With inclusion of triple excitations, errors in energetics are less than 0.9 eV and thereby capturing 90%, 95%, and 98% of the relaxation-correlation energies for C, O, and Ne, respectively....

  7. Ordered and disordered models of local structure around Ag cations in silver borate glasses based on x-ray absorptio n near-edge structure spectroscopy

    Šipr, Ondřej; Dalba, G.; Rocca, F.

    2004-01-01

    Roč. 69, - (2004), 134201/1-134201/16. ISSN 0163-1829 R&D Projects: GA ČR GA202/02/0841 Institutional research plan: CEZ:AV0Z1010914 Keywords : disordered systems * structural analysis * XANES * silver * borate glasses Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.075, year: 2004

  8. The competitive growth of cubic domains in Ti(1-x)AlxN films studied by diffraction anomalous near-edge structure spectroscopy.

    Pinot, Y; Tuilier, M-H; Pac, M-J; Rousselot, C; Thiaudière, D

    2015-11-01

    Titanium and aluminium nitride films deposited by magnetron sputtering generally grow as columnar domains made of oriented nanocrystallites with cubic or hexagonal symmetry depending on Al content, which are embedded in more disordered grain boundaries. The substitution of Al atoms for Ti in the cubic lattice of the films improves their resistance to wear and oxidation, allowing their use as protective coatings. Ti K-edge X-ray absorption spectroscopy, which probes both crystallized and more disordered grain boundaries, and X-ray diffraction anomalous fine structure, which is sensitive to short- and long-range order within a given crystallized domain, are carried out on a set of Ti(1-x)AlxN films deposited by magnetron sputtering on Si substrates. Attention is paid to the shape of the pre-edge region, which is sensitive to the symmetry of the site occupied by Ti atoms, either octahedral in face-centred-cubic Ti-rich (TiN, Ti0.54Al0.46N) samples or tetrahedral in hexagonal-close-packed Al-rich (Ti0.32Al0.68N) films. In order to obain information on the titanium environment in the well crystallized areas, subtraction of the smooth part of the energy-dependent structure factor for the Bragg reflections is applied to the pre-edge region of the diffraction anomalous data in order to restore their spectroscopic appearance. A flat pre-edge is related to the typical octahedral environment of Ti atoms for cubic reflections. The difference observed between pre-edge spectra associated with face-centred-cubic 200 and 111 Bragg reflections of Ti0.54Al0.46N is assigned to Ti enrichment of 111 large well ordered domains compared with the more disordered 200 ones. The sharp peak observed in the spectrum recorded from the hexagonal 002 peak of Ti0.32Al0.68N can be regarded as a standard for the pure tetrahedral Ti environment in hexagonal-close-packed nitride. PMID:26524309

  9. High resolution near edge x-ray spectroscopy

    A technique to suppress the core-hole lifetime broadening in near- edge x-ray spectroscopy is presented. A simple theoretical explanation based on total energy conservation in the fluorescence process is given to explain the improved resolution. The experimental arrangement is shown together with an application to the LIII edge of dysprosium. Furthermore, the application of high-resolution fluorescence spectroscopy in the study of magnetism is presented. The spin-resolved absorption spectra from MnF2 are shown as an example

  10. Near-edge band structures and band gaps of Cu-based semiconductors predicted by the modified Becke-Johnson potential plus an on-site Coulomb U

    Diamond-like Cu-based multinary semiconductors are a rich family of materials that hold promise in a wide range of applications. Unfortunately, accurate theoretical understanding of the electronic properties of these materials is hindered by the involvement of Cu d electrons. Density functional theory (DFT) based calculations using the local density approximation or generalized gradient approximation often give qualitative wrong electronic properties of these materials, especially for narrow-gap systems. The modified Becke-Johnson (mBJ) method has been shown to be a promising alternative to more elaborate theory such as the GW approximation for fast materials screening and predictions. However, straightforward applications of the mBJ method to these materials still encounter significant difficulties because of the insufficient treatment of the localized d electrons. We show that combining the promise of mBJ potential and the spirit of the well-established DFT + U method leads to a much improved description of the electronic structures, including the most challenging narrow-gap systems. A survey of the band gaps of about 20 Cu-based semiconductors calculated using the mBJ + U method shows that the results agree with reliable values to within ±0.2 eV

  11. Catalyst Chemical State during CO Oxidation Reaction on Cu(111) Studied with Ambient-Pressure X-ray Photoelectron Spectroscopy and Near Edge X-ray Adsorption Fine Structure Spectroscopy.

    Eren, Baran; Heine, Christian; Bluhm, Hendrik; Somorjai, Gabor A; Salmeron, Miquel

    2015-09-01

    The chemical structure of a Cu(111) model catalyst during the CO oxidation reaction in the CO+O2 pressure range of 10-300 mTorr at 298-413 K was studied in situ using surface sensitive X-ray photoelectron and adsorption spectroscopy techniques [X-ray photoelectron spectroscopy (XPS) and near edge X-ray adsorption fine structure spectroscopy (NEXAFS)]. For O2:CO partial pressure ratios below 1:3, the surface is covered by chemisorbed O and by a thin (∼1 nm) Cu2O layer, which covers completely the surface for ratios above 1:3 between 333 and 413 K. The Cu2O film increases in thickness and exceeds the escape depth (∼3-4 nm) of the XPS and NEXAFS photoelectrons used for analysis at 413 K. No CuO formation was detected under the reaction conditions used in this work. The main reaction intermediate was found to be CO2(δ-), with a coverage that correlates with the amount of Cu2O, suggesting that this phase is the most active for CO oxidation. PMID:26275662

  12. Near edge X-ray absorption mass spectrometry on coronene

    Reitsma, G.; Deuzeman, M. J.; Hoekstra, R.; Schlathölter, T. [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747AG Groningen (Netherlands); Boschman, L. [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747AG Groningen (Netherlands); Kapteyn Astronomical Institute, University of Groningen, Groningen (Netherlands); Hoekstra, S. [Van Swinderen Institute, University of Groningen, Groningen (Netherlands)

    2015-01-14

    We have investigated the photoionization and photodissociation of free coronene cations C{sub 24}H{sub 12}{sup +} upon soft X-ray photoabsorption in the carbon K-edge region by means of a time-of-flight mass spectrometry approach. Core excitation into an unoccupied molecular orbital (below threshold) and core ionization into the continuum both leave a C 1s vacancy, that is subsequently filled in an Auger-type process. The resulting coronene dications and trications are internally excited and cool down predominantly by means of hydrogen emission. Density functional theory was employed to determine the dissociation energies for subsequent neutral hydrogen loss. A statistical cascade model incorporating these dissociation energies agrees well with the experimentally observed dehydrogenation. For double ionization, i.e., formation of intermediate C{sub 24}H{sub 12}{sup 3+⋆}trications, the experimental data hint at loss of H{sup +} ions. This asymmetric fission channel is associated with hot intermediates, whereas colder intermediates predominantly decay via neutral H loss.

  13. Solution spectroelectrochemical cell for in situ X-ray absorption fine structure

    A purpose-built spectroelectrochemical cell for in situ fluorescence XAFS (X-ray Absorption Fine Structure) measurements of bulk solution species during constant-potential electrolysis is described. The cell performance was demonstrated by the collection of europium L3-edge XANES (X-ray Absorption Near Edge Structure) throughout the course of electrolysis of an aqueous solution of EuCl3·6H2O in 1 M H2SO4. The europium L3-edge resonances reported here for the EuIII and EuII ions demonstrate that their 2p3/2 → 5d electronic transition probabilities are not the same

  14. Diurnal Variation and Spatial Distribution Effects on Sulfur Speciation in Aerosol Samples as Assessed by X-Ray Absorption Near-Edge Structure (XANES)

    Siwatt Pongpiachan; Kanjana Thumanu; Warangkana Na Pattalung; Phoosak Hirunyatrakul; Itthipon Kittikoon; Kin Fai Ho; Junji Cao

    2012-01-01

    This paper focuses on providing new results relating to the impacts of Diurnal variation, Vertical distribution, and Emission source on sulfur K-edge XANES spectrum of aerosol samples. All aerosol samples used in the diurnal variation experiment were preserved using anoxic preservation stainless cylinders (APSCs) and pressure-controlled glove boxes (PCGBs), which were specially designed to prevent oxidation of the sulfur states in PM10. Further investigation of sulfur K-edge XANES spectra rev...

  15. Effects of sulfation level on the desulfation behavior of pre-sulfated Pt BaO/Al2O3 lean NOx trap catalysts: a combined H2 Temperature-Programmed Reaction, in-situ sulfur K-edge X-ray Absorption Near-Edge Spectroscopy, X-ray Photoelectron Spectroscopy, and Time-Resolved X-ray Diffraction Study

    Desulfation by hydrogen of pre-sulfated Pt(2wt%) BaO(20wt%)/Al2O3 with various sulfur loading (S/Ba = 0.12, 0.31 and 0.62) were investigated by combining H2 temperature programmed reaction (TPRX), x-ray photoelectron spectroscopy (XPS), in-situ sulfur K-edge x-ray absorption near-edge spectroscopy (XANES), and synchrotron time-resolved x-ray diffraction (TR-XRD) techniques. We find that the amount of H2S desorbed during the desulfation in the H2 TPRX experiments is not proportional to the amount of initial sulfur loading. The results of both in-situ sulfur K-edge XANES and TR-XRD show that at low sulfur loadings, sulfates were transformed to a BaS phase and remained in the catalyst, rather than being removed as H2S. On the other hand, when the deposited sulfur level exceeded a certain threshold (at least S/Ba = 0.31) sulfates were reduced to form H2S, and the relative amount of the residual sulfide species in the catalyst was much less than at low sulfur loading. Unlike samples with high sulfur loading (e.g., S/Ba = 0.62), H2O did not promote the desulfation for the sample with S/Ba of 0.12, implying that the formed BaS species originating from the reduction of sulfates at low sulfur loading are more stable to hydrolysis. The results of this combined spectroscopy investigation provide clear evidence to show that sulfates at low sulfur loadings are less likely to be removed as H2S and have a greater tendency to be transformed to BaS on the material, leading to the conclusion that desulfation behavior of Pt BaO/Al2O3 lean NOx trap catalysts is markedly dependent on the sulfation levels.

  16. Methods of Determining Lead Speciation in Fly Ash by X-ray Absorption Fine-Structure Spectroscopy and a Sequential Extraction Procedure

    Funatsuki, Atsushi; Takaoka, Masaki; Oshita, Kazuyuki; Takeda, Nobuo

    2012-01-01

    Understanding the chemical state of lead in fly ash generated from a waste thermal treatment is important, since the toxicity and solubility of the element depends on its chemical state. This study identified three potential methods for obtaining quantitative information regarding the chemical state of lead in fly ash: X-ray absorption near edge structure (XANES) analysis, extended X-ray absorption fine structure (EXAFS) analysis, and the sequential extraction procedure. The result of this pr...

  17. Extended-x-ray-absorption-fine-structure study of small Fe molecules isolated in solid neon

    We have used rare gas matrix isolation techniques in combination with extended x-ray absorption fine structure (EXAFS) to study the variation in interatomic distances for small Fe molecules in solid neon. A considerable contraction in the interatomic distances was observed for the metal molecules. An Fe-Fe distance of 2.03 +- l0.03 A for the lowest concentration of metal was observed. This is in good agreement with early EXAFS measurements in Fe2-Ar. We also carried out a careful study of the x-ray-absorption near-edge structure (XANES), and observed the appearance of considerable structure for a 1.5-at. % Fe sample. The XANES spectra were analyzed in terms of 1s-to-(3d,4s) and 1s-to-4p transitions

  18. Structural sound absorption in liquid metals

    Present article is devoted to structural sound absorption in liquid metals. The study of sound absorption in liquid metals shown that in all studied objects the structural absorption of sound was observed. The mechanism of structural relaxation in molten metal was revealed.

  19. Solvation structure of the halides from x-ray absorption spectroscopy

    Antalek, Matthew; Pace, Elisabetta; Hedman, Britt; Hodgson, Keith O.; Chillemi, Giovanni; Benfatto, Maurizio; Sarangi, Ritimukta; Frank, Patrick

    2016-07-01

    Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, and a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (-0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions.

  20. Self-assembled carbon nanotubes on gold: polarization-modulated infrared reflection-absorption spectroscopy, high-resolution X-ray photoemission spectroscopy, and near-edge X-ray absorption fine structure spectroscopy study

    Kocharova, N.; Leiro, J.; Lukkari, J.; Heinonen, M.; Skála, T.; Šutara, F.; Škoda, M.; Vondráček, Martin

    2008-01-01

    Roč. 24, - (2008), s. 3235-3243. ISSN 0743-7463 R&D Projects: GA MŠk(CZ) LC06058 Institutional research plan: CEZ:AV0Z10100521 Keywords : carbon nanotubes * XPS * NEXAFS Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.097, year: 2008

  1. Local Structure Determination of Carbon/Nickel Ferrite Composite Nanofibers Probed by X-ray Absorption Spectroscopy.

    Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

    2015-11-01

    Carbon/NiFe2O4 composite nanofibers have been successfully prepared by electrospinning method using a various concentration solution of Ni and Fe nitrates dispersed into polyacrylonitride (PAN) solution in N,N' dimethylformamide. The phase and mophology of PAN/NiFe2O4 composite samples were characterized and investigated by X-ray diffraction and scanning electron microscopy. The magnetic properties of the prepared samples were measured at ambient temperature by a vibrating sample magnetometer. It is found that all composite samples exhibit ferromagnetism. This could be local-structurally explained by the existed oxidation states of Ni2+ and Fe3+ in the samples. Moreover, local environments around Ni and Fe ions could be revealed by X-ray absorption spectroscopy (XAS) measurement including X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS). PMID:26726677

  2. Influence of near-edge processes in the elemental analysis using X-ray emission-based techniques

    Gurjeet Singh; Sunil Kumar; N Singh; J Goswamy; D Mehta

    2011-02-01

    The near-edge processes, such as X-ray absorption fine structure (XAFS) andresonant Raman scattering (RRS), are not incorporated in the available theoretical attenuation coefficients, which are known to be reliable at energies away from the shell/subshell ionization thresholds of the attenuator element. Theoretical coefficients are generally used to estimate matrix corrections in routine quantitative elemental analysis based on various X-ray emission techniques. A tabulation of characteristic X-ray energies across the periodic table is provided where those X-rays are expected to alter the attenuation coefficients due to XAFS from a particular shell/subshell of the attenuator element. The influence of XAFS to the attenuation coefficient depends upon the atomic environment and the photoelectron wave vector, i.e., difference in energies of incident X-ray and the shell/subshell ionization threshold of the attenuator element. Further, the XAFS at a shell/subshell will significantly alter the total attenuation coefficient if the jump ratio at that shell/subshell is large, e.g., the K shell, L3 subshell and M5 subshell. The tabulations can be considered as guidelines so as to know what can be expected due to XAFS in typical photon-induced X-ray emission spectrometry.

  3. X-ray Absorption Spectroscopy

    Yano, Junko; Yachandra, Vittal K.

    2009-07-09

    This review gives a brief description of the theory and application of X-ray absorption spectroscopy, both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), especially, pertaining to photosynthesis. The advantages and limitations of the methods are discussed. Recent advances in extended EXAFS and polarized EXAFS using oriented membranes and single crystals are explained. Developments in theory in understanding the XANES spectra are described. The application of X-ray absorption spectroscopy to the study of the Mn4Ca cluster in Photosystem II is presented.

  4. Structural characterization of the Co/Cr multilayers by x-ray-absorption spectroscopy

    We have performed Cr and Co K-edge x-ray-absorption measurements to investigate the dependence of local electronic and atomic structures on the Cr-layer thickness in epitaxial Co(11-bar00) (40 A)/Cr(211) (tCr) (tCr=2, 3, 5, 7, and 9 A) multilayers. The Cr K x-ray-absorption near-edge fine structure (XANES) spectra of the Co/Cr multilayers indicate an abrupt transition of the Cr layer from hcp to bcc structure when the thickness of the Cr layer is increased to exceed ∼5 A or three atomic layers. Our results offer an upper limit for the ability of the Co/Cr interface to stabilize the hcp structure in the thin Cr layer. The numbers of nearest-neighbor and next-nearest-neighbor atoms in the Cr and Co layers determined by extended x-ray-absorption fine-structure measurements performed at the Cr and Co K edge, respectively, are consistent with the XANES results

  5. X-ray absorption spectroscopy: EXAFS and XANES - A versatile tool to study the atomic and electronic structure of materials

    X-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-ray Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, they will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and sample limitations

  6. Absorption enhancement in graphene photonic crystal structures.

    Khaleque, Abdul; Hattori, Haroldo T

    2016-04-10

    Graphene, a single layer of carbon atoms arranged in a honeycomb lattice, is attracting significant interest because of its potential applications in electronic and optoelectronic devices. Although graphene exhibits almost uniform absorption within a large wavelength range, its interaction with light is weak. In this paper, the enhancement of the optical absorption in graphene photonic crystal structures is studied: the structure is modified by introducing scatterers and mirrors. It is shown that the absorption of the graphene photonic crystal structure can be enhanced about four times (nearly 40%) with respect to initial reference absorption of 9.8%. The study can be a useful tool for investigating graphene physics in different optical settings. PMID:27139857

  7. A comparison of fine structures in high-resolution x-ray-absorption spectra of various condensed organic molecules.

    Schoell, A; Zou, Y; Huebner, D; Urquhart, S G; Schmidt, Th; Fink, R; Umbach, E

    2005-07-22

    We report on a high-resolution C-K and O-K near-edge x-ray-absorption fine-structure (NEXAFS) study of large aromatic molecules in condensed thin films, namely, anhydrides 1,4,5,8-naphthalene-tetracarboxylic acid dianhydride, 3,4,9,10-perylene-tetracarboxylic acid dianhydride, benzoperylene-(1,2)-dicarboxylic acid anhydride, and 1,8-naphthalene-dicarboxylic acid anhydride and the quinoic acenaphthenequinone. Due to the high-energy resolution of the third-generation synchrotron source BESSY II we observe large differences in the NEXAFS fine structures even for very similar molecules, resulting in a wealth of new information. The rich fine structure can unambiguously be assigned to the coupling of electronic transitions to vibronic excitations. Backed by ab initio calculations we present a detailed analysis of the spectra that allows the complete interpretation of the near-edge features. It also yields information on the vibronic properties in the electronically excited state as well as on the response of the electronic system upon core excitation. The strong differences in the electron-vibron coupling for different molecules are discussed. PMID:16095371

  8. Re and Br X-ray Absorption Near-Edge Structure Study of the Ground and Excited States of [ReBr(CO)3(bpy)] Interpreted by DFT and TDDFT Calculations

    Záliš, Stanislav; Milne, C. J.; Nahhas, A. E.; Blanco-Rodríguez, A. M.; van der Veen, R. M.; Vlček Jr., Antonín

    2013-01-01

    Roč. 52, č. 10 (2013), s. 5775-5785. ISSN 0020-1669 R&D Projects: GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : carbonyl-bipyridine complexes * density functional theory * order regular approximation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.794, year: 2013

  9. Role of defects in BiFeO₃ multiferroic films and their local electronic structure by x-ray absorption spectroscopy

    Ravalia, Ashish; Vagadia, Megha; Solanki, P. S.; Shah, N. A.; Kuberkar, D. G., E-mail: dgkuberkar@rediffmail.com [Department of Physics, Saurashtra University, Rajkot 360 005 (India); Gautam, S.; Chae, K. H. [Nano Material Analysis Centre, Korean Institute of Science and Technology, Seoul 136-79 (Korea, Republic of); Asokan, K. [Inter University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi 110 067 (India)

    2014-10-21

    Present study reports the role of defects in the electrical transport in BiFeO₃ (BFO) multiferroic films and its local electronic structure investigated by near-edge X-ray absorption fine structure. Defects created by high energy 200 MeV Ag⁺¹⁵ ion irradiation with a fluence of ∼5 × 10¹¹ ions/cm² results in the increase in structural strain and reduction in the mobility of charge carriers and enhancement in resistive (I-V) and polarization (P-E) switching behaviour. At higher fluence of ∼5 × 10¹² ions/cm², there is a release in the structural strain due to local annealing effect, resulting in an increase in the mobility of charge carriers, which are released from oxygen vacancies and hence suppression in resistive and polarization switching. Near-edge X-ray absorption fine structure studies at Fe L₃,₂- and O K-edges show a significant change in the spectral features suggesting the modifications in the local electronic structure responsible for changes in the intrinsic magnetic moment and electrical transport properties of BFO.

  10. Intestinal absorption of specific structured triacylglycerols

    Mu, Huiling; Høy, Carl-Erik

    2001-01-01

    To clarify the intestinal absorption pathway of medium-chain fatty acids from MMM-type structured triaclyglycerols containing both medium- and long-chain fatty acids, we studied the lymphatic transport of 1,3-dioctanoyl-2-linoleoyl-sn- glycerol (8:0/18:2/8:0), 1,3-didecanoyl-2-linoleoyl...... activated into CoA, and reacylated into triacylglycerols in the enterocyte, The hydrolysis of MLM-type STAG is predominantly partial hydrolysis, whereas part of the STAG can also be hydrolyzed to free glycerol and free fatty acids. - Mu, H., and CE. Hoy. Intestinal absorption of specific structured...

  11. Radiation Absorption Mechanism in Nonvolatile MNOS Structure

    2002-01-01

    The γ-ray radiation will speed up the discharge of the stored charge in nonvolatile MNOS structure. The radiation absorption mechanism to enhance the discharge is discussed. A direct radiation emission model from the interface traps distributing both in energy level and in space is given. The theoretical results based on this model are in good agreement with experimental measurement.

  12. Determination of hexavalent chromium in plastic certified reference materials by X-ray absorption fine structure analysis

    Ohata, Masaki; Matsubayashi, Nobuyuki

    X-ray absorption fine structure (XAFS) analysis with transmission mode was used to determine the percentages of hexavalent chromium {Cr(VI)} in total Cr in plastic certified reference materials (CRMs). Cr-K edge X-ray absorption near-edge structure (XANES) spectra were observed and the normalized pre-edge peaks of the spectrum where absorption data was summed was acquired for the determination of Cr(VI). Examination of different number of data point and range of photon energy for summed absorption of the pre-edge peak resulted in reproducible absorption data, though the measurements were carried out at different beam time and beam line. The concentrations of Cr(VI) in the plastic CRMs were also estimated from both the certified value of total Cr and the determined percentage of Cr(VI). The analytical procedure and the estimated concentrations can be useful for the determination of Cr(VI) in plastics with respect to RoHS (restriction of the use of hazardous substances in electrical and electronics equipment) directive.

  13. Determination of hexavalent chromium in plastic certified reference materials by X-ray absorption fine structure analysis

    Ohata, Masaki, E-mail: m-oohata@aist.go.jp [Inorganic Standard Section, Inorganic Analytical Chemistry Division, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST) (Japan); Matsubayashi, Nobuyuki [Super-Spectroscopy System Research Group, Research Institute of Instrumentation Frontier (RIIF), National Institute of Advanced Industrial Science and Technology (AIST) (Japan)

    2014-03-01

    X-ray absorption fine structure (XAFS) analysis with transmission mode was used to determine the percentages of hexavalent chromium {Cr(VI)} in total Cr in plastic certified reference materials (CRMs). Cr-K edge X-ray absorption near-edge structure (XANES) spectra were observed and the normalized pre-edge peaks of the spectrum where absorption data was summed was acquired for the determination of Cr(VI). Examination of different number of data point and range of photon energy for summed absorption of the pre-edge peak resulted in reproducible absorption data, though the measurements were carried out at different beam time and beam line. The concentrations of Cr(VI) in the plastic CRMs were also estimated from both the certified value of total Cr and the determined percentage of Cr(VI). The analytical procedure and the estimated concentrations can be useful for the determination of Cr(VI) in plastics with respect to RoHS (restriction of the use of hazardous substances in electrical and electronics equipment) directive.

  14. Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

    The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called 'molecular movie' within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes

  15. Multiple scattering approach to X-ray absorption spectroscopy

    2003-01-01

    In this paper we present the state of the art of the theoretical background needed for analyzing X-ray absorption spectra in the whole energy range. The multiple-scattering (MS) theory is presented in detail with some applications on real systems. We also describe recent progress in performing geometrical fitting of the XANES (X-ray absorption near-edge structure) energy region and beyond using a full multiple-scattering approach.

  16. Clarifying the chemical state of additives in membranes for polymer electrolyte fuel cells by X-ray absorption fine structure

    Tanuma, Toshihiro; Itoh, Takanori

    2016-02-01

    Cerium and manganese compounds are used in the membrane for polymer electrolyte fuel cells (PEFCs) as radical scavengers to mitigate chemical degradation of the membrane. The chemical states of cerium and manganese in the membrane were investigated using a fluorescence X-ray absorption fine structure (XAFS) technique. Membrane electrode assemblies (MEAs) were subjected to open circuit voltage (OCV) condition, under which hydroxyl radicals attack the membrane; a shift in absorption energy in X-ray absorption near edge structure (XANES) spectra was compared between Ce- and Mn-containing membranes before and after OCV testing. In the case of the Ce-containing MEA, there was no significant difference in XANES spectra before and after OCV testing, whereas in the case of the Mn-containing MEA, there was an obvious shift in XANES absorption energy after OCV testing, indicating that Mn atoms with higher valence state than 2+ exist in the membrane after OCV testing. This can be attributed to the difference in the rate of reduction; the reaction of Ce4+ with ·OOH is much faster than that of Mn3+ with ·OOH, leaving some of the Mn atoms with higher valence state. It was confirmed that cerium and manganese redox couples reduced the attack from radicals, mitigating membrane degradation.

  17. X-Ray Absorption Fine Structure Investigation of Copper(II) Mixed Ligand Complexes with Pyridinedicarboxylic Acid as Primary Ligand

    Dar, D. Ah.; Gaur, A.; Soni, B.; Shrivastava, B. D.; Prasad, J.; Srivastava, K.; Jha, S. N.; Bhattacharyya, D.

    2015-05-01

    The X-ray absorption fine structure (XAFS) spectra at the K-edge of the copper complexes Cu(PDC)(Mim)3 H2O ( 1) and Cu(PDC)2(EA)2H2O ( 2) (where PDC - Pyridine-2,3-dicarboxylic acid, Mim - 2-methylimidazole, and EA - ethyl acetate) have been investigated. The experimental extended X-ray absorption fine structure data of complex 1 have been analyzed by fitting the theoretical model generated from its own crystallographic data. The crystallographic data for complex 2 are not available. It has been found by comparing the intensity of the pre-edge peaks and X-ray absorption near edge structure features of complexes 1 and 2 that both complexes possess square pyramidal geometry around the copper centers and thus complex 2 is analogous to complex 1. Hence, the theoretical model generated for complex 1 has been fitted to the experimental EXAFS data of complex 2 to determine the structural parameters of complex 2. The coordination geometry of both complexes has been depicted. Further, the chemical shifts have been used to determine the oxidation state as well as to estimate the effective nuclear charge on the copper atom.

  18. Structural characterization of bismuth molybdates by x-ray absorption spectroscopy and powder neutron diffraction profile analysis

    Antonio, M.R.; Teller, R.G.; Sandstorm, D.R.; Mehicic, M.; Brazdil, J.F.

    1988-05-19

    By use of synchrotron radiation, high-quality X-ray absorption data have been recorded for three bismuth molybdate phases with the general composition Bi/sub 2/O/sub 3/ x nMoO/sub 3/, for n = 3 (..cap alpha..-phase) n = 2 (..beta..-phase), and n = 1 (..gamma..-phase). The results of these bismuth L/sub 3/-edge and molybdenum K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) studies provide structural insights about the local environments of the Bi/sup 3 +/ and Mo/sup 6 +/ ions. Also, the structure of ..beta..-Bi/sub 2/O/sub 3/ x 2MoO/sub 3/ was investigated by the use of time-of-flight powder neutron diffraction. The profile analysis of the neutron data for ..beta..-bismuth molybdate (monoclinic, P2/sub 1//n, a = 11.9515 (4) A, b = 10.7993 (4) A, c = 11.8805 (4) A, ..beta.. = 90.142 (5)/sup 0/, and Z = 8) revealed that the bismuth and molybdenum cations are present in a fluorite-like sublattice.

  19. Intestinal absorption of specific structured triacylglycerols

    Mu, Huiling; Høy, Carl-Erik

    2001-01-01

    -sn-glycerol (10:0/18:2/10:0), and 1,3-didodecanoyl-2-linoleoyl-sn-glycerol (12:0/18:2/12:0) in a rat model. Safflower oil was used in the absorption study in order to compare the absorption of medium- chain fatty acids and long-chain fatty acids, The triacylglycerol species of lymph Lipids were separated on a...... lymph lipids after administration of the specific structured triacylglycerols (STAG), The recoveries of 8:0/18:2/8:0, 10:0/18:2/10:0, and 12:0/18:2/12:0 were 0.6%, 12%, and 5%, respectively, Several new triacylglycerol species were detected in the lymph Lipids, including MLL-, LLL-, and MMM...

  20. Coherent perfect absorption in photonic structures

    Baldacci, Lorenzo; Tredicucci, Alessandro

    2016-01-01

    The ability to drive a system with an external input is a fundamental aspect of light-matter interaction. The coherent perfect absorption (CPA) phenomenon extends to the general multibeam interference phenomenology the well known critical coupling concepts. This interferometric control of absorption can be employed to reach full delivery of optical energy to nanoscale systems such as plasmonic nanoparticles, and multi-port interference can be used to enhance the absorption of a nanoscale device when it is embedded in a strongly scattering system, with potential applications to nanoscale sensing. Here we review the two-port CPA in reference to photonic structures which can resonantly couple to the external fields. A revised two-port theory of CPA is illustrated, which relies on the Scattering Matrix formalism and is valid for all linear two-port systems with reciprocity. Through a semiclassical approach, treating two-port critical coupling conditions in a non-perturbative regime, it is demonstrated that the st...

  1. Surface Enhance Infrared Absorption in nanogap structures

    Li, Yajing; Zolotavin, Pavlo; Natelson, Douglas

    Understanding the energy dissipation at the interface of molecules and metal nanostructures is of interest. We fabricate self-aligned gold nanostructures with nanometer-scale interelectrode spacing. Those gold nanostructures support highly hybridized plasmon modes with great enhanced local electric field. Previous studies have proven those structures to be suitable substrates for surface-enhanced Raman spectroscopy with single-molecule sensitivity, which enables the study of molecular vibrational and electronic physics. We propose those structures as possible probes of the energy dissipation at the nanometer gap. By measuring the absorption spectrum of molecules assembled in the junction, we can estimate the local filed intensity at the gap and discuss the plasmonic responses of these self-aligned structures under infrared excitation.

  2. Communication: Systematic shifts of the lowest unoccupied molecular orbital peak in x-ray absorption for a series of 3d metal porphyrins

    García Lastra, Juan Maria; Cook, P. L.; Himpsel, F. J.; Rubio, A.

    2010-01-01

    Porphyrins are widely used as dye molecules in solar cells. Knowing the energies of their frontier orbitals is crucial for optimizing the energy level structure of solar cells. We use near edge x-ray absorption fine structure (NEXAFS) spectroscopy to obtain the energy of the lowest unoccupied...

  3. Synchrotron X-Ray Absorption Spectroscopy Study of Self-Assembled Nanoparticles Synthesized from Fe(acac)3 and Pt(acac)2

    Chokprasombat, K.; Sirisathitkul, C; Harding, P.; S. Chandarak; R. Yimnirun

    2012-01-01

    The synchrotron X-ray absorption technique was used to complement electron microscopy in the investigation of nanoparticles synthesized from the coreduction of iron acetylacetonate, Fe(acac)3 and platinum acetylacetonate, Pt(acac)2. A much higher Pt composition than Fe leads to an extended X-ray absorption fine structure (EXAFS) spectrum for the sample that differs from that of fcc FePt nanoparticles. Most importantly, X-ray absorption near-edge structure (XANES) spectra clearly indicate the ...

  4. X-Ray Absorption and Scattering by Interstellar Grains

    Hoffman, John A

    2015-01-01

    Interstellar abundance determinations from fits to X-ray absorption edges often rely on the following false assumptions: (1) the grains are "optically thin" at the observed X-ray wavelengths, and (2) scattering is insignificant and can be ignored. We show instead that scattering contributes significantly to the attenuation of X-rays for realistic dust grain size distributions and substantially modifies the spectrum near absorption edges of elements present in grains. The dust attenuation modules used in major X-ray spectral fitting programs do not take this into account. We show that the consequences of neglecting scattering on the determination of interstellar elemental abundances are modest; however, scattering (along with uncertainties in the grain size distribution) must be taken into account when near-edge extinction fine structure is used to infer dust mineralogy. We advertise the benefits and accuracy of anomalous diffraction theory for both X-ray halo analysis and near edge absorption studies. An open...

  5. Free carrier absorption in quantum cascade structures

    Carosella, F.; Ndebeka-Bandou, C.; Ferreira, R.; Dupont, E; K. Unterrainer; Strasser, G.; Wacker, Andreas; Bastard, G.

    2011-01-01

    We show that the free carrier absorption in Quantum Cascade Lasers is very small and radically different from the classical Drude result on account of the orthogonality between the direction of the carrier free motion and the electric field of the laser emission. A quantum mechanical calculation of the free carrier absorption and inter-subband oblique absorption induced by interface defects, coulombic impurities and optical phonon absorption/emission is presented for QCL's with a double quant...

  6. Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

    Thin films were prepared using glass precursors obtained in the ternary system NaPO3-BaF2-WO3 and the binary system NaPO3-WO3 with high concentrations of WO3 (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten LI and LIII absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO6) and that these films are free of tungstate tetrahedral units (WO4). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO6 octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O- and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (above 40% molar) attributed to the formation of WO6 clusters

  7. Synchrotron X-ray absorption spectroscopy study of local structure transformation behavior in perovskite Ba(Ti,Zr)O3 system

    Highlights: • Synthesis, global structure was studied by XRD technique. • The local structure of the Ti ions in the Ba(Ti,Zr)O3 using XAS technique. • EXAFS and XANES analysis showed that Ti-displacement lead to the phase transition. • The results were confirmed by XANES simulation and EXAFS fitting. • This work deals with application of a novel Synchrotron. - Abstract: In this work, the change of the local atomic structure in BaTi1−xZrxO3 ceramics was investigated by synchrotron X-ray absorption spectroscopy technique. The X-ray Absorption Near-Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectra at the Ti K-edge were measured and compared with simulated spectra. The results show that an increase of Zr content in Ba(Ti,Zr)O3 lattice structure affected significantly the phase transition behavior and the local structure surrounding the Ti absorbing atom. More importantly, the information on the locally determined structures and its relation to the phase transition characteristic from relaxor ferroelectric to polar clusters in Ba(Ti,Zr)O3 system were obtained and discussed

  8. The nanoscale structure and unoccupied valence electronic states in FeSe1-xTex chalcogenides probed by X-ray absorption measurements.

    Hacisalihoglu, M Y; Paris, E; Joseph, B; Yanmaz, E; Saini, N L

    2015-07-21

    We have studied the nanoscale structure and unoccupied electronic states in FeSe1-xTex by a combined analysis of Se K, Te L1 and Fe K-edges X-ray absorption measurements. Extended X-ray absorption fine structure (EXAFS) results show that iron-chalcogen (Fe-Se and Fe-Te) distances in ternary FeSe1-xTex are similar to those measured for binary FeSe and FeTe. The local Fe-Se/Te distances determined by different absorption edges fit well in the characteristic Z-plot of random alloys, providing unambiguous support to the inhomogeneous nanoscale structure of the ternary FeSe1-xTex system. X-ray absorption near-edge structure (XANES) spectra reveal a gradual evolution of the unoccupied valence electronic states as a function of Te-substitution in FeSe1-xTex. The Fe 3d-Se 4p/Te 5p hybridization is found to decrease with Te-substitution, accompanied by an increase in unoccupied Se 4p states and a decrease in unoccupied Te 5p states. The results are discussed in the frame of local inhomogeneity in the FeSe1-xTex system driven by random alloying of Se/Te atoms. PMID:26099493

  9. Desulfurization and structural transformation of thiophene on the Pt(111) surface

    The temperature dependence of near-edge x-ray absorption fine-structure spectra above the C K edge and S L/sub 2,3/ edge for thiophene (C4H4S) on Pt(111) reveals changes in the chemisorption geometry and the cleavage of the carbon-sulfur bond. Our results suggest the formation of a metallocycle intermediate after desulfurization with the S atom replaced by a Pt surface atom. The near-edge x-ray absorption fine-structure results are corroborated by thermal desorption, x-ray photoemission, and electron-energy-loss data

  10. The crack energy absorptive capacity of composites with fractal structure

    This paper discusses the energy absorptive capacity of composites with fibers of fractal structures. It is found that this kind of structure may increase the absorption energy during the crack propagation and hence the fracture toughness of composites. (author). 10 refs, 6 figs, 2 tabs

  11. X-ray absorption near the edge structure and X-ray photoelectron spectroscopy studies on pyrite prepared by thermally sulfurizing iron films

    This paper reports how pyrite films were prepared by thermal sulfurization of magnetron sputtered iron films and characterized by x-ray absorption near edge structure spectra and x-ray photoelectron spectroscopy on a 4B9B beam line at the Beijing Synchrotron Radiation Facility. The band gap of the pyrite agrees well with the optical band gap obtained by a spectrophotometer. The octahedral symmetry of pyrite leads to the splitting of the d orbit into t2g and eg levels. The high spin and low spin states were analysed through the difference of electron exchange interaction and the orbital crystal field. Only when the crystal field splitting is higher than 1.5 eV, the two weak peaks above the white lines can appear, and this was approved by experiments in the present work. (atomic and molecular physics)

  12. Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

    Lea Nowack; Daniel Grolimund; Vallerie Samson; Federica Marone; Vanessa Wood

    2016-01-01

    Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition...

  13. Shell structure of pancakes and the absorption spectra of quasars

    The formation of the absorption lines of atomic hydrogen in the spectra of distant quasars is considered. A model is constructed of the formation of shells of a pancake formed in the adiabatic picture of the generation of the large-scale structure of the universe. It is shown that the absorption lines can form doublets and the equivalent widths of the corresponding lines are calculated. The physical conditions corresponding to the observed heavy-element absorption spectra are discussed

  14. X-ray absorption fine structure spectroscopic determination of plutonium speciation at the Rocky Flats environmental technology

    Lezama-pacheco, Juan S [Los Alamos National Laboratory; Conradson, Steven D [Los Alamos National Laboratory; Clark, David L [Los Alamos National Laboratory

    2008-01-01

    X-ray Absorption Fine Structure spectroscopy was used to probe the speciation of the ppm level Pu in thirteen soil and concrete samples from the Rocky Flats Environmental Technology Site in support of the site remediation effort that has been successfully completed since these measurements. In addition to X-ray Absorption Near Edge Spectra, two of the samples yielded Extended X-ray Absorption Fine Structure spectra that could be analyzed by curve-fits. Most of these spectra exhibited features consistent with PU(IV), and more specificaJly, PuO{sub 2+x}-type speciation. Two were ambiguous, possibly indicating that Pu that was originally present in a different form was transforming into PuO{sub 2+x}, and one was interpreted as demonstrating the presence of an unusual Pu(VI) compound, consistent with its source being spills from a PUREX purification line onto a concrete floor and the resultant extreme conditions. These experimental results therefore validated models that predicted that insoluble PuO{sub 2+x} would be the most stable form of Pu in equilibrium with air and water even when the source terms were most likely Pu metal with organic compounds or a Pu fire. A corollary of these models' predictions and other in situ observations is therefore that the minimal transport of Pu that occurred on the site was via the resuspension and mobilization of colloidal particles. Under these conditions, the small amounts of diffusely distributed Pu that were left on the site after its remediation pose only a negligible hazard.

  15. X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites

    Gandhiraman, Ram P.; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E.; Chen, Bin; Meyyappan, M.

    2014-01-01

    The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties...

  16. Electronic structure of copper phthalocyanine : An experimental and theoretical study of occupied and unoccupied levels

    Evangelista, Fabrizio; Carravetta, Vincenzo; Stefani, Giovanni; Jansik, Branislav; Alagia, Michele; Stranges, Stefano; Ruocco, Alessandro

    2007-01-01

    An experimental and theoretical study of the electronic structure of copper phthalocyanine (CuPc) molecule is presented. We performed x-ray photoemission spectroscopy (XPS) and photoabsorption [x-ray absorption near-edge structure (XANES)] gas phase experiments and we compared the results with self-

  17. XANES determination of chromium oxidation states in glasses: comparison with optical absorption spectroscopy

    Villain, Olivier; Calas, Georges; Galoisy, Laurence; Cormier, Laurent; Hazemann, Jean-Louis

    2007-01-01

    The oxidation state of chromium in glasses melted in an air atmosphere with and without refining agents was investigated by Cr K-edge X-ray Absorption Near-Edge Structure (XANES) and optical absorption spectroscopy. A good agreement in the relative proportion of Cr(III) and Cr(VI) is obtained between both methods. We show that the chemical dependence of the absorption coefficient of Cr(III) is less important in XANES than in optical absorption spectroscopy. The comparison of glasses melted un...

  18. Energy absorption in sandwich laminate structures

    White, Robert

    2010-01-01

    The significant result of this thesis is that the energy absorption of a sandwich laminate can be estimated using a simple spring force model. This means for a maritime vessel that the maximum survivable impact speed of the vessel can be estimated using nothing more than the speed of the craft and the mass ratio of the craft and the impactor. The calculation requires one to know the sandwich equivalent spring constant which is shown to be closely related to foam core shear and compressive mod...

  19. Asymmetry and the Nucleosynthetic Signature of Nearly Edge-lit Detonation in White Dwarf Cores

    Chamulak, David A.; Meakin, Casey A.; Seitenzahl, Ivo R.; Truran, James W.

    2012-01-01

    Most of the leading explosion scenarios for Type Ia supernovae involve the nuclear incineration of a white dwarf star through a detonation wave. Several scenarios have been proposed as to how this detonation may actually occur, but the exact mechanism and environment in which it takes place remain unknown. We explore the effects of an off-center initiated detonation on the spatial distribution of the nucleosynthetic yield products in a toy model—a pre-expanded near Chandrasekhar-mass white dwarf. We find that a single-point near edge-lit detonation results in asymmetries in the density and thermal profiles, notably the expansion timescale, throughout the supernova ejecta. We demonstrate that this asymmetry of the thermodynamic trajectories should be common to off-center detonations where a small amount of the star is burned prior to detonation. The sensitivity of the yields on the expansion timescale results in an asymmetric distribution of the elements synthesized as reaction products. We tabulate the shift in the center of mass of the various elements produced in our model supernova and find an odd-even pattern for elements past silicon. Our calculations show that off-center single-point detonations in carbon-oxygen white dwarfs are marked by significant composition asymmetries in their remnants which bear potentially observable signatures in both velocity and coordinate space, including an elemental nickel mass fraction that varies by a factor of 2-3 from one side of the remnant to the other.

  20. Asymmetry and the Nucleosynthetic Signature of Nearly Edge-Lit Detonation in White Dwarf Cores

    Chamulak, David A; Seitenzahl, Ivo R; Truran, James W

    2011-01-01

    Most of the leading explosion scenarios for Type Ia supernovae involve the nuclear incineration of a white dwarf star through a detonation wave. Several scenarios have been proposed as to how this detonation may actually occur, but the exact mechanism and environment in which it takes place remain unknown. We explore the effects of an off-center initiated detonation on the spatial distribution of the nucleosynthetic yield products in a toy model - a pre-expanded near Chandrasekhar-mass white dwarf. We find that a single near edge-lit detonation results in asymmetries in the density and thermal profiles, notably the expansion timescale, throughout the supernova. We demonstrate that this asymmetry of the thermodynamic trajectories should be common to off-center detonations where a small amount of the star is burned prior to detonation. The asymmetry stems from the fact that in one hemisphere the propagation direction of the detonation wave is largely in the direction of final (radial) expansion, whereas in the ...

  1. ASYMMETRY AND THE NUCLEOSYNTHETIC SIGNATURE OF NEARLY EDGE-LIT DETONATION IN WHITE DWARF CORES

    Most of the leading explosion scenarios for Type Ia supernovae involve the nuclear incineration of a white dwarf star through a detonation wave. Several scenarios have been proposed as to how this detonation may actually occur, but the exact mechanism and environment in which it takes place remain unknown. We explore the effects of an off-center initiated detonation on the spatial distribution of the nucleosynthetic yield products in a toy model—a pre-expanded near Chandrasekhar-mass white dwarf. We find that a single-point near edge-lit detonation results in asymmetries in the density and thermal profiles, notably the expansion timescale, throughout the supernova ejecta. We demonstrate that this asymmetry of the thermodynamic trajectories should be common to off-center detonations where a small amount of the star is burned prior to detonation. The sensitivity of the yields on the expansion timescale results in an asymmetric distribution of the elements synthesized as reaction products. We tabulate the shift in the center of mass of the various elements produced in our model supernova and find an odd-even pattern for elements past silicon. Our calculations show that off-center single-point detonations in carbon-oxygen white dwarfs are marked by significant composition asymmetries in their remnants which bear potentially observable signatures in both velocity and coordinate space, including an elemental nickel mass fraction that varies by a factor of 2-3 from one side of the remnant to the other.

  2. The structure of the homogeneous oxidation catalyst, Mn(II)-Br(-I)x, in supercritical water: An x-ray absorption fine structure study

    Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure of Mn(II) and Br(-I) ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr2 in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH2 and Mn-Br are 2.11 and 2.46 ?, respectively. Direct contact ion pairs form with about 2 Br(-I) ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr2, below 1.0 m, changes from essentially [Mn(II)(H2O)6]+2 to [Mn(II)(H2O)2(Br)2] in supercritical water (scH2O). When an excess of a Br(-I) ion is added, the bromide coordination increases and the number of water molecules decreases. The results show that the initial MnBr2 catalyst in scH2O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO

  3. Quasi-static energy absorption of hollow microlattice structures

    Liu, YL; Schaedler, TA; Jacobsen, AJ; Chen, X

    2014-12-01

    We present a comprehensive modeling and numerical study focusing on the energy quasi-static crushing behavior and energy absorption characteristics of hollow tube microlattice structures. The peak stress and effective plateau stress of the hollow microlattice structures are deduced for different geometrical parameters which gives volume and mass densities of energy absorption, D-v and D-m, scale with the relative density, (rho) over bar, as D-v similar to (rho) over bar (1) (5) and D-m similar to (rho) over bar (0 5), respectively, fitting very well to the experimental results of both 60 degrees inclined and 90 degrees predominately microlattices. Then the strategies for energy absorption enhancement are proposed for the engineering design of microlattice structures. By introducing a gradient in the thickness or radius of the lattice members, the buckle propagation can be modulated resulting in an increase in energy absorption density that can exceed 40%. Liquid filler is another approach to improve energy absorption by strengthening the microtruss via circumference expansion, and the gain may be over 100% in terms of volume density. Insight into the correlations between microlattice architecture and energy absorption performance combined with the high degree of architecture control paves the way for designing high performance microlattice structures for a range of impact and impulse mitigation applications for vehicles and structures. (C) 2014 Elsevier Ltd. All rights reserved.

  4. In-situ X-Ray Absorption Spectroscopy (XAS) Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction

    Gorlin, Yelena; Lassalle-Kaiser, Benedikt; Benck, Jesse D.; Gul, Sheraz; Webb, Samuel M; Yachandra, Vittal K.; Yano, Junko; Jaramillo, Thomas F.

    2013-01-01

    In-situ x-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in-situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using x-ray absorption near edge structure (XANES) and extended x-r...

  5. Absorption lines and the radio structure of quasars

    High angular resolution radio observations at lambda6cm of 20 quasars are presented, all but two of which have been selected from a sample used by previous authors for a survey of absorption lines. The additional two, 1246-057 and 1333 + 286, are quasars with broad absorption lines and appear to be radio quiet. The radio structures for the entire sample of 66 sources of the previous authors are summarized and an investigation is made of whether the radio structure might provide clues on understanding the origin of the absorption lines in the range Zsub(em)-Zsub(ab) approx. 3000-18000 kms-1. The frequency of occurrence of absorption lines appears to be similar for both radio and optically selected quasars. (author)

  6. Electronic structure and optic absorption of phosphorene under strain

    Duan, Houjian; Yang, Mou; Wang, Ruiqiang

    2016-07-01

    We studied the electronic structure and optic absorption of phosphorene (monolayer of black phosphorus) under strain. Strain was found to be a powerful tool for the band structure engineering. The in-plane strain in armchair or zigzag direction changes the effective mass components along both directions, while the vertical strain only has significant effect on the effective mass in the armchair direction. The band gap is narrowed by compressive in-plane strain and tensile vertical strain. Under certain strain configurations, the gap is closed and the energy band evolves to the semi-Dirac type: the dispersion is linear in the armchair direction and is gapless quadratic in the zigzag direction. The band-edge optic absorption is completely polarized along the armchair direction, and the polarization rate is reduced when the photon energy increases. Strain not only changes the absorption edge (the smallest photon energy for electron transition), but also the absorption polarization.

  7. Arbitrarily thin metamaterial structure for perfect absorption and giant magnification

    Jin, Yi; Xiao, Sanshui; Mortensen, N. Asger;

    2011-01-01

    In our common understanding, for strong absorption or amplification in a slab structure, the desire of reducing the slab thickness seems contradictory to the condition of small loss or gain. In this paper, this common understanding is challenged. It is shown that an arbitrarily thin metamaterial ...... perfect absorption, while this is not required for giant magnification. Detailed analysis for the existence of the critical angle and physical explanation for these abnormal phenomena are given. © 2011 Optical Society of America....

  8. Metallic subwavelength structures for a broadband infrared absorption control

    Biener, Gabriel; Niv, Avi; Kleiner, Vladimir; Hasman, Erez

    2007-04-01

    We present a method to control the absorption of a resonator by using a subwavelength structure consisting of thin metallic plates that behaves as a metamaterial film. We demonstrate the ability to tailor the conductivity of such a metallic subwavelength structure to achieve a resonator with the desired impedance matching for the mid-infrared range. This approach provides for broadband, as well as broad-angle, enhanced absorption. Theoretical analyses, as well as experimental results of the optical properties of a metallic NiCr structure at 8-12 μm spectral range are introduced.

  9. Local structure of Fe in Fe-doped misfit-layered calcium cobaltite: An X-ray absorption spectroscopy study

    Polycrystalline Ca3Co4−xFexO9+δ ceramics (x=0, 0.01, 0.03, 0.05) were fabricated using a simple thermal hydro-decomposition method and a spark plasma sintering technique. Thermoelectric property measurements showed that increasing Fe concentration resulted in a decrease in electrical resistivity, thermopower and thermal conductivity, leading to an improvement in the dimensionless figure-of-merit, >35% for x=0.05 at 1073 K. An X-ray absorption spectroscopy technique was used to investigate the local structure of Fe ions in the Ca3Co4−xFexO9+δ structure for the first time. By fitting data from the extended X-ray absorption fine structure (EXAFS) spectra and analyzing the X-ray absorption near-edge structure (XANES) spectra incorporated with first principle simulation, it was shown that Fe was substituted for Co in the the Ca2CoO3 (rocksalt, RS) layer rather than in the CoO2 layer. Variation in the thermoelectric properties as a function of Fe concentration was attributed to charge transfer between the CoO2 and the RS layers. The origin of the preferential Fe substitution site was investigated considering the ionic radii of Co and Fe and the total energy of the system. - Graphical abstract: The Fe K-edge XANES spectra of: (a) experimental result in comparison to the simulated spectra when Fe atoms were substituted in the RS layer; (b) with magnetic moment; (c) without magnetic moment, and in the CoO2 layer; (d) with magnetic moment and (e) without magnetic moment. Highlights: • Synthesis, structural studies, and thermoelectric properties of Ca3Co4−xFexO9+δ. • Direct evidence for the local structure of the Fe ions in the Ca3Co4−xFexO9+δ using XAS analysis. • EXAFS and XANES analysis showed that Fe was likely to be situated in the RS layer structure. • Changes in TE property with Fe content was due to charge transfer between the CoO2 and the RS layers. • Total energy calculation showed energetically favorable Fe substitution in the RS layer

  10. Improved self-absorption correction for extended x-ray absorption fine-structure measurements

    Booth, C.H.; Bridges, F.

    2003-06-04

    Extended x-ray absorption fine-structure (EXAFS) data collected in the fluorescence mode are susceptible to an apparent amplitude reduction due to the self-absorption of the fluorescing photon by the sample before it reaches a detector. Previous treatments have made the simplifying assumption that the effect of the EXAFS on the correction term is negligible, and that the samples are in the thick limit. We present a nearly exact treatment that can be applied for any sample thickness or concentration, and retains the EXAFS oscillations in the correction term.

  11. ABSORPTIVE OPTICAL BISTABILITY IN HYBRID LASER STRUCTURE

    Tan Chee Leong

    2010-06-01

    Full Text Available A hybrid bistable semiconductor laser structure consisting of an edge-emitting laser as a gain region and a vertical cavity laser as an absorber region, which translates lateral emission to vertical emission is analyzed. The device is modeled using appropriately modified rate equations and simulated using PSPICE circuit simulator. The dc sweep exhibits bistability. The hysterisis width of the bistable characteristics is found to depend on the reverse dc sweep, source resistance, and temperature. It is also noticed that the threshold currents and the hysterisis width can be controlled by the physical dimensions of gain and absorber regions and the driver circuit parameters. Turn-on delay decreases as the input current is increased.

  12. Cerium oxide nanoparticles coated by surfactant sodium bis(2-ethylhexyl) sulphosuccinate (AOT): local atomic structures and x-ray absorption spectroscopic studies

    Cerium oxide nanoparticles coated by sodium bis(2-ethylhexyl) sulphosuccinate (AOT) were prepared by using a microemulsion method. Transmission electron microscopy revealed an average particle size of 2-3 nm. X-ray diffraction showed that the cerium oxide nanoparticles retain the CeF2-type cubic structures like the bulk crystal. The intermediate valence of formally tetravalent compounds had been detected by x-ray-absorption near-edge structure (XANES) spectra of Ce LIII absorption in bulk CeO2 and the cerium oxide nanoparticles. Two well resolved white lines can be assigned to the electron configurations of 4f0L and 4f1L, respectively, where L denotes a ligand hole. At the same time, the cerium oxide nanoparticles also showed the structural features of trivalent compounds, in comparison to the trivalent Ce(NO3)3·6H2O. Four Lorentzian functions and two arctan functions were used to fit the normalized XANES spectra. The extended x-ray-absorption fine-structure (EXAFS) technique was used to probe the local atomic structures around the absorber Ce. The multielectron excitation effect on the EXAFS spectra was eliminated. A core-shell model was used to deduce the near-neighbour structural parameters around cerium. Bulk CeO2 with eight oxygen atoms located at 2.343 A was used as the reference sample to extract the backscattering amplitude and phase shift of the Ce-O bond. One half of the atoms locate at the core part with the CeF2-type cubic structures (eight oxygens at 2.343 A around Ce), the other half of the atoms are amorphous phase located in the shell part (surface of the nanoparticles) with approximately Ce2O3 structural features (averaged seven oxygens at 2.50 A around Ce). (author)

  13. Dynamic energy absorption characteristics of hollow microlattice structures

    Liu, YL; Schaedler, TA; Chen, X

    2014-10-01

    Hollow microlattice structures are promising candidates for advanced energy absorption and their characteristics under dynamic crushing are explored. The energy absorption can be significantly enhanced by inertial stabilization, shock wave effect and strain rate hardening effect. In this paper we combine theoretical analysis and comprehensive finite element method simulation to decouple the three effects, and then obtain a simple model to predict the overall dynamic effects of hollow microlattice structures. Inertial stabilization originates from the suppression of sudden crushing of the microlattice and its contribution scales with the crushing speed, v. Shock wave effect comes from the discontinuity across the plastic shock wave front during dynamic loading and its contribution scales with e. The strain rate effect increases the effective yield strength upon dynamic deformation and increases the energy absorption density. A mechanism map is established that illustrates the dominance of these three dynamic effects at a range of crushing speeds. Compared with quasi-static loading, the energy absorption capacity a dynamic loading of 250 m/s can be enhanced by an order of magnitude. The study may shed useful insight on designing and optimizing the energy absorption performance of hollow microlattice structures under various dynamic loads. (C) 2014 Elsevier Ltd. All rights reserved.

  14. Absorption-reduced waveguide structure for efficient terahertz generation

    Pálfalvi, L., E-mail: palfalvi@fizika.ttk.pte.hu [Institute of Physics, University of Pécs, Ifjúság ú. 6, 7624 Pécs (Hungary); Fülöp, J. A. [MTA-PTE High-Field Terahertz Research Group, Ifjúság ú. 6, 7624 Pécs (Hungary); Szentágothai Research Centre, University of Pécs, Ifjúság ú. 20, 7624 Pécs (Hungary); Hebling, J. [Institute of Physics, University of Pécs, Ifjúság ú. 6, 7624 Pécs (Hungary); MTA-PTE High-Field Terahertz Research Group, Ifjúság ú. 6, 7624 Pécs (Hungary); Szentágothai Research Centre, University of Pécs, Ifjúság ú. 20, 7624 Pécs (Hungary)

    2015-12-07

    An absorption-reduced planar waveguide structure is proposed for increasing the efficiency of terahertz (THz) pulse generation by optical rectification of femtosecond laser pulses with tilted-pulse-front in highly nonlinear materials with large absorption coefficient. The structure functions as waveguide both for the optical pump and the generated THz radiation. Most of the THz power propagates inside the cladding with low THz absorption, thereby reducing losses and leading to the enhancement of the THz generation efficiency by up to more than one order of magnitude, as compared with a bulk medium. Such a source can be suitable for highly efficient THz pulse generation pumped by low-energy (nJ-μJ) pulses at high (MHz) repetition rates delivered by compact fiber lasers.

  15. Energy absorption characteristics of nano-composite conical structures

    The effect of the filler material on the energy absorption capabilities of polyamide 6 composite structures is studied in details in the present paper. The axial dynamic and quasi-static collapse of conical structures was conducted using a high energy drop tower, as well as Instron 5500R electro-mechanical testing machine. The impact event was recorded using a high-speed camera and the fracture surface was investigated using scanning electron microscopy (SEM). The obtained results indicate an important influence of filler material on the energy absorption capabilities of the polymer composites. A significant increase in specific energy absorption (SEA) is observed in polyamide 6 (PA6) reinforced with nano-silica particles (SiO2) and glass-spheres (GS), whereas addition of montmorillonite (MMT) did not change the SEA parameter.

  16. Energy absorption characteristics of nano-composite conical structures

    Silva, F.; Sachse, S.; Njuguna, J.

    2012-09-01

    The effect of the filler material on the energy absorption capabilities of polyamide 6 composite structures is studied in details in the present paper. The axial dynamic and quasi-static collapse of conical structures was conducted using a high energy drop tower, as well as Instron 5500R electro-mechanical testing machine. The impact event was recorded using a high-speed camera and the fracture surface was investigated using scanning electron microscopy (SEM). The obtained results indicate an important influence of filler material on the energy absorption capabilities of the polymer composites. A significant increase in specific energy absorption (SEA) is observed in polyamide 6 (PA6) reinforced with nano-silica particles (SiO2) and glass-spheres (GS), whereas addition of montmorillonite (MMT) did not change the SEA parameter.

  17. Absorption-reduced waveguide structure for efficient terahertz generation

    An absorption-reduced planar waveguide structure is proposed for increasing the efficiency of terahertz (THz) pulse generation by optical rectification of femtosecond laser pulses with tilted-pulse-front in highly nonlinear materials with large absorption coefficient. The structure functions as waveguide both for the optical pump and the generated THz radiation. Most of the THz power propagates inside the cladding with low THz absorption, thereby reducing losses and leading to the enhancement of the THz generation efficiency by up to more than one order of magnitude, as compared with a bulk medium. Such a source can be suitable for highly efficient THz pulse generation pumped by low-energy (nJ-μJ) pulses at high (MHz) repetition rates delivered by compact fiber lasers

  18. Multiple-scattering calculations of x-ray-absorption spectra

    A high-order multiple-scattering (MS) approach to the calculation of polarized x-ray-absorption spectra, which includes both x-ray-absorption fine structure and x-ray-absorption near-edge structure, is presented. Efficient calculations in arbitrary systems are carried out by using a curved-wave MS path formalism that ignores negligible paths, and has an energy-dependent self-energy and MS Debye-Waller factors. Embedded-atom background absorption calculations on an absolute energy scale are included. The theory is illustrated for metallic Cu, Cd, and Pt. For these cases the MS expansion is found to converge to within typical experimental accuracy, both to experiment and to full MS theories (e.g., band structure), by using only a few dozen important paths, which are primarily single-scattering, focusing, linear, and triangular

  19. Application of x-ray absorption fine structure (XAFS) to local-order analysis in Fe-Cr maghemite-like materials

    Montero-Cabrera, M. E., E-mail: elena.montero@cimav.edu.mx; Fuentes-Cobas, L. E.; Macías-Ríos, E. [Centro de Investigación en Materiales Avanzados, Chihuahua, 31136, México (Mexico); Fuentes-Montero, M. E. [Universidad Autónoma de Chihuahua, Chihuahua, 31000, México (Mexico)

    2015-07-23

    The maghemite-like oxide system γ-Fe{sub 2-x}Cr{sub x}O{sub 3} (x=0.75, 1 and 1.25) was studied by X-ray absorption fine structure (XAFS) and by synchrotron radiation X-ray diffraction (XRD). Measurements were performed at the Stanford Synchrotron Radiation Lightsource at room temperature, at beamlines 2-1, 2-3 and 4-3. High-resolution XRD patterns were processed by means of the Rietveld method. In cases of atoms being neighbors in the Periodic Table, the order/disorder degree of the considered solutions is indiscernible by “normal” (absence of “anomalous scattering”) diffraction experiments. Thus, maghemite-like materials were investigated by XAFS in both Fe and Cr K-edges to clarify, via short-range structure characterization, the local ordering of the investigated system. Athena and Artemis graphic user interfaces for IFEFFIT and FEFF8.4 codes were employed for XAFS spectra interpretation. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure (XANES) transitions were performed. By analysis of the Cr K-edge XANES, it has been confirmed that Cr is located in an octahedral environment. Fitting of the extended X-ray absorption fine structure (EXAFS) spectra was performed under the consideration that the central atom of Fe is allowed to occupy octa- and tetrahedral positions, while Cr occupies only octahedral ones. Coordination number of neighboring atoms, interatomic distances and their quadratic deviation average were determined for x=1, by fitting simultaneously the EXAFS spectra of both Fe and Cr K-edges. The results of fitting the experimental spectra with theoretical standards showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO{sub 3})

  20. Application of x-ray absorption fine structure (XAFS) to local-order analysis in Fe-Cr maghemite-like materials

    The maghemite-like oxide system γ-Fe2-xCrxO3 (x=0.75, 1 and 1.25) was studied by X-ray absorption fine structure (XAFS) and by synchrotron radiation X-ray diffraction (XRD). Measurements were performed at the Stanford Synchrotron Radiation Lightsource at room temperature, at beamlines 2-1, 2-3 and 4-3. High-resolution XRD patterns were processed by means of the Rietveld method. In cases of atoms being neighbors in the Periodic Table, the order/disorder degree of the considered solutions is indiscernible by “normal” (absence of “anomalous scattering”) diffraction experiments. Thus, maghemite-like materials were investigated by XAFS in both Fe and Cr K-edges to clarify, via short-range structure characterization, the local ordering of the investigated system. Athena and Artemis graphic user interfaces for IFEFFIT and FEFF8.4 codes were employed for XAFS spectra interpretation. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure (XANES) transitions were performed. By analysis of the Cr K-edge XANES, it has been confirmed that Cr is located in an octahedral environment. Fitting of the extended X-ray absorption fine structure (EXAFS) spectra was performed under the consideration that the central atom of Fe is allowed to occupy octa- and tetrahedral positions, while Cr occupies only octahedral ones. Coordination number of neighboring atoms, interatomic distances and their quadratic deviation average were determined for x=1, by fitting simultaneously the EXAFS spectra of both Fe and Cr K-edges. The results of fitting the experimental spectra with theoretical standards showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO3)

  1. An x-ray absorption spectroscopic study of the electronic structure and bonding of rare-earth orthoferrites

    Rare-earth orthoferrites, REFeO3 (RE=rare earth; Y), are tremendously adaptable compounds that are being investigated for use in a wide variety of applications including gas sensors, vehicle catalytic converters, and solid-oxide fuel cells. They also exhibit interesting magnetic properties such as high-temperature antiferromagnetism, making them useful for data storage applications. The compounds adopt a distorted perovskite-type structure where the tilt angle of the octahedra increases (Fe-O-Fe bond angle decreases) as the size of the rare-earth atom decreases. Despite intensive study of the physical properties of these compounds, very few studies have investigated how the bonding and electronic structure of these systems change with substitution of the RE. X-ray absorption near-edge spectroscopy (XANES) is a technique well-suited for such a study, and, in view of this, Fe L-, Fe K- and O K-edge spectra from a series of REFeO3 compounds (RE=La, Pr, Nd, Sm, Eu, Gd, Ho, Yb, Y) have been collected, and are presented here. Fe L-edge spectra show that Fe is octahedrally coordinated and that the Fe-centered octahedra do not appear to distort with changes in the identity of the RE. The Fe K-edge spectra contain an intersite hybrid peak, which is an ill-studied feature that is attributed to non-local transitions of 1s electrons to 3d states on the next-nearest-neighbor atom that are hybridized with 4p states on the absorbing atom through O 2p states. In this study, it is shown that the intensity of this feature is strongly dependent on the Fe-O-Fe bond angle; the lower the Fe-O-Fe bond angle, the less intense the intersite hybrid peak is. (paper)

  2. X-ray absorption spectroscopy for element selective investigations of structure, valence and magnetism in doped oxides

    Full text: The use of x-ray absorption spectroscopy (XAS) and in particular x-ray linear dichroism (XLD) and x-ray magnetic circular dichroism (XMCD) offers the possibility to study a range of physical properties with element specificity. The combination of XAS at the near edge (XANES) and XLD allows to separately determine the valence state and the local structural environment of dopant atoms, cationic and anionic sublattice in doped oxides. This approach was used for epitaxial films of Co-doped ZnO, Co/Al-codoped ZnO, Co/N-codoped ZnO, Gd-doped ZnO, and Fe/N-codoped TiO2 to determine the incorporation of the respective dopant atoms into the host lattice, its valence state, and at the same time assure phase pureness of the material, when the XANES and XLD measurements are combined with respective simulations. Especially for the Co-doped ZnO system a comprehensive set of quality indicators based on XAS could be established which assure that Co substitutes for Zn and the formation of metallic Co precipitations can be ruled out. In addition, XMCD allows to study the sublattice magnetization of the dopant which can be compared to integral SQUID magnetometry and by that establishing, that e.g. Co-doped ZnO is an anisotropic paramagnet. Signs of ferromagnetic order could be directly attributed to the presence of metallic Co precipitations which could be evidenced by a combination of XANES and transmission electron microscopy. Recently, unprecedented high field XMCD measurements up to 17 Tesla have allowed to quantify the next cation neighbor exchange interaction which has been shown to be antiferromagnetic as inferred before. Here the concept of the comprehensive XAS-based approach will be reviewed to illustrate how XANES allows to determine the valence, XLD the local structure and XMCD the magnetic properties of dopant atoms and host material separately. (author)

  3. Characterization of Metalloproteins and Biomaterials by X-ray Absorption Spectroscopy and X-ray Diffraction

    Frankær, Christian Grundahl

    and R6) were solved by single crystal X-ray diffraction (XRD) to 1.40 Å, 1.30 Å and 1.80 Å resolution, respectively. The zinc coordination in each conformation was studied by XAS including both extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge structure...... the zinc coordination in the T3-sites, in particular. Furthermore, XANES spectra for the zinc sites in T6 and R6 insulin were successfully calculated using finite difference methods, and the bond distances and angles were optimized from a quantitative XANES analysis. T6 insulin was furthermore...

  4. X-ray absorption fine structure spectroscopy and X-ray diffraction study of cementitious materials derived from coal combustion by-products

    Cementitious materials derived from coal combustion by-products have been investigated by means of X-ray diffraction (XRD) and S and Ca K-edge X-ray absorption fine structure (XAFS) spectroscopy. The XRD analysis revealed that these materials are a complex mixture of a small amount of quartz [SiO2] and three calcium-bearing compounds: hannebachite [CaSO3·1/2H2O], gypsum [CaSO4·2H2O] and ettringite [(Ca6(Al(OH)6)2(SO4)3·26H2O)]. Analysis of the S XAFS data focused on deconvolution of the X-ray absorption near-edge structure (XANES) regions of the spectra. This analysis established that sulfate and sulfite are the two major sulfur forms, with a minor thiophenic component contained in unburned carbon in the fly ash. Increasing sulfate and decreasing sulfite correlated well with increasing gypsum and ettringite and decreasing hannebachite content in the samples. Different calcium compounds were identified primarily through simple comparison of the Ca K-edge XANES and radial structure functions (RSFs) of the cementitious samples with those of reference compounds. Because of the complex coordination chemistry of calcium in these materials, it was difficult to obtain detailed local atomic environment information around calcium beyond the first Ca-O peak. Analysis of the extended X-ray absorption fine structure (EXAFS) and the RSF gave average Ca-O distances in the range 2.44-2.5 A, with each calcium atom surrounded roughly by eight oxygen atoms. In certain samples, the average Ca-O distances were close to that in ettringite (2.51 A), suggesting that these samples have higher ettringite content. The results of S and Ca K-edges XAFS and the XRD data were in reasonable agreement

  5. Sulfur X-ray absorption fine structure in porous Li–S cathode films measured under argon atmospheric conditions

    Müller, Matthias, E-mail: matthias.mueller@ptb.de [Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, 10587 Berlin (Germany); Choudhury, Soumyadip [Leibniz-Institut für Polymerforschung, Hohe Strasse 6, 01069 Dresden (Germany); Technische Universität Dresden, Physical Chemistry of Polymeric Materials ,01062 Dresden (Germany); Gruber, Katharina [VARTA Micro Innovation GmbH, Stremayrgasse 9, 8010 Graz (Austria); Cruz, Valene B. [Universität Ulm, Institut für Elektrochemie, 89069 Ulm (Germany); Helmholtz-Institut Ulm (HIU), 89069 Ulm (Germany); Fuchsbichler, Bernd [VARTA Micro Innovation GmbH, Stremayrgasse 9, 8010 Graz (Austria); Jacob, Timo [Universität Ulm, Institut für Elektrochemie, 89069 Ulm (Germany); Helmholtz-Institut Ulm (HIU), 89069 Ulm (Germany); Koller, Stefan [VARTA Micro Innovation GmbH, Stremayrgasse 9, 8010 Graz (Austria); Stamm, Manfred [Leibniz-Institut für Polymerforschung, Hohe Strasse 6, 01069 Dresden (Germany); Technische Universität Dresden, Physical Chemistry of Polymeric Materials ,01062 Dresden (Germany); Ionov, Leonid [Leibniz-Institut für Polymerforschung, Hohe Strasse 6, 01069 Dresden (Germany); Beckhoff, Burkhard [Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, 10587 Berlin (Germany)

    2014-04-01

    In this paper we present the first results for the characterization of highly porous cathode materials with pore sizes below 1 μm for Lithium Sulfur (Li–S) batteries by Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. A novel cathode material of porous carbon films fabricated with colloidal array templates has been investigated. In addition, an electrochemical characterization has been performed aiming on an improved correlation of physical and chemical parameters with the electrochemical performance. The performed NEXAFS measurements of cathode materials allowed for a chemical speciation of the sulfur content inside the cathode material. The aim of the presented investigation was to evaluate the potential of the NEXAFS technique to characterize sulfur in novel battery material. The long term goal for the characterization of the battery materials is the sensitive identification of undesired side reactions, such as the polysulfide shuttle, which takes place during charging and discharging of the battery. The main drawback associated with the investigation of these materials is the fact that NEXAFS measurements can usually only be performed ex situ due to the limited in situ instrumentation being available. For Li–S batteries this problem is more pronounced because of the low photon energies needed to study the sulfur K absorption edge at 2472 eV. We employed 1 μm thick Si{sub 3}N{sub 4} windows to construct sealed argon cells for NEXAFS measurements under ultra high vacuum (UHV) conditions as a first step towards in situ measurements. The cells keep the sample under argon atmosphere at any time and the X-ray beam passes mainly through vacuum which enables the detection of the low energy X-ray emission of sulfur. Using these argon cells we found indications for the presence of lithium polysulfides in the cathode films whereas the correlations to the offline electrochemical results remain somewhat ambiguous. As a consequence of these findings one

  6. Temperature dependence of the local structure of YBa2Cu3O/sub 7-//sub δ/ with varying oxygen content: An x-ray-absorption study

    The local structure of YBa2Cu3O/sub y/ determined using x-ray-absorption fine structure (XAFS) agrees well with the long-range order given by diffraction results for both oxygen-rich, orthorhombic (y = 6.98 and 6.87) and oxygen-deficient, tetragonal (y = 6.15) compounds. The x-ray-absorption near-edge structure supports the conclusion that, as y = 7 goes to y = 6, the O is removed from the chains and the chain Cu atoms, Cu(1), becomes monovalent with a linear O-Cu-O structural configuration and a 3d/sup 10/ electronic configuration, as in Cu2O. For the XAFS analysis, structural standards were determined, and these standards worked well not only for the Cu first-neighbor O environment but also for the Cu second-neighbor metal-atom environment out to 4 A. A detailed multipeak analysis reproduced the XAFS spectra well and yielded structural parameters that agree with diffraction. The temperature dependence of the structural parameters shows only a smooth variation, with no significant anomalies. The Cu-X distances have a negligible to a small positive change with temperature, consistent with the lattice expansion. The exception is the Cu-Ba distances which change substantially; the Cu(1)-Ba distance increases and the Cu(2)-Ba distance decreases. This indicates that the Ba moves away from the Cu(1)-O chains and toward the Cu(2)-O planes with increasing temperature and that anharmonicity plays a role. This motion is larger for the oxygen-depleted compound than for the fully oxygenated material. The in-plane Cu-O first-neighbor vibrations exhibit no significant softening with temperature

  7. Polarized X-ray absorption spectra and electronic structure of molybdenite (2H-MoS2)

    Li, Dien; Bancroft, G. M.; Kasrai, M.; Fleet, M. E.; Feng, X. H.; Tan, K. H.

    1995-03-01

    Polarized S K- and L-edge, Mo L3- and L2-edge x-ray absorption near-edge structure (XANES) of natural molybdenite (2H-MoS2) have been measured with synchrotron radiation. These results are qualitatively interpreted using the energy band model of molybdenite and provide important information on the unoccupied states of molybdenite. The valence band (VB) maximum of molybdenite is characterized by fully occupied Mo 4dz 2, and the conduction band (CB) minimum of molybdenite is characterized by unoccupied Mo 4d states. The unoccupied Mo 4d band is split into two sub-bands, designated as t{2g/-}/t{2g/+}and e{g/-}/e{g/+}sets. Although the relative energy of these two sets are difficult to be evaluated, probably the former has the lower energy than the latter, both two sets have the combination wave functions of the other unoccupied Mo 4d components, rather than the simple 4dx 2 — y2 and 4dxy states. The unoccupied Mo 4d sub-bands contain significant DOS of both S 3 p- and 3 s-like states, indicating strong hybridization with S 3s and 3 p states. In the lower energy sub-band, the DOS of the S pz- and px,y-like states are very similar. However, in the higher energy sub-band, the DOS of the S 3 px,y-like state is lower than that of the S 3pz state. Polarized S K-edge XANES also reveal the features of antibonding S pz- and px,y-like states in molybdenite. The feature assigned to the S 3 pz-like states is stronger and sharper, and shifts to lower energy by about 2 eV relative to that for the S 3 px,y-like states.

  8. An X-ray Absorption Fine Structure study of Au adsorbed onto the non-metabolizing cells of two soil bacterial species

    Song, Zhen; Kenney, Janice P.L.; Fein, Jeremy B.; Bunker, Bruce A. (Notre)

    2015-02-09

    Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has been observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.

  9. Model galactic coronae: Ionization structure and absorption-line spectra

    We describe a general model for a gaseous galactic corona, and demonstrate that it is in harmony with a variety of observational and theoretical constraints. We then compute the ionization equilibria of H, He, C, N, O, Si, and S atoms in the corona and determine the strengths of resonance absorption lines arising therein. To this end, we obtain approximate cross sections for ionization of the heavy-element ions by photons of energy E/sub γ/< or =100 eV.We use our results first to discuss the expected absorption spectrum of our Galaxy's corona. Subsequently, we discuss in detail the relevance of our computed equilibria to the suggestion that galactic coronae produce some redshift systems in quasar absorption spectra. Because our model coronae are not isothermal, the ionization structure existing along various lines of sight through them is not in accord with the concept of ''reasonable ionization equilibrium'': a concept assumed to be valid in most analyses of quasar spectra. However, our calculations indicate that typically one well-established redshift system in each quasar absorption spectrum could arise in the corona of an intervening galaxy. This is the number expected from statistical arguments if quasar redshifts are fully cosmological in origin

  10. X-ray absorption spectroscopy of Mn doped ZnO thin films prepared by rf sputtering technique

    A set of r.f. sputter deposited ZnO thin films prepared with different Mn doping concentrations have been characterised by Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Spectroscopy (XANES) measurements at Zn, Mn and O K edges and at Mn L2,3 edges apart from long range structural characterisation by Grazing Incident X-ray Diffraction (GIXRD) technique. Magnetic measurements show room temperature ferromagnetism in samples with lower Mn doping which is however, gets destroyed at higher Mn doping concentration. The results of the magnetic measurements have been explained using the local structure information obtained from EXAFS and XANES measurements

  11. X-RAY ABSORPTION ON URANIUM SYSTEMS AT VARIOUS THRESHOLDS

    Kalkowski, G.; Kaindl, G.; Brewer, W.; Krone, W

    1986-01-01

    We have studied the near edge X-ray absorption fine structure of various metallic and non-metallic U compounds at the L3, M3, M4,5, N4,5, and O4,5 thresholds using transmission and total-electron-yield techniques. At the L3 thresholds, a chemical shift of ≈4 eV between trivalent and tetravalent U compounds is observed, which drops to ≈2eV between the latter and hexavalent U systems. This indicates extended 5f character and a 5f count close to two in the high oxidation states. The M4,5 thresho...

  12. Partially Absorbed Comptonization Spectrum from the Nearly Edge-on Source X1822-371

    Iaria, R.; Di Salvo, T.; Burderi, L.; Robba, N. R.

    2001-08-01

    We report the results of a spectral analysis over the range 0.1-200 keV performed on the dipping source X1822-371 observed by BeppoSAX. We find the best fit to the continuum using a partially covered Comptonization model, representing scattering of soft seed photons by electrons at a temperature of ~4.8 keV, without the presence of any soft blackbody emission. The equivalent hydrogen column obtained for the absorbed component is ~4.5×1022 cm-2, an order of magnitude larger than the Galactic absorption for this source, and the covering fraction is ~71%. Because the inclination angle of X1822-371 to the line of sight is ~85°, this model gives a reasonable scenario for the source: the Comptonized spectrum could come from an extended accretion disk corona (ADC), probably the only region that can be directly observed as a result of the high inclination. The excess matter producing the partial covering could be close to the equatorial plane of the system, above the outer disk, occulting the emission from the inner disk and the inner part of the ADC. An iron emission line is also present at ~6.5 keV with an equivalent width of ~150 eV. We argue that this strong iron line cannot be explained as reflection of the Comptonized spectrum by the accretion disk. It is probably produced in the ADC. An emission line at ~1.9 keV (with an equivalent width of ~54 eV) and an absorption edge at ~8.7 keV (with an optical depth of ~0.1) are also required to fit this spectrum. These features are probably produced by highly ionized iron (Fe XXIV) present in the outer part of the ADC, where the plasma density is ~1011-1012 cm-3 and ionized plasma is present.

  13. Nano-structured titanium and aluminium nitride coatings: Study by grazing incidence X-ray diffraction and X-ray absorption and anomalous diffraction

    Tuilier, M.-H., E-mail: marie-helene.tuilier@uha.fr [Universite de Haute Alsace (UHA), Laboratoire Physique et Mecanique Textile (LPMT), EA 4365 -conventionnee au CNRS, Equipe PPMR, F-68093 Mulhouse (France); Pac, M.-J. [Universite de Haute Alsace (UHA), Laboratoire Physique et Mecanique Textile (LPMT), EA 4365 - conventionnee au CNRS, Equipe PPMR, F-68093 Mulhouse (France); Anokhin, D.V. [Universite de Haute Alsace (UHA), CNRS, Institut de Science des Materiaux de Mulhouse (IS2M), LRC 7228, F-68093 Mulhouse (France); Moscow State University, Faculty of Fundamental Physical and Chemical Engineering, 119991, Moscow, GSP-1, 1-51 Leninskie Gory (Russian Federation); Ivanov, D.A. [Universite de Haute Alsace (UHA), CNRS, Institut de Science des Materiaux de Mulhouse (IS2M), LRC 7228, F-68093 Mulhouse (France); Rousselot, C. [Universite de Franche-Comte, FEMTO-ST (UMR CNRS 6174), F-25211 Montbeliard (France); Thiaudiere, D. [Synchrotron Soleil, Saint Aubin, F-91192 Gif sur Yvette (France)

    2012-12-30

    Titanium and aluminium nitride thin films, Ti{sub 1-x}Al{sub x}N (x = 0, x = 0.5, x = 0.68), deposited by reactive magnetron sputtering on silicon substrates are investigated by combining two different X-ray diffraction experiments carried out using synchrotron radiation. Grazing-incidence X-ray diffraction and Ti K-edge diffraction anomalous near edge structure spectroscopy provide information on the micro- and nano-structure of the films respectively, which play a crucial role in the functionality of coatings. The spectroscopic data of Ti{sub 0.50}Al{sub 0.50}N film show that Ti atoms in crystallized domains and grain boundaries are all in octahedral cubic local order, but their growth mode is quite different. It is found that the crystallized part of the Ti{sub 0.50}Al{sub 0.50}N film has a single-crystalline nature, whereas the TiN one presents a fibrillar microstructure. For Ti{sub 0.32}Al{sub 0.68}N film, grazing-incidence X-ray diffraction provides information on the uniaxial texture along the [001] direction of the hexagonal lattice. A sharp Ti K pre-edge peak is observed in diffraction anomalous near edge spectrum that definitely shows that Ti atoms are incorporated in the hexagonal lattice of those fibrillar domains. Moreover, the difference observed between Ti K-edge diffraction anomalous and X-ray absorption pre-edge regions proves that a significant part of Ti atoms is located in nanocrystallites with cubic symmetry outside of the crystallized domains. - Highlights: Black-Right-Pointing-Pointer We study nano and micro-structures of TiN, Ti{sub 0.50}Al{sub 0.50}N and Ti{sub 0.32}Al{sub 0.68}N films. Black-Right-Pointing-Pointer Anomalous diffraction solves the crystallized part regardless of grain boundaries. Black-Right-Pointing-Pointer TiN microstructure is fibrillar, Ti{sub 0.5}Al{sub 0.5}N presents single crystalline domains. Black-Right-Pointing-Pointer For Ti{sub 0.32}Al{sub 0.68}N, Ti atoms are located in nanocrystallites with cubic symmetry

  14. Incorporation of pertechnetate and perrhenate into corroded steel surfaces studied by X-ray absorption fine structure spectroscopy

    Batch reaction experiments and solid-phase characterization analyses were completed to examine the uptake of dissolved perrhenate [Re(VII)] or pertechnetate [Tc(VII)] by A-516 steel coupons that corroded in simulated groundwater solutions or dilute water. The goal was to identify the mechanism(s) that control the uptake of 99Tc by corrosion products on carbon steel in the presence of dilute solutions. X-ray absorption fine structure spectroscopy (XAFS) was used to study the oxidation states of Re and Tc incorporated into the corroded steel coupon surfaces. X-ray fluorescence maps showed that the corroded coupons contain localized regions enriched in Re or Tc. The Re L3 near edge XAFS results for the coupons reacted with Re-spiked waters were consistent with nearly all of the sorbed Re being present as perrhenate and not significantly reduced to Re(IV). Linear combination fits of the extended XAFS signals for the perrhenate and ReIVO2 standards indicate that Re sorbed to the steel coupons corroded in simulated J-13 (a relatively dilute Na-HCO3-CO3 groundwater) and even more dilute waters consists of a maximum of 5 and 10% Re(IV), respectively. The fluorescence results also showed that the Re concentrations increased with increasing time of exposure to the X-ray beam, which suggests that the perrhenate ions are only weakly bonded to the matrix of the corrosion product. In contrast to the Re results, the Tc K edge XAFS results for the coupons reacted in 99Tc-spiked waters indicate that most of the sorbed Tc had been reduced to Tc(IV). The shape of the near edge and extended fine structure is similar to the Tc(IV)-hydrous ferric oxide (HFO) and not the TcO2 . nH2O standard. Differences were noted in the XAFS results for steel coupons reacted with waters spiked with 0.001 vs. 0.1 mmol/L 99Tc in that much more of the sorbed Tc from 0.001 mmol/L 99Tc experiments was in the form of pertechnetate. Comparison of the XAFS results for coupons reacted with 0.001 mmol/L 99Tc

  15. Photo-Darkening Kinetics and Structural Anisotropic Modifications in the Chalcogenide Glass Arsenic Trisulfide: a Study of Kinetic X-Ray Absorption Spectroscopy

    Lee, Jay Min

    1990-08-01

    The purpose of the study is to investigate the mechanisms involved with photo-induced atomic structural modifications in the chalcogenide glass As_2 S_3. This glass exhibits the reversible effects of photo-darkening followed by thermal bleaching. We observed the time behavior of photo-induced properties under the influence of linearly polarized band -gap light. In a macroscopic optical investigation, we monitor optical changes in the photo-darkening process, and in a local structural probe we study kinetic (or time -resolved dispersive) x-ray absorption spectroscopy. Our observations center on kinetic phenomena and structural modifications induced by polarized excitation of lone-pair orbitals in the chalcogenide glass. Experimental results include the following observations: (i) The polarity of the optically induced anisotropy is critically dependent on the intensity and the polarization of the band-gap irradiation beam. (ii) The near edge peak height in x-ray absorption spectra shows subtle but sensitive change during the photo-darkening process. (iii) Photon intensity dependent dichroic kinetics reflect a connection between the optically probed macroscopic property and the x-ray probed local anisotropic structure. Analysis of the x-ray absorption results includes a computer simulation of the polarized absorption spectra. These results suggest that specific structural units tend to orient themselves with respect to the photon polarization. A substantial part of the analysis involves a major effort in dealing with the x-ray kinetic data manipulation and the experimental difficulties caused by a synchrotron instability problem. Based on our observations, we propose a possible mechanism for the observed photo-structural modifications. Through a model of computer relaxed photo-darkening kinetics, we support the notion that a twisting of a specific intermediate range order structure is responsible for local directional variations and global network distortions. In the

  16. Partially Absorbed Comptonization Spectrum from the Nearly Edge-on Source X 1822-371

    Iaria, R; Burderi, L; Robba, N R

    2001-01-01

    We report the results of a spectral analysis over the range 0.1-200 keV performed on the dipping source X 1822-371 observed by BeppoSAX. We find the best fit to the continuum using a partially covered Comptonization model, due to scattering off soft seed photons by electrons at a temperature of ~4.8 keV, without the presence of any soft blackbody emission. The equivalent hydrogen column obtained for the absorbed component is ~4.5 10^{22} cm^{-2}, an order of magnitude larger than the Galactic absorption for this source, and the covering fraction is ~71%. Because the inclination angle of X 1822-371 to the line of sight is ~85^\\circ, this model gives a reasonable scenario for the source: the Comptonized spectrum could come from an extended accretion disk corona (ADC), probably the only region that can be directly observed due to the high inclination. The excess of matter producing the partial covering could be close to the equatorial plane of the system, above the outer disk, occulting the emission from the inn...

  17. Study on accumulation mechanism of cadmium in rice (oriza sativa L.) by micro-XRF imaging and x-ray absorption fine structure analysis utilizing synchrotron radiation

    This paper reports on the distribution of Cd and essential elements in the stems of rice plants, 'Nipponbare' and 'Milyang 23', measured by synchrotron radiation micro-XRF imaging. X-ray absorption near edge structure (XANES) analysis was applied to estimate the chemical forms of Cd in the roots, stems and leaves, aiming to reveal the mechanisms of Cd transport in rice. The results show that the Cd concentration of 'Nipponbare' was found to be higher than that of 'Milyang 23' at the root, although there was no significant difference between these two cultivars at the shoot. In addition, the distribution of Cd and the essential elements inside the plant were clearly revealed by micro-XRF imaging. It was found that Cd was also localized to the bundle. The Cd K-edge XANES analysis indicated that Cd was bound to sulfur in the root for both rice plants. Furthermore, the content of Cd combining with S (Cd-S) in the stem of 'Nipponbare' became 1.5 times higher after exposing to Cd for a long time, while only a slight change in the stem of 'Milyang 23' was found. In contrast with the stem, the leaf of 'Nipponbare' contained a lower Cd-S content than that of the control after a long-term exposure, while that of 'Milyang 23' became higher. In conclusion, the difference in the chemical form of Cd at the shoots affected the different accumulation behaviors of Cd between 'Nipponbare' and 'Milyang 23'. (author)

  18. An in situ sample environment reaction cell for spatially resolved x-ray absorption spectroscopy studies of powders and small structured reactors

    Zhang, Chu; Gustafson, Johan; Merte, Lindsay R.; Evertsson, Jonas [Division of Synchrotron Radiation Research, Lund University, Box 118, SE-221 00 Lund (Sweden); Norén, Katarina; Carlson, Stefan; Svensson, Håkan [MAX IV Laboratory, Lund University, Box 118, SE-221 00 Lund (Sweden); Carlsson, Per-Anders [Competence Centre for Catalysis, Chalmers University of Technology, SE-412 96 Göteborg (Sweden)

    2015-03-15

    An easy-to-use sample environment reaction cell for X-ray based in situ studies of powders and small structured samples, e.g., powder, pellet, and monolith catalysts, is described. The design of the cell allows for flexible use of appropriate X-ray transparent windows, shielding the sample from ambient conditions, such that incident X-ray energies as low as 3 keV can be used. Thus, in situ X-ray absorption spectroscopy (XAS) measurements in either transmission or fluorescence mode are facilitated. Total gas flows up to about 500 ml{sub n}/min can be fed while the sample temperature is accurately controlled (at least) in the range of 25–500 °C. The gas feed is composed by a versatile gas-mixing system and the effluent gas flow composition is monitored with mass spectrometry (MS). These systems are described briefly. Results from simultaneous XAS/MS measurements during oxidation of carbon monoxide over a 4% Pt/Al{sub 2}O{sub 3} powder catalyst are used to illustrate the system performance in terms of transmission XAS. Also, 2.2% Pd/Al{sub 2}O{sub 3} and 2% Ag − Al{sub 2}O{sub 3} powder catalysts have been used to demonstrate X-ray absorption near-edge structure (XANES) spectroscopy in fluorescence mode. Further, a 2% Pt/Al{sub 2}O{sub 3} monolith catalyst was used ex situ for transmission XANES. The reaction cell opens for facile studies of structure-function relationships for model as well as realistic catalysts both in the form of powders, small pellets, and coated or extruded monoliths at near realistic conditions. The applicability of the cell for X-ray diffraction measurements is discussed.

  19. Romania's road to Euro zone. From structural balance to structural balance corrected for absorption

    Aura-Gabriela SOCOL

    2013-02-01

    Full Text Available The sovereign-debt crisis in the European Union has determined the necessity to reform the signal indicators for the analysis of the public finances' sustainability. In this context, many of the developing/emerging countries consider that the informational value provided by the structural budget balance indicator is insufficient, especially during the periods characterized by absorption. The present study suggests the transition from classical structural budget balance (CAB in the structural balance corrected for absorption (CAAB and supports the use of an improved indicator of the structural budget balance with a superior informational relevance for the macro-economic policies decision makers. Based on the economic literature we will demonstrate that the structural budget balance indicator should be improved, in order to also take into consideration the deviation of the current account balance from its sustainable level, particularly in the stage of the economic cycle characterized by high absorption.

  20. A New Look at the Structural Properties of Trisodium Uranate Na3UO4

    SMITH ANNA; RAISON Philippe; MARTEL LAURA; PRIEUR DAMIEN; CHARPENTIER THIBAULT; Wallez, G.; Suard, E.; Scheinost, Andreas; HENNIG Christoph; Martin, P.; Kvashnina, Kristina; CHEETHAM A.k.; KONINGS Rudy

    2014-01-01

    The crystal structure of trisodium uranate, which forms following the interaction between sodium and hyperstoichiometric urania, has been solved for the first time using powder X-ray and neutron diffraction, X-ray absorption near-edge structure spectroscopy, and solid-state 23Na multiquantum magic angle spinning nuclear magnetic resonance. The compound, isostructural with Na3BiO4, has monoclinic symmetry, in space group P2/c. Moreover, it has been shown that this structure can accommodate som...

  1. Application of relativistic scattering theory of x rays to diffraction anomalous fine structure in Cu

    Arola, E.; Strange, Paul

    1998-01-01

    We apply our recent first-principles formalism of magnetic scattering of circularly polarized x rays to a single Cu crystal. We demonstrate the ability of our formalism to interpret the crystalline environment related near-edge fine structure features in the resonant x-ray scattering spectra at the Cu K absorption edge. We find good agreement between the computed and measured diffraction anomalous fine structure features of the x-ray scattering spectra.

  2. Experimental and theoretical study of electronic structure of lutetium bi-phthalocyanine

    Bidermane, Ieva; Lüder, Johann; Boudet, S.; Zhang, T.; Ahmadi, S.; Grazioli, C.; Bouvet, M.; Rusz, Jan; Sanyal, Biplab; Eriksson, Olle; Brena, Barbara; Puglia, Carla; Witkowski, N.

    2013-01-01

    Using Near Edge X-Ray Absorption Fine Structure (NEXAFS) Spectroscopy, the thickness dependent formation of Lutetium Phthalocyanine (LuPc2) films on a stepped passivated Si(100)2x1 reconstructed surface was studied. Density functional theory (DFT) calculations were employed to gain detailed insights into the electronic structure. Photoelectron spectroscopy measurements have not revealed any noticeable interaction of LuPc2 with the H-passivated Si surface. The presented study can be considered...

  3. Quasar absorption spectra and the structure of the universe

    Analysis of the spacing between absorption-line systems in quasar spectra and comparison against deep optical survey data for the separation between superclusters of galaxies indicates that the absorption originates in the superclusters. Supported by analogous data on the absorbing gas in the galactic and Magellanic Cloud halos, this inference sharpens theoretical conclusions as to the properties of superclusters. The problem of the unidentified quasar absorption lines is discussed

  4. Quasar absorption spectra and the structure of the universe

    Doroshkevich, A.G.

    1984-03-01

    Analysis of the spacing between absorption-line systems in quasar spectra and comparison against deep optical survey data for the separation between superclusters of galaxies indicates that the absorption originates in the superclusters. Supported by analogous data on the absorbing gas in the galactic and Magellanic Cloud halos, this inference sharpens theoretical conclusions as to the properties of superclusters. The problem of the unidentified quasar absorption lines is discussed.

  5. Structural studies using X-ray absorption and scattering techniques

    The thesis presents extended X-ray absorption fine structure, EXAFS, and large angle X-ray scattering, LAXS, techniques; instrumentation, data collection and reduction, and applications. These techniques have been used to determine the structures of magnesium halides and organomagnesium halides in diethyl ether and tetrahydrofuran solution. The iodides were used for the LAXS measurements and Br K edge EXAFS data were collected for the corresponding bromides. Two different complexes are present in the diethyl ether solution of magnesium iodide; a polymeric chain-type structure where magnesium is tetrahedrally coordinated, as well as dimeric complex with octahedrally coordinated magnesium. Solvated MgI+ is the dominating species in tetrahydrofuran solution. The organomagnesium halides are present in diethyl ether solution as both solvated monomeric and dimeric complexes. Magnesium coordinates a halide ion, an alkyl or aryl group and four solvent molecules octahedrally in the monomeric complex. In the dimeric complex magnesium is octahedrally coordinated by two bridging halide ions, an alkyl or aryl group and three solvent molecules. The distribution of monomeric and dimeric complexes in various solutions are given by a dimerisation constant, Kdl. The results indicate that the Schlenk equilibrium is present in these solutions, however, in an extended form. In diethyl ether solution, where MgX2 does not dissociate, no MgX2 complex and thereby no Schlenk equilibrium has been observed. In tetrahydrofuran solution MgI2 has dissociated into mainly MgI+ and I-. This indicates that the concentration of MgI2 is low and that the Schlenk equilibrium should be expanded even further to include the dissociation equilibrium of the magnesium halide. In the thesis Fe K edge EXAFS data collected for the semireduced form of protein A of methane monooxygenase from Methylococcus capsulatus, are also presented. (139 refs.)

  6. Utilization of synchrotron radiation in analytical chemistry. Soft X-ray emission and absorption spectroscopy

    Synchrotron soft X-ray spectroscopy includes three major types of spectroscopy such as X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES), and X-ray photoelectron spectroscopy (XPS). This paper takes up XAS and XES of soft X-rays, and briefly describes the principle. XAS is roughly classified into XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure), and XANES is mainly used in the analysis based on XAS of soft X-rays. As the examples of the latest soft X-ray analyses, the following are introduced: (1) bandgap of boron implantation diamond and the local structure of boron, (2) catalytic sites in solid fuel cell carbon electrode, and (3) soft X-ray analysis under atmospheric pressure. (A.O.)

  7. Absorption spectra of quasars and the structure of the Universe

    The analysis of the distribution of the distances between the systems of absorption lines in the quasars' spectra and the comparison of this distribution with the distribution of the distances between superclusters in the deep optical surveys are carried out. It is shown that the systems of absorption lines are connected with superclusters of galaxies. The comparison of the absorbing gas parameters with the data for coronae of the Galaxy and of the Magellanic Clouds confirms this connection and permits to revise conclusions of the theory on the properties of superclusters. The problem of unidentified absorption lines in the quasars spectra is discussed

  8. Crystal and local atomic structure of Co-doped MgFeBO_4 warwickites

    Kazak, N. V.; Platunov, M. S.; Knyazev, Yu. V.; Ivanova, N. B.; Zubavichus, Y. V.; Veligzhanin, A. A.; Vasiliev, A. D.; Bezmaternykh, L. N.; Bayukov, O. A.; Arauzo, A.; Bartolomé, J.; Lamonova, K. V.; Ovchinnikov, S. G.

    2014-01-01

    Single crystalline MgFeBO_4, Mg_0.5Co_0.5FeBO_4 and CoFeBO_4 have been grown by the flux method. The samples have been characterized by X-ray spectral analysis, X-ray diffraction and X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra have been measured at the Fe andCoK-edges over a wide temperature range (6.5 - 300 K). The composition, the charge state and local environment of both Fe and Co atoms have b...

  9. Multiple-scattering approach to the x-ray-absorption spectra of perovskite-type compounds

    Kitamura, Michihide; Muramatsu, Shinji; Sugiura, Chikara

    1988-04-01

    The metal K x-ray-absorption near-edge structure has been calculated for the first time from a multiple-scattering formalism for the perovskite-type compounds KMnF3, KFeF3, KCoF3, KNiF3, and KZnF3. The calculation includes the effects of a core hole and of Madelung corrections for crystal potentials. It is shown that the results including the lifetime-broadening effect are in good agreement with the experiment of Shulman et al.

  10. X-ray absorption study of tribofilms from ZDDP and overbased salicylate detergents

    Yong Wan; M. Kasrai; G.M. Bancroft

    2009-01-01

    The interaction of overbased salicylate detergents with zinc dialkyldithiophosphates (ZDDP) and its effect on the formation of tribofilms under boundary lubrication have been studied by means of X-ray absorption near-edge structure spectroscopy. The results show that addition of metallic detergents to neat ZDDP results in the change of surface chemistry of the tribofilm formed from neat ZDDP. Calcium from detergents is digested in the tribofilm. For the high overbased detergents, the deposit of overbasing agent CaCO3 in the tribofilm is also observed along with the formation of calcium phosphate in tribofilms.

  11. Applications of EXAFS to studies of the structure of amorphous and microcrystalline solids

    The subject is discussed under the headings: introduction; outline of underlying theory (relationship of EXAFS and elastic scattering techniques; limitations of EXAFS); examples of experimental studies (EXAFS studies of metallic glasses; alkali and alkaline earth cations in amorphous oxides; precipitation in Cu-Al alloys; structure of bimetallic clusters in Pt-Ir catalysts); x-ray absorption near-edge spectra (XANES). (U.K.)

  12. Operando X-ray absorption and infrared fuel cell spectroscopy

    Lewis, Emily A.; Kendrick, Ian; Jia, Qingying; Grice, Corey; Segre, Carlo U.; Smotkin, Eugene S. (NuVant); (IIT); (NEU)

    2011-11-17

    A polymer electrolyte fuel cell enables operando X-ray absorption and infrared spectroscopy of the membrane electrode assembly catalytic layer with flowing fuel and air streams at controlled temperature. Time-dependent X-ray absorption near edge structure spectra of the Pt and Ni edge of Pt based catalysts of an air-breathing cathode show that catalyst restructuring, after a potential step, has time constants from minutes to hours. The infrared Stark tuning plots of CO adsorbed on Pt at 100, 200, 300 and 400 mV vs. hydrogen reference electrode were obtained. The Stark tuning plots of CO adsorbed at 400 mV exhibit a precipitous drop in frequency coincident with the adsorption potential. The turn-down potential decreases relative to the adsorption potential and is approximately constant after 300 mV. These Stark tuning characteristics are attributed to potential dependent adsorption site selection by CO and competitive adsorption processes.

  13. X-ray-absorption spectra in KrF2 and FeCl2: theory

    Theoretical x-ray-absorption near-edge structure (XANES) and extended x-ray-absorption fine structure (EXAFS) of molecular and crystalline KrF2 and gas-phase FeCl2 have been obtained by using a modified Xα scattered-wave procedure. EXAFS calculations are made in the single-scattering approximation. Effects of multiple scattering near the absorption edge have been investigated by comparing predicted XANES and EXAFS spectra in the near-edge region. Two exchange-correlation potentials, Xα and energy-dependent Dirac (ED), were incorporated in the EXAFS calculations. Comparison between experimental and theoretical results confirm that the ED potential is more valid for EXAFS spectra. Molecular field splitting as well as resonance coupling were demonstrated by comparing the theoretical XANES of the isolated KrF2 molecule to that of FeCl2. The single-particle XANES calculation of molecular FeCl2 is compared with the experimental crystalline FeCl2 results of Stern. 37 references, 8 figures, 1 table

  14. Sulfur K-edge X-ray absorption spectroscopy of petroleum asphaltenes and model compounds

    The utility of sulfur K-edge X-ray absorption spectroscopy for the determination and quantification of sulfur forms in petroleum asphaltenes has been investigated. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra were obtained for a selected group of model compounds and for several petroleum asphaltene samples. For the model compounds the sulfur XANES was found to vary widely from compound to compound and to provide a fingerprint for the form of sulfur involved. The use of third derivatives of the spectra enabled discrimination of mixtures of sulfidic and thiophenic model compounds and allowed approximate quantification of the amount of each component in the mixtures and in the asphaltene samples. These results represent the first demonstration that nonvolatile sulfur forms can be distinguished and approximately quantified by direct measurement

  15. X-ray absorption studies of battery materials

    McBreen, J.

    1996-10-01

    X-ray absorption spectroscopy (XAS) is ideal for {ital in}{ital situ} studies of battery materials because both the probe and signal are penetrating x rays. The advantage of XAS being element specific permits investigation of the environment of a constituent element in a composite material. This makes it very powerful for studying electrode additives and corrosion of individual components of complex metal hydride alloys. The near edge part of the spectrum (XANES) provides information on oxidation state and site symmetry of the excited atom. This is particularly useful in study of corrosion and oxidation changes in cathode materials during charge/discharge cycle. Extended fine structure (EXAFS) gives structural information. Thus the technique provides both chemical and structural information. Since XAS probes only short range order, it can be applied to study of amorphous electrode materials and electrolytes. This paper discusses advantages and limitations of the method, as well as some experimental aspects.

  16. Structure and Mass Absorption of Hypothetical Terrestrial Black Holes

    VanDevender, A. P.; VanDevender, J. Pace

    2011-01-01

    The prospect of mini black holes, either primordial or in planned experiments at the Large Hadron Collider, interacting with the earth motivate us to examine how they may be detected and the scope of their impact on the earth. We propose that the more massive of these objects may gravitationally bind matter without significant absorption. Since the wave functions of gravitationally bound atoms orbiting a black hole are analogous to those of electrons around a nucleus, we call such an object t...

  17. Linear optical absorption spectra of mesoscopic structures in intense THz fields: Free-particle properties

    Johnsen, Kristinn; Jauho, Antti-Pekka

    1998-01-01

    We theoretically study the effect of THz radiation on the linear optical absorption spectra of semiconductor structures. A general theoretical framework, based on nonequilibrium Green functions, is formulated and applied to the calculation of linear optical absorption spectrum for several nonequi...

  18. Quantum chemistry studies of the O K-edge X-ray absorption in WO3 and AWO3

    Bocharov, Dmitry; Kuzmin, Alexei; Purans, Juris; Zhukovskii, Yuri

    2010-01-01

    In this work we present an interpretation of experimental O K-edge x-ray absorption near edge structure (XANES) in perovskite-type WO3 and AWO3 compounds (A = H and Na) using three different first principles approaches: (i) full-multiple-scattering (FMS) formalism (the real-space FEFF code), (ii) hybrid density functional theory (DFT) method with partial incorporation of exact Hartree-Fock exchange using formalism of the linear combination of atomic orbitals (LCAO) as implemented in the CRYST...

  19. Electronic structure, bonding, charge distribution, and x-ray absorption spectra of the (001) surfaces of fluorapatite and hydroxyapatite from first principles

    Rulis, Paul; Yao, Hongzhi; Ouyang, Lizhi; Ching, W. Y.

    2007-12-01

    Fluorapatite (FAP) and hydroxyapatite (HAP) are two very important bioceramic crystals. The (001) surfaces of FAP and HAP crystals are studied by ab initio density functional calculations using a supercell slab geometry. It is shown that in both crystals, the O-terminated (001) surface is more stable with calculated surface energies of 0.865 and 0.871J/m2 for FAP and HAP, respectively. In FAP, the two surfaces are symmetric. In HAP, the orientation of the OH group along the c axis reduces the symmetry such that the top and bottom surfaces are no longer symmetric. It is revealed that the atoms near the surface and subsurface are significantly relaxed especially in the case of HAP. The largest relaxations occurred via the lateral movements of the O ions at the subsurface level. The electronic structures of the surface models in the form of layer-by-layer resolved partial density of states for all the atoms show systematic variation from the surface region toward the bulk region. The calculated Mulliken effective charge on each type of atom and the bond order values between cations (Ca, P) and anions (O, F) show different charge transfers and bond strength variations from the bulk crystal values. Electron charge density calculations show that the surfaces of both FAP and HAP crystals are mostly positively charged due to the presence of Ca ions at the surface. The positively charged surfaces have implications for the absorption on apatite surfaces of water and other organic molecules in an aqueous environment which are an important part of its bioactivity. The x-ray absorption near-edge structure (XANES) spectra ( Ca-K , O-K , F-K , P-K , and P-L3 edges) of both the surface models and the bulk crystals are calculated and compared. The calculations use a supercell approach which takes into account the electron-core-hole interaction. It is shown that the site-specific XANES spectra show significant differences between atoms near the surface and in the bulk and are very

  20. The local structure and optical absorption characteristic investigation on Fe doped TiO2 nanoparticles

    Zhao, Tianxing; Huang, Junheng; He, Jinfu; Liu, Qinghua; Pan, Zhiyun; Wu, Ziyu

    2014-01-01

    The local structures and optical absorption characteristic of Fe doped TiO2 nanoparticles synthesized by the sol-gel method were characterized by X-ray Diffraction (XRD), X-ray absorption fine structure spectroscopy (XAFS) and UV-Vis absorption spectroscopy (UV-Vis). XRD patterns show that all Fe-doped TiO2 samples have the characteristic anatase structure. Accurate Fe and Ti K-edge EXAFS analysis further reveal that all Fe atoms replace Ti atoms in the anatase lattice. The analysis of UV-Vis data shows a red shift to the visible range. According to the above results, we claim that substitutional Fe atoms lead to the formation of structural defects and new intermediate energy levels appear, narrowing the band gap and extending the optical absorption edge towards the visible region.

  1. EXAFS (Extended X-Ray Absorption Fine Structure): theory and applications

    EXAFS (Extended X-Ray Absorption Fine Structure) is introduced in a general way and the qualities of such a techique are shown. Some examples of applications of EXAFS in several branches of science are presented. (L.C.)

  2. XANES and IR spectroscopy study of the electronic structure and chemical composition of porous silicon on n- and p-type substrates

    Lenshin, A. S., E-mail: lenshinas@phys.vsu.ru; Kashkarov, V. M.; Seredin, P. V. [Voronezh State University (Russian Federation); Spivak, Yu. M.; Moshnikov, V. A. [LETI St. Petersburg State Electrotechnical University (Russian Federation)

    2011-09-15

    The differences in the electronic structure and composition of porous silicon samples obtained under identical conditions of electrochemical etching on the most commonly used n- and p-type substrates with different conductivities are demonstrated by X-ray absorption near-edge spectroscopy (XANES) and Fourier transform IR spectroscopy (FTIR) methods. It is shown that significantly higher oxidation and saturation with hydrogen is observed for the porous layer on n-type substrates.

  3. XANES and IR spectroscopy study of the electronic structure and chemical composition of porous silicon on n- and p-type substrates

    The differences in the electronic structure and composition of porous silicon samples obtained under identical conditions of electrochemical etching on the most commonly used n- and p-type substrates with different conductivities are demonstrated by X-ray absorption near-edge spectroscopy (XANES) and Fourier transform IR spectroscopy (FTIR) methods. It is shown that significantly higher oxidation and saturation with hydrogen is observed for the porous layer on n-type substrates.

  4. Communication: Systematic shifts of the lowest unoccupied molecular orbital peak in x-ray absorption for a series of 3d metal porphyrins

    García-Lastra, J. M.; Cook, P. L.; Himpsel, F.J.; Rubio, A.

    2010-01-01

    Porphyrins are widely used as dye molecules in solar cells. Knowing the energies of their frontier orbitals is crucial for optimizing the energy level structure of solar cells. We use near edge x-ray absorption fine structure (NEXAFS) spectroscopy to obtain the energy of the lowest unoccupied molecular orbital (LUMO) with respect to the N1s core level of the molecule. A systematic energy shift of the N1s to LUMO transition is found along a series of 3d metal octaethylporphyrins and explained ...

  5. Electron-Vibration Structure of Absorption Spectra of Resazurine

    T.N. Sakun

    2011-01-01

    Full Text Available In the work the experimental and theoretical investigation of the spectral characteristics of a resazurin molecule are carried out. Comparison of results of experimental and theoretical researches has allowed showing, that the spectrum of absorption in the visible region is formed by quantum transitions between electronic states of the molecule, and also by the electron-vibration interaction. In the work the method of reception of theoretical results with the control of molecule symmetry is offered. It has allowed to receive the completely coordinated theoretical and experimental results both by position and by size of the extinction factor and to find out the nature of all quantum transitions and oscillatory frequencies. It is shown, that strips of absorption in the visible region of the spectrum are formed at participation of the totally symmetrical vibrations of the molecule among which the greatest participation stand out vibrations with frequencies in the region of 478 cm – 1, 1467 cm – 1, and also by group of oscillatory frequencies in the region of 1800-2000 cm – 1 which were less than found theoretically for the basic state of the molecule because the degree of loosening of the bonds that responsible for specified vibrations, increases at excitation of the molecule.

  6. Metal incorporated M-DNA: structure, magnetism, optical absorption

    Mizoguchi, Kenji

    2011-09-01

    DNA is an interesting material from the viewpoint of the materials science. This paper discusses the electronic states of the metal incorporated M-DNA complexes with several species of metal ions. M-DNA prepared by the ordinary methanol precipitation technique has been investigated with ESR, STM and optical absorption, and concluded that the metal ion hydrated with several water molecules locates in between the bases of a base pair and that the divalent metal ions are incorporated into DNA in place of two Na cations as the counter ion for PO-4in the DNA backbones. Only in Fe-DNA, it was confirmed that the Fe2+ in the FeCl2 aqueous solution reacts with DNA to form Fe-DNA complex with Fe3+, where the charge would transfer to DNA. Within 30 min, the hydrolysis of Fe2+ to form Fe3+O(OH) did not occur in the FeCl2 aqueous solution at room temperature. The optical absorption spectra of Fe-DNA is similar to that for FeCl3 with the ionic character, but definitely differs from that of Fe3+O(OH) with the covalent bonding nature, suggesting the ionic character of Fe3+ in Fe-DNA. Finally, the possible two kinds of electronic states for Zn-DNA with different bonding nature will be discussed in relation to the recent report on Zn-DNA.

  7. Radio Structures of Compact Quasars with Broad Absorption Lines

    Kunert-Bajraszewska, Magdalena; Gawroński, Marcin P.

    2010-05-01

    Broad absorption lines (BALs), seen in a small fraction of both the radio-quiet and radio-loud quasar populations, are probably caused by the outflow of gas with high velocities and are part of the accretion process. The presence of BALs is due to a geometrical effect and/or it is connected with the quasar evolution. Using the final release of FIRST survey combined with a catalog of BAL QSOs from SDSS/DR3, we have constructed a new sample of compact radio-loud BAL QSOs, which constitutes the majority of radio-loud BAL QSOs. The main goal of this project is to study the origin of BALs by analysis of the BAL QSOs radio morphology, orientation, and jet evolution using the European VLBI Network (EVN) at 1.6 GHz and the Very Long Baseline Array (VLBA) at 5 and 8.4 GHz.

  8. Study on the electronic structures and absorption spectra for sheelite- and the sheelite-like structures lead tungstate crystal

    The electronic structures and absorption spectra of perfect crystals and crystals containing lead vacancy Vpb2- for both sheelite(PbWO4) and sheelite-like(Pb7.5W8O32) structures have been calculated using density functional theory with the lattice structure optimized. The optical properties of lead tungstate exhibit anisotropy. Numerical calculation shows that the absorption spectra of the sheelite structure crystal containing Vpb2- exhibit additional absorption bands in the visible and near ultra-violet ranges. However, this is not the case for other structures of the PWO crystals such as the sheelite structure crystal without lead vacancy and the sheelite-like structure crystal with or without lead vacancy

  9. Analysis of local structure and chemical state by using in-house XAFS

    X-ray absorption near-edge structure (XANES) is useful to analysis of the valence of selected element or the symmetry surrounding it. XAFS measurements by using in-house X-ray absorption spectrometer have high potential to apply to analyze the local structure or the electronic states of materials, it is not so popular recently with increasing the use of synchrotron facilities has become prevailing into various fields. The capacity of the in-house XAFS is shown in this paper along with some examples of experiments by a spectrometer with X-ray generator of only 3 kW. (author)

  10. Study on the improved structure of dye-sensitized solar cells for enhancing light absorption

    LIU Yong; SHEN Hui; DENG Youjun

    2007-01-01

    The absorption coefncients of N719 or N3 dyes at the longer wavelength region (>600 nm)are not enough to catch photons efficiently,but the solar spectrum has a large photon flux in the wavelength region between 500 and 1,000 nm,so it is desirable to enhance the absorption of light by the dye-sensitized solar cells(DSSC)to achieve higher efficiencies.To solve this problem,an improved structure Of DSSC for enhancing light absorption is introduced in this paper, and I-V characteristics of DSSC are measured to illustrate the enhancement of the light absorption and efficiency.As a result,the improved DSSC exhibits higher light absorption and solar-to-electric conversion efficiency than traditional DSSC.

  11. Anomalous absorption of bulk shear sagittal acoustic waves in a layered structure with viscous fluid

    Gramotnev, D K; Nieminen, T A; Gramotnev, Dmitri K.; Mather, Melissa L.; Nieminen, Timo A.

    2003-01-01

    It is demonstrated theoretically that the absorptivity of bulk shear sagittal waves by an ultra-thin layer of viscous fluid between two different elastic media has a strong maximum (in some cases as good as 100%) at an optimal layer thickness. This thickness is usually much smaller than the penetration depths and lengths of transverse and longitudinal waves in the fluid. The angular dependencies of the absorptivity are demonstrated to have significant and unusual structure near critical angles of incidence. The effect of non-Newtonian properties and non-uniformities of the fluid layer on the absorptivity is also investigated. In particular, it is shown that the absorption in a thin layer of viscous fluid is much more sensitive to non-zero relaxation time(s) in the fluid layer than the absorption at an isolated solid-fluid interface.

  12. The nature of arsenic in uranium mill tailings by X-ray absorption spectroscopy

    In order to understand the evolving world of environmental issues, the ability to characterize and predict the stability and bioavailability of heavy metal contaminants in mine waste is becoming increasingly more important. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopies were used to characterize a series of synthetic and natural samples associated with mine tailings processing. XANES was shown to be excellent as a tool to rapidly differentiate oxidation states of arsenic within the samples. The EXAFS spectra provided information on the mineralogy of the precipitated raffinate and tailings and showed that these samples are composed of a mixture of amorphous ferric arsenates, adsorbed arsenates and a mixture of other poorly ordered arsenates. (authors)

  13. New theoretical investigation resolving discrepancies of atomic form factors and attenuation coefficients in the near-edge soft x-ray regime

    Full text: Reliable knowledge of the complex X-ray form factor and the photoelectric attenuation coefficient is required for crystallography, medical diagnosis, refractive index studies and XAFS. Discrepancies between currently used theoretical approaches of 200% exist for numerous elements from 1 keV to 3 keV X-ray energies. This work derives new theoretical results in near-edge soft X-ray regions and improves upon the theoretical uncertainty in these regions by a factor of 10. This work was also reported in J.Phys.Chem.Ref.Data (2000)

  14. Study of UCI4 structure and absorption spectra

    The two halides ThCl4 and ThBr4, which are isomorphic at room temperature, have a comparable behaviour when the temperature is lowered. The resonance line of the halogen isotope is split into two lines at a temperature of 96 K for ThBr4 and 70 K for ThCl4. These data confirm the observation of a phase transition first detected by Raman Spectroscopy. Though UCl4 is isomorphic with ThCl4 and ThBr4 at room temperature, it behaves differently versus temperature. The experiments performed from 4,2K to room temperature showed there is only one site for the halogen. UCl4 does not present a phase transition. Once some informations have been gathered on the matrices, optical absorption spectra on ThCl4:U4+ and UCl4 monocristals have been recorded in the visible and infrared ranges at 4,2 K and at room temperature. These spectra have many vibronic lines. To give a first interpretation of the pure electronic lines of U4+-ThCl4 and UCl4 studies on U4+-ThBr4 have been used, in particular the zero phonon lines which correspond to a Dsub(2d) symmetry, have been selected in comparison with the work done on ThBr4:U4+. The energy levels in ThCl4:U4+ and UCl4 have been fitted to the electrostatic parameters F0, F2,F4, F6, the spin orbit parameter, the configuration interaction parameters α, β, γ and crystal field parameters B02, B04, B44, B06, B46

  15. Plasmonic structure integrated single-photon detector configurations to improve absorptance and polarization contrast

    Mária Csete; Gábor Szekeres; András Szenes; Anikó Szalai; Gábor Szabó

    2014-01-01

    Configurations capable of maximizing both the absorption component of system detection efficiency and the achievable polarization contrast were determined for 1550 nm polarized light illumination of different plasmonic structure integrated superconducting nanowire single-photon detectors (SNSPDs) consisting of p = 264 nm and P = 792 nm periodic niobium nitride (NbN) patterns on silica substrate. Global effective NbN absorptance maxima appear in case of p/s-polarized light illumination in S/P-...

  16. Wide-band underwater acoustic absorption based on locally resonant unit and interpenetrating network structure

    The interpenetrating network structure provides an interesting avenue to novel materials. Locally resonant phononic crystal (LRPC) exhibits excellent sound attenuation performance based on the periodical arrangement of sound wave scatters. Combining the LRPC concept and interpenetrating network glassy structure, this paper has developed a new material which can achieve a wide band underwater strong acoustic absorption. Underwater absorption coefficients of different samples were measured by the pulse tube. Measurement results show that the new material possesses excellent underwater acoustic effects in a wide frequency range. Moreover, in order to investigate impacts of locally resonant units, some defects are introduced into the sample. The experimental result and the theoretical calculation both show that locally resonant units being connected to a network structure play an important role in achieving a wide band strong acoustic absorption. (condensed matter: structure, thermal and mechanical properties)

  17. The Effect of Heat on Structural Characteristics and Water Absorption Behavior of Agave Fibers

    Saikia, Dip

    2008-04-01

    The structural characteristics and water absorptions behavior agave fibers were investigated over a range of temperature by using XRD, IR, TG and gravimetric methods. Three distinct thermal processes were observed during heating the fiber in the temperature range 310-760 K in air, oxygen and nitrogen invariably. The cellulose structures of the fibers were unaffected on heating up to 450 K. The samples showed thermal decomposition processes beyond 500 K. Fibers displayed a two-stage diffusion behavior. The structural parameters and kinetic of water absorption of the fibers at specific temperatures were analyzed.

  18. Syntheses and absorption-structure relationships of some new photosensitizer cyanine dyes

    H A Shindy; A I M Koraiem

    2002-04-01

    New biheterocyclic compound was synthesized as starting material to prepare new photosensitizers mono-, tri-, substituted tri-, azadimethine and mixed cyanine dyes. Absorption-structure relationship of the synthesized cyanine dyes were determined by studying their electronic spectral behaviour in ethanol. The structure of the compounds were identified by elemental analysis, IR and 1H NMR spectral data.

  19. Polyphenols from Bee Pollen: Structure, Absorption, Metabolism and Biological Activity

    Anna Rzepecka-Stojko

    2015-12-01

    Full Text Available Bee pollen constitutes a natural source of antioxidants such as phenolic acids and flavonoids, which are responsible for its biological activity. Research has indicated the correlation between dietary polyphenols and cardioprotective, hepatoprotective, anti-inflammatory, antibacterial, anticancerogenic, immunostimulating, antianaemic effects, as well as their beneficial influence on osseous tissue. The beneficial effects of bee pollen on health result from the presence of phenolic acids and flavonoids which possess anti-inflammatory properties, phytosterol and linolenic acid which play an anticancerogenic role, and polysaccharides which stimulate immunological activity. Polyphenols are absorbed in the alimentary tract, metabolised by CYP450 enzymes, and excreted with urine and faeces. Flavonoids and phenolic acids are characterised by high antioxidative potential, which is closely related to their chemical structure. The high antioxidant potential of phenolic acids is due to the presence and location of hydroxyl groups, a carboxyl group in the immediate vicinity of ortho-diphenolic substituents, and the ethylene group between the phenyl ring and the carboxyl group. As regards flavonoids, essential structural elements are hydroxyl groups at the C5 and C7 positions in the A ring, and at the C3′ and C4′ positions in the B ring, and a hydroxyl group at the C3 position in the C ring. Furthermore, both, the double bond between C2 and C3, and a ketone group at the C4 position in the C ring enhance the antioxidative potential of these compounds. Polyphenols have an ideal chemical structure for scavenging free radicals and for creating chelates with metal ions, which makes them effective antioxidants in vivo.

  20. Acoustic contributions of a sound absorbing blanket placed in a double panel structure: Absorption Versus Transmission

    Doutres, Olivier; 10.1121/1.3458845

    2010-01-01

    The objective of this paper is to propose a simple tool to estimate the absorption vs. transmission loss contributions of a multilayered blanket unbounded in a double panel structure and thus guide its optimization. The normal incidence airborne sound transmission loss of the double panel structure, without structure-borne connections, is written in terms of three main contributions; (i) sound transmission loss of the panels, (ii) sound transmission loss of the blanket and (iii) sound absorption due to multiple reflections inside the cavity. The method is applied to four different blankets frequently used in automotive and aeronautic applications: a non-symmetric multilayer made of a screen in sandwich between two porous layers and three symmetric porous layers having different pore geometries. It is shown that the absorption behavior of the blanket controls the acoustic behavior of the treatment at low and medium frequencies and its transmission loss at high frequencies. Acoustic treatment having poor sound ...

  1. The effects of processing variables on the energy absorption of composite crash structures

    Turner, Thomas A.

    2004-01-01

    Environmental pressures are driving automotive manufacturers towards light weight cost efficient structures. Composite materials have been shown to display high specific energy absorption levels thus offering opportunities for mass reduction over conventional steel structures. Whilst composites display these specific advantages, the mechanisms by which energy is absorbed are more complex and are preventing widespread acceptance of composite structures. This work aims to further scientific und...

  2. X-ray absorption study of intermediate valence in Sm1-xGdxS alloys

    X-ray absorption near edge structure (XANES) measurements above LH edge of Sm are employed to study the intermediate valence in Sm1-xGdxS(0.05 ≤ x ≤ 0.30) alloys. The split white lines at the LH edge of Sm are used to determine the average valence of SM in these alloys. The internal chemical pressure generated by substitution of smaller trivalent cation, Gd, for Sm drives the latter to a higher valence. Sm valence increases smoothly first and then undergoes an abrupt increment at a critical concentration of 16 at.% of Gd. At concentration of Gd higher than 16 at. % the increase in Sm valence is smooth and small. The data for Sm average valence for Sm1-xGdxS alloys obtained by LH absorption edges shows fair agreement with other techniques

  3. [Study on removing the lamp spectrum structure in differential optical absorption spectroscopy].

    Qu, Xiao-ying; Li, Yu-jin

    2010-11-01

    Differential optical absorption spectroscopy (DOAS) technique has been used to measure trace gases in the atmosphere by their strongly structured absorption of radiation in the UV and visible spectral range, and nowadays this technique has been widely utilized to measure trace polluted gases in the atmosphere e.g. SO2, NO2, O3, HCHO, etc. However, there exists lamp (xenon lamp or deuteriumlamp) spectrum structure in the measured band (300-700 nm) of the absorption spectra of atmosphere, which badly impacts on precision of retrieving the concentration of trace gases in the atmosphere. People home and abroad generally employ two ways to handle this problem, one is segmenting band retrieving method, another is remedial retrieving method. In the present paper, a new retrieving method to deal with this trouble is introduced. The authors used moving-window average smoothing method to obtain the slow part of the absorption spectra of atmosphere, then achieved the lamp (xenon lamp in the paper) spectrum structure in the measured band of the absorption spectra of atmosphere. The authors analyzed and retrieved the measured spectrum of the atmosphere, and the result is better than the forenamed ways. Chi-square of residuum is 2.995 x 10(-4), and this method was proved to be able to avoid shortcoming of choosing narrowband and disadvantage of discovering the new component of atmosphere in retrieving the concentration of air pollutants and measuring the air pollutants. PMID:21284148

  4. Invisible structures in the X-ray absorption spectra of actinides

    Highlights: • The X-ray absorption spectra of actinides are discussed with an emphasis atomic multiplet theory, charge transfer theory and crystal field theory. • Resonant inelastic X-ray emission spectra (RIXS) reveal many new features in the X-ray absorption spectra of actinides. • The new range of RIXS beamlines will become an important tool in the determination of the electronic structure of actinides. - Abstract: The X-ray absorption spectra of actinides are discussed with an emphasis on the fundamental effects that influence their spectral shape, including atomic multiplet theory, charge transfer theory and crystal field theory. Many actinide spectra consist of a single peak and it is shown that the use of resonant inelastic X-ray emission spectra (RIXS) has the potential to reveal many new features in the X-ray absorption spectra of actinides. The new range of RIXS beamlines will allow the determination of new structures in the X-ray absorption spectra that have been hitherto invisible. This has the potential to become an important tool in the determination of the electronic structure of actinides

  5. X-ray absorption study of the CuO2 plane in Nd2-xCexCuO4-δ

    The local structure of the CuO2 planes in Nd2-xCexCuO4-δ (x=0, 0.15; δ∼0.01) has been examined by temperature-dependent Cu K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. Three different Cu-O distances can be extracted up to at least 100 K, indicating that the atomic structure of the CuO2 planes deviates from the T' structure much more than it was expected. Positions of the displaced O1 atoms for x=0.15 were obtained from comparative analysis of the experimental and calculated polarized Cu K-edge X-ray absorption near-edge structure, taking into account many-body excitations in the CuO2 planes

  6. The impurity optical absorption and structure of conduction band in 6H-SiC

    The investigation of absorption spectra in n-type nitrogen doped 6H-SiC crystals from the near infrared up to fundamental band region at polarization of electric field (E) of the light wave relatively the optical axis (C) for E parallel to C and E perpendicular to C has been carried out. It is for the first time that at E parallel to C a slight absorption band with maximum at 2.85 eV has been investigated. All absorption bands observed were caused by photoionization of donors (nitrogen) with electron transition in to above-lying minima of the conduction band situated at different critical points of the Brillouin zone. The analysis of data obtained and experimental data available on the photoionization of nitrogen, alongside with theoretical data on the structure of the conduction band make it possible to propose the structure and symmetry of additional extrema in Brillouin zone for 6H-SiC

  7. Contrasting phytoplankton community structure and associated light absorption characteristics of the western Bay of Bengal

    Pandi, Sudarsana Rao; Kiran, Rayaprolu; Sarma, Nittala S.; Srikanth, A. S.; Sarma, V. V. S. S.; Krishna, M. S.; Bandyopadhyay, D.; Prasad, V. R.; Acharyya, T.; Reddy, K. G.

    2014-01-01

    Absorption spectra, particulate pigments, and hydrochemical constituents were measured in the western Bay of Bengal (BoB) during July-August 2010 when influence of river discharge is at peak. Chromophoric dissolved organic matter (CDOM) absorption coefficient (aCDOM(440)) displayed a significant inverse linear relationship with salinity in the surface waters implying conservative mixing of marine and terrestrial end members. The northern part of the study area is influenced by discharge from the river Ganga and a dominant terrestrial CDOM signal is seen. The southern part receives discharge from peninsular rivers with corresponding signals of higher CDOM than the linear model would indicate and higher UV-specific absorption coefficient (SUVA) indicating more aged and humified DOM. Lower contribution of CDOM to total non-water absorption and higher phytoplankton biomass (chlorophyll a absorption coefficient, aph(440)) but lower chlorophyll a specific phytoplankton absorption coefficient (a{ph/*}(440)) characterize the northern part, compared to the southern part. Chlorophyll b had a distinct linear relationship with chlorophyll a in the latter. The size index (SI) indicated dominance of microphytoplankton in the northern and nano and picophytoplankton in the southern parts. Chlorophyll a is significantly related to a{ph/*}(440) by an inverse power model in the northern part but by an inverse linear model in the southern part. Our study suggests that knowledge of the phytoplankton community structure is essential to improve chlorophyll a algorithm in the coastal Bay of Bengal.

  8. Extended X-ray absorption fine structure investigation of nitrogen stabilized expanded austenite

    Oddershede, Jette; Christiansen, Thomas; Ståhl, Kenny;

    2010-01-01

    As-delivered austenitic stainless steel and nitrogen stabilized expanded austenite, both fully nitrided and denitrided (in H2), were investigated with Cr, Fe and Ni extended X-ray absorption fine structure. The data shows pronounced short-range ordering of Cr and N. For the denitrided specimen the...

  9. Generalized Ramsauer-Townsend effect in extended x-ray-absorption fine structure

    Theoretical backscattering amplitude and phase functions, B(k) and phi(k), used in extended x-ray-absorption fine structure (EXAFS) studies show strong features in their k dependence which can be identified as a ''generalized Ramsauer-Townsend effect.'' This effect is studied in detail for elements with atomic number 78≤Z≤90

  10. Characterization of green copper phase pigments in Egyptian artifacts with X-ray absorption spectroscopy and principal components analysis

    The characterization of materials in historical artifacts can contribute significantly to their preservation and understanding; however, sampling and characterization are ideally performed using non-destructive approaches. The analysis of green pigments from Egyptian artifacts presents a further challenge as responses to laboratory based techniques have proven unsuccessful in many cases. An alternative approach is the use of non-destructive X-ray absorption near-edge structure spectroscopy, which was performed on a reference set of copper-containing green minerals and other compounds. Data projection using principal component analysis was used to explore the spectral data structures and to illustrate the relationship between the spectra and copper speciation, resulting in a calibration or training set of the reference materials used. Data from the training set were compared with samples from Egyptian artifacts. The combination of X-ray absorption spectroscopy with principal components analysis provides a novel approach in archeometry and the characterization of objects of cultural heritage