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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. 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)

  10. 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

  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 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.

  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 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.

  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. 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)

  11. 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...

  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. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  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. 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.

  14. 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.

  15. 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.

  16. 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)

  17. 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

  18. 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.

  19. 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.

  20. 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)

  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

    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.; 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.

  1. 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 ...

  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. 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.

  10. 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

  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

    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)

  20. 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})

  1. 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)

  2. 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)

  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. 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...

  16. 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

  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. 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.

  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. 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 ...

  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. 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

  4. [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

  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

  11. Numerical and experimental study of the effect of microslits on the normal absorption of structural metamaterials

    Ruiz, H.; Claeys, C. C.; Deckers, E.; Desmet, W.

    2016-03-01

    Resonant metamaterials are emerging as novel concepts to reduce noise levels in targeted frequency zones, so-called stop bands. The metamaterial concept improves acoustic behaviour through an increase of the insertion loss. This paper concerns a first investigation on the absorption capabilities of a resonant metamaterial when thermo-viscous effects are incorporated via the addition of microslits. In a previous work, a resonant metamaterial was obtained through the inclusion of resonating structures into cavities of an open honeycomb assembly. In this study, the air gap of the honeycomb structure is reduced so as to provide viscous losses for the travelling waves. Considering that the created resonant structures with open cavities are rigid, an equivalent fluid model is used to calculate the acoustical properties of a so called microslit metamaterial. It is demonstrated that the unit cell structure can be divided into parallel elements for which the acoustic impedance can be computed via the transfer matrix approach TMM in parallel and series. Likewise, it is shown that the structural response can be predicted by FEM models allowing studying the structural effects separately from the viscous-thermal effects predicted by the equivalent fluid model. Moreover, the combined effect of both approaches is shown experimentally where it is observed that: (i) The absorption of the resonant metamaterial is increased by the addition of microslits, (ii) the modes of the test sample appear as small peaks on the absorption curve of the microslit metamaterial, (iii) the structural modes are grouped below and above the stop band and, (iv) the resonant structures do not lead to additional absorption in the stop band region. Analytical models are compared to experimental measurements to validate the models and to show the potential of this material assembly.

  12. A new type of artificial structure to achieve broadband omnidirectional acoustic absorption

    Zheng, L.-Y.

    2013-10-18

    We present a design for a two-dimensional omnidirectional acoustic absorber that can achieve 98.6% absorption of acoustic waves in water, forming an effective acoustic black hole. This artificial black hole consists of an absorptive core coated with layers of periodically distributed polymer cylinders embedded in water. Effective medium theory describes the response of the coating layers to the acoustic waves. The polymer parameters can be adjusted, allowing practical fabrication of the absorber. Since the proposed structure does not rely on resonances, it is applicable to broad bandwidths. The design might be extended to a variety of applications.

  13. A new type of artificial structure to achieve broadband omnidirectional acoustic absorption

    Li-Yang Zheng

    2013-10-01

    Full Text Available We present a design for a two-dimensional omnidirectional acoustic absorber that can achieve 98.6% absorption of acoustic waves in water, forming an effective acoustic black hole. This artificial black hole consists of an absorptive core coated with layers of periodically distributed polymer cylinders embedded in water. Effective medium theory describes the response of the coating layers to the acoustic waves. The polymer parameters can be adjusted, allowing practical fabrication of the absorber. Since the proposed structure does not rely on resonances, it is applicable to broad bandwidths. The design might be extended to a variety of applications.

  14. Structural and electrical properties of In-implanted Ge

    Feng, R., E-mail: ruixing.feng@anu.edu.au; Kremer, F.; Mirzaei, S.; Medling, S. A.; Ridgway, M. C. [Department of Electronic Materials Engineering, Research School of Physics and Engineering, Australian National University, Canberra, Australian Capital Territory 0200 (Australia); Sprouster, D. J. [Nuclear Science and Technology Department, Brookhaven National Laboratory, Upton, New York 11973 (United States); Decoster, S. [Instituut voor Kern-en Stralingsfysica, KU Leuven, 3001 Leuven (Belgium); Glover, C. J. [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia); Russo, S. P. [Department of Applied Physics, School of Applied Sciences, RMIT University, Melbourne 3001 (Australia)

    2015-10-28

    We report on the effects of dopant concentration on the structural and electrical properties of In-implanted Ge. For In concentrations of ≤ 0.2 at. %, extended x-ray absorption fine structure and x-ray absorption near-edge structure measurements demonstrate that all In atoms occupy a substitutional lattice site while metallic In precipitates are apparent in transmission electron micrographs for In concentrations ≥0.6 at. %. Evidence of the formation of In-vacancy complexes deduced from extended x-ray absorption fine structure measurements is complimented by density functional theory simulations. Hall effect measurements of the conductivity, carrier density, and carrier mobility are then correlated with the substitutional In fraction.

  15. Possible atomic structures responsible for the sub-bandgap absorption of chalcogen-hyperdoped silicon

    Single-crystal silicon was hyperdoped with sulfur, selenium, and tellurium using ion implantation and nanosecond laser melting. The hyperdoping of such chalcogen elements led to strong and wide sub-bandgap light absorption. Annealing the hyperdoped silicon, even at low temperatures (such as 200–400 °C), led to attenuation of the sub-bandgap absorption. To explain the attenuation process, we modeled it as chemical decomposition reaction from an optically absorbing structure to a non-absorbing structure. Attenuation of the experimental absorption coefficient was fit using the Arrhenius equation. From the fitted data, we extracted the reaction activation energies of S-, Se-, and T-hyperdoped silicon as 0.338 ± 0.029 eV, 0.471 ± 0.040 eV, and 0.357 ± 0.028 eV, respectively. We discuss these activation energies in terms of the bond energies of chalcogen–Si metastable bonds, and suggest that several high-energy interstitial sites, rather than substitutional sites, are candidates for the atomic structures that are responsible for the strong sub-bandgap absorption of chalcogen hyperdoped silicon

  16. Possible atomic structures responsible for the sub-bandgap absorption of chalcogen-hyperdoped silicon

    Wang, Ke-Fan [Institute for Computational Materials Science, School of Physics and Electronics, Henan University, Kaifeng 475004 (China); Key Laboratory of Semiconductor Materials Science, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083 (China); Shao, Hezhu [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Liu, Kong; Qu, Shengchun, E-mail: qsc@semi.ac.cn, E-mail: wangyx@henu.edu.cn; Wang, Zhanguo [Key Laboratory of Semiconductor Materials Science, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083 (China); Wang, Yuanxu, E-mail: qsc@semi.ac.cn, E-mail: wangyx@henu.edu.cn [Institute for Computational Materials Science, School of Physics and Electronics, Henan University, Kaifeng 475004 (China)

    2015-09-14

    Single-crystal silicon was hyperdoped with sulfur, selenium, and tellurium using ion implantation and nanosecond laser melting. The hyperdoping of such chalcogen elements led to strong and wide sub-bandgap light absorption. Annealing the hyperdoped silicon, even at low temperatures (such as 200–400 °C), led to attenuation of the sub-bandgap absorption. To explain the attenuation process, we modeled it as chemical decomposition reaction from an optically absorbing structure to a non-absorbing structure. Attenuation of the experimental absorption coefficient was fit using the Arrhenius equation. From the fitted data, we extracted the reaction activation energies of S-, Se-, and T-hyperdoped silicon as 0.338 ± 0.029 eV, 0.471 ± 0.040 eV, and 0.357 ± 0.028 eV, respectively. We discuss these activation energies in terms of the bond energies of chalcogen–Si metastable bonds, and suggest that several high-energy interstitial sites, rather than substitutional sites, are candidates for the atomic structures that are responsible for the strong sub-bandgap absorption of chalcogen hyperdoped silicon.

  17. Research on EM pulse protection property of plasma-microwave absorptive material-plasma sandwich structure

    2010-01-01

    A plasma-microwave absorptive material (MAM)-plasma sandwich structure is presented to protect the electronic device against high power electromagnetic pulse. The model of electromagnetic wave reflected by and transmitting through the structure is established. Based on the characteristic parameters of plasma generated by discharge and usual MAM, the electromagnetic transmissive properties of the sandwich structure are investigated by the method of finite difference in time domain. The results indicate that in a rather broad frequency range, the electromagnetic attenuations by the structure are obviously better than the sum of attenuations resulted from plasma and MAM respectively. The models and results presented are instructive for electromagnetic pulse protection.

  18. Atomic structure of Mn-rich nanocolumns probed by x-ray absorption spectroscopy

    Rovezzi, M.; Devillers, T.; Arras, E.; d'Acapito, F.; Barski, A.; Jamet, M.; Pochet, P.

    2008-06-01

    In this letter, we have used the extended x-ray-absorption fine-structure (EXAFS) technique to investigate the structure of Mn-rich self-organized nanocolumns grown by low temperature molecular beam epitaxy. The EXAFS analysis has shown that Mn-rich nanocolumns exhibit a complex local structure that cannot be described by a simple substitutional model. Additional interatomic distances had to be considered in the EXAFS model which are in excellent agreement with the structure of a Ge-3Mn building block tetrahedron of Ge3Mn5.

  19. Electronic structure of the organic semiconductor copper tetraphenylporphyrin (CuTPP)

    The electronic structure of thin films of the organic semiconductor copper tetraphenylporphyrin (CuTPP) has been studied using synchrotron radiation-excited resonant soft X-ray emission spectroscopy (RSXE), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, and X-ray photoemission spectroscopy (XPS). The C and N partial density of states for both the valence and conduction band electronic structure has been determined, while XPS was used to provide information on the chemical composition and the oxidation states of the copper. Good agreement was found between the experimental measurements of the valence and conduction bands and the results of density functional theory calculations.

  20. Energy structure and absorption spectra of colloidal CdS nanocrystals in gelatin matrix

    Korolev, N. V.; Smirnov, M. S.; Ovchinnikov, O. V.; Shatskikh, T. S.

    2015-04-01

    We investigate the energy structure of colloidal CdS nanocrystals by measuring the UV-vis absorption spectra. Nanocrystals were synthesized by sol-gel method in a gelatin matrix in the size range from 2.5 to 3.9 (±0.2) nm. In order to interpret the UV-vis absorption spectra we calculate the energy spectrum of electron quasi-stationary states using the model of open nanocrystal as well as the hole stationary spectrum in a two-band approach. It is shown that the main contribution to the absorption spectrum is made by interband transitions 1S3/2→1Se and 1P3/2→1Pe, and its shape is determined by the size distribution of nanoparticles. For this system the estimated values of the effective masses of the heavy hole and light hole are 1.44m0 and 0.28m0, respectively.

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

    Csete, Maria; Szenes, Andras; Szalai, Aniko; Szabo, Gabor

    2014-01-01

    Configurations capable of maximizing both absorptance and 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 NbN absorptance maxima appear in case of p/s-polarized light illumination in S/P-orientation (gamma=90 azimuthal angle) and the highest polarization contrast is attained in S-orientation of all devices. Common nanophotonical origin of absorptance enhancement is collective resonance on nano-cavity-gratings with different profiles, which is promoted by coupling between localized modes in quarter wavelength MIM nano-cavities and laterally synchronized Brewster-Zenneck-type surface waves in integrated SNSPDs possessing a three-quarter-wavelength-scaled periodicity. The spectral sensitivity and dispersion characteristics reveal that device design specific optimal configurations...

  2. Theory of x-ray absorption: a Bethe-Salpeter approach

    Shirley, Eric L.

    2002-03-01

    First-principles calculations of x-ray absorption spectra of solids is a well-established field. The best known and most used treatments are probably those based on real-space multiple-scattering theory. Such Green's Function approaches are particular useful for incorporating electron damping effects (self-energy effects) that broaden spectral features at high electron kinetic energy. Near-edge structure can also be treated, and it can also be treated in super-cell calculations. In this talk, I will present results obtained using an alternative, reciprocal-space approach based on solving the Bethe-Salpeter equation, which is related to the Bethe-Salpeter method used to treat valence excitation signatures in optical absorption spectra. This amounts to solving the coupling equations of motion for the electron-core hole pair that is produced by x-ray absorption. Mutual localization of the electron and core hole in real space is realized by permitting the electron to exist as a wave-packet of Bloch states peaked near the core hole, governed by the excitation process and ensuing electron core-hole attraction. Because this approach permits state-of-the-art electron band structure calculations to be used to evaluate the electron wave function, this approach is particularly well suited for detailed near-edge structure. In presenting the approach and results obtained, particular attention is focused on (1) the role of the electron-hole interaction, (2) the need to deal with core-hole screening accurately, (3) the evaluation of accurate transition matrix elements between core states and Bloch states, and (4) computational-time scaling issues. This work has been done in collaboration with J.A. Soininen, J.J. Rehr, E.K. Chang, and others. This work was supported in part by the U.S. Deparment of Energy (DOE) Grant DE-FG03-97ER45623 and facilitated by the DOE Computational Materials Science Network (CMSN).

  3. A new analysis of fine-structure constant measurements and modelling errors from quasar absorption lines

    Wilczynska, Michael R.; Webb, John K.; King, Julian A.; Murphy, Michael T.; Bainbridge, Matthew B.; Flambaum, Victor V.

    2015-12-01

    We present an analysis of 23 absorption systems along the lines of sight towards 18 quasars in the redshift range of 0.4 ≤ zabs ≤ 2.3 observed on the Very Large Telescope (VLT) using the Ultraviolet and Visual Echelle Spectrograph (UVES). Considering both statistical and systematic error contributions we find a robust estimate of the weighted mean deviation of the fine-structure constant from its current, laboratory value of Δα/α = (0.22 ± 0.23) × 10-5, consistent with the dipole variation reported in Webb et al. and King et al. This paper also examines modelling methodologies and systematic effects. In particular, we focus on the consequences of fitting quasar absorption systems with too few absorbing components and of selectively fitting only the stronger components in an absorption complex. We show that using insufficient continuum regions around an absorption complex causes a significant increase in the scatter of a sample of Δα/α measurements, thus unnecessarily reducing the overall precision. We further show that fitting absorption systems with too few velocity components also results in a significant increase in the scatter of Δα/α measurements, and in addition causes Δα/α error estimates to be systematically underestimated. These results thus identify some of the potential pitfalls in analysis techniques and provide a guide for future analyses.

  4. The Effects of MNC Parent Effort and Social Structure on Subsidiary Absorptive Capacity

    Schleimer, Stephanie Christine; Pedersen, Torben

    2014-01-01

    Although the literature provides ample evidence that the global transfer and local implementation of knowledge represents a key advantage for multinational corporations (MNCs), we lack comparable understanding as to whether knowledge-creating MNC parents can actively expand the absorptive capacity...... of their subsidiaries. Using a teacher–student lens, this study examines the combined impact of specific structural mechanisms and motivational processes by MNC parents on the ability of 216 subsidiaries to absorb parent-initiated marketing strategies. The findings reveal that MNC parents can indeed...... cultivate subsidiaries’ ability to appropriate marketing knowledge through a combination of adopting specific social structures and investing in particular efforts. However, the effect of social structure on subsidiary absorptive capacity is indirect, and accounted for by the parents’ intensity of effort....

  5. Instruments and practices concerning the absorption and use of structural and cohesion funds in Romania

    Ani MATEI

    2015-06-01

    Full Text Available In view to improve the competitiveness and economic growth as well as to diminish the gaps between Romania and the EU developed states, the Structural and Cohesion Funds represent an outstanding source of investment. The operationalisation of the structural instruments is paramount for a sustainable socio- economic development. After Romania joined the European Union, during the programming period 2007-2013, Romania has been allocated approximately 19.21 billion euro from Structural and Cohesion Funds and Romania’s contribution (including private sources to complement the EU investments was forecasted to reach at least 5.6 billion euro. The absorption of Structural and Cohesion Funds has represented one of the major priorities of the Government of Romania since the approval of the Operational Programmes, Romania being among the first Member States whose Operational Programmes were approved by the European Commission. The difficulties faced since the very beginning of implementatio n have overlapped with the effects of the economic and financial crisis, thus the absorption rate was under the previous expectations. The management authorities and the beneficiaries have also faced multiple and complex problems. The current paper aims to present the institutional mechanisms, instruments and practices for the absorption and use of structural funds in Romania, focusing on the main problems and challenges during the implementation process.

  6. Soft x-ray absorption spectroscopy on Co doped ZnO: structural distortions and electronic structure

    Kowalik, I. A.; Guziewicz, E.; Godlewski, M.; Arvanitis, D.

    2016-05-01

    We present soft x-ray absorption spectra from a series of Co doped ZnO films. We discuss systematic variations of the Co L-edge white line intensity and multiplet features for this series of samples. We document sizeable differences in the electronic state of the Co ionic cores, as well as in the local environment of the host lattice atoms, characterised by means of x-ray absorption spectra at the O K-edge and Zn L-edges. Model calculations allow to correlate the observed effects to small structural distortions of the ZnO lattice.

  7. Traces of Defects in the Electronic Structure of Porous Ni-Ti Alloys

    O.M.Ozkendir; E.Cengiz; E.T(i)rasoglu; Mehmet Kaya; I.H.Karahan; N.Orhan

    2013-01-01

    The electronic structures of Ni-Ti shape-memory alloy samples were investigated by X-ray absorption fine structure (XAFS) spectroscopy both experimentally and theoretically.In the experimental section,the samples were measured at low temperature to determine the persistent traces of both preheating process and atomic concentration effects on the crystal and electronic structure by X-ray absorption near-edge structure (XANES)spectroscopy.As a second step,the extended-X-ray absorption fine structure (EXAFS) calculations,which are based on different choices of one electron potentials according to Ti coordinations by using the real space multiple scattering method FEFF 8.2 code,were performed.The crystallographic and electronic structures of the porous Ni-Ti alloys were tested at various temperatures ranging from 5 to 1323 K.

  8. Soft X-ray absorption analysis in the multi-purpose beamline BL10 at New SUBARU (3). Liquid organic compounds and engine oil

    Soft X-ray absorption spectra of liquid unsaturated aliphatic compounds and engine oil samples were measured at a multi-purpose beamline BL10 in NewSUBARU. Liquid samples were casted on clean gold substrates and their X-ray absorption near-edge structure (XANES) were successfully measured with a total electron yield (TEY) method under the vacuum of 10-5 Pa. In the unsaturated aliphatic compounds, π* and σ* peaks which depend on the length of alkyl substituents can be clearly observed. In the deteriorated engine oil samples, anti-oxidizing agents disappeared and alkyl chains were formed by opening the C=C double bonds. It is therefore confirmed that liquid organic samples can be analyzed by soft X-ray absorption spectroscopy in BL10/NS. (author)

  9. Local structure analysis of magnetic transparent conducting films by x-ray spectroscopy

    We prepared Mn-doped indium-tin oxide (ITO) films on glass substrates by radio-frequency magnetron sputtering and investigated local structures surrounding Mn ions in the films by x-ray absorption spectroscopy. The Fourier transform of the extended x-ray absorption fine structure (EXAFS) spectrum indicated that the Mn ions preferably substitute the In ions at the b sites of the In2O3 lattice. According to the threshold energy obtained from the inflection point of the edge in the x-ray absorption near edge structure (XANES) spectrum, the valence of the Mn ions was evaluated to range from  +2 to  +3. These x-ray absorption spectroscopic data are useful for revealing the origin of the magnetism of the Mn-doped ITO films. (paper)

  10. Interstellar X-Ray Absorption Spectroscopy of the Crab Pulsar with the LETGS

    Paerels, Frits; Weisskopf, Martin C.; Tennant, Allyn F.; ODell, Stephen L.; Swartz, Douglas A.; Kahn, Steven M.; Behar, Ehud; Becker, Werner; Whitaker, Ann F. (Technical Monitor)

    2001-01-01

    We study the interstellar X-ray absorption along the line of sight to the Crab Pulsar. The Crab was observed with the Low Energy Transmission Grating Spectrometer on the Chandra X-ray Observatory, and the pulsar, a point source, produces a full resolution spectrum. The continuum spectrum appears smooth, and we compare its parameters with other measurements of the pulsar spectrum. The spectrum clearly shows absorption edges due to interstellar Ne, Fe, and O. The O edge shows spectral structure that is probably due to O bound in molecules or dust. We search for near-edge structure (EXAFS) in the O absorption spectrum. The Fe L absorption spectrum is largely due to a set of unresolved discrete n=2-3 transitions in neutral or near-neutral Fe, and we analyze it using a new set of dedicated atomic structure calculations, which provide absolute cross sections. In addition to being interesting in its own right, the ISM absorption needs to be understood in quantitative detail in order to derive spectroscopic constraints on possible soft thermal radiation from the pulsar.

  11. Synthesis, crystal structures, and two-photon absorption of a series of cyanoacetic acid triphenylamine derivatives.

    Hao, Fuying; Li, Dandan; Zhang, Qiong; Li, Shengli; Zhang, Shengyi; Zhou, Hongping; Wu, Jieying; Tian, Yupeng

    2015-11-01

    A specific series of chromophores (CN1, CN2, CN3, and CN4) have been synthesized, in which contained a triphenylamine moiety as the electron donor (D), a cyanoacetic acid moiety as the electron acceptor (A), vinylene or phenylethyne as the π-bridge, and ethyoxyl groups as auxiliary electron donor (D') to construct the D-π-A or D'-D-π-A molecular configuration. Photophysical properties of them were systematically investigated. These results show that the chromophores display a solvatochromism (blue shift) and large Stokes shifts for their absorption bands with increasing polarity of the solvent. Furthermore, the chromophore CN4 shows the strongest intensity of two-photon excited fluorescence and largest two-photon absorption cross section (2783 GM) in the near infrared region. Finally, the connections between the structures and properties are systematically investigated relying on the information from linear and nonlinear optical properties, crytsal structures and quantum chemical calculation. PMID:26119354

  12. Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework

    Coriani, Sonia; Koch, Henrik

    2015-11-01

    We present a simple scheme to compute X-ray absorption spectra (e.g., near-edge absorption fine structure) and core ionisation energies within coupled cluster linear response theory. The approach exploits the so-called core-valence separation to effectively reduce the excitation space to processes involving at least one core orbital, and it can be easily implemented within any pre-existing coupled cluster code for low energy states. We further develop a perturbation correction that incorporates the effect of the excluded part of the excitation space. The correction is shown to be highly accurate. Test results are presented for a set of molecular systems for which well converged results in full space could be generated at the coupled cluster singles and doubles level of theory only, but the scheme is straightforwardly generalizable to all members of the coupled cluster hierarchy of approximations, including CC3.

  13. X-ray absorption for the study of warm dense matter

    Levy, A; Dorchies, F; Harmand, M; Fourment, C; Hulin, S; Peyrusse, O; Santos, J J [Universite de Bordeaux - CNRS - CEA, CELIA, Talence, F-33405 France (France); Antici, P; Audebert, P; Fuchs, J; Lancia, L; Mancic, A; Nakatsutsumi, M [LULI, Ecole Polytechnique, 91128 Palaiseau Cedex (France); Mazevet, S; Recoules, V; Renaudin, P [CEA-DIF, 91680 Bruyeres-le-Chatel (France); Fourmaux, S [INRS-Energie et Materiaux, 1650 bd. L Boulet, J3X1S2 Varennes, Quebec (Canada)

    2009-12-15

    A time-resolved ultrafast x-ray spectrometer is developed in order to extract the x-ray absorption near-edge spectroscopy (XANES) structure of an Al sample in the warm dense matter regime. In this context, an intense, broadband, short (ps) x-ray source based on the M-band emission from high-Z plasmas is optimized to maximize the photon flux around the Al K-edge. An experiment is reported, devoted to probe a solid Al foil isochorically heated by laser-produced protons up to 3 eV. The experimental x-ray spectra lead to an estimation of the electron temperature with an accuracy of 15%. In good agreement with two different theoretical approaches, the observed progressive smoothing of the XANES structures is clearly related to a significant loss of ion-ion correlation.

  14. Electronic topological transition in zinc under pressure: An x-ray absorption spectroscopy study

    Zinc metal has been studied at high pressure using x-ray absorption spectroscopy. In order to investigate the role of the different degrees of hydrostaticity on the occurrence of structural anomalies following the electronic topological transition, two pressure transmitting media have been used. Results show that the electronic topological transition, if it exists, does not induce an anomaly in the local environment of compressed Zn as a function of hydrostatic pressure and any anomaly must be related to a loss of hydrostaticity of the pressure transmitting medium. The near-edge structures of the spectra, sensitive to variations in the electronic density of states above the Fermi level, do not show any evidence of electronic transition whatever pressure transmitting medium is used

  15. A feasibility study on oxidation state of arsenic in cut tobacco, mainstream cigarette smoke and cigarette ash by X-ray absorption spectroscopy

    This work describes the application of synchrotron-based X-ray Absorption Near-Edge Structure spectroscopy to study the oxidation state of arsenic in cigarette mainstream smoke, cut tobacco and cigarette ash. The level of arsenic in the total particulate matter of the smoke is approximately 1 ppm for the standard research reference cigarette 2R4F and its replacement 3R4F. Smoke particulate samples collected by a conventional glass-fiber membrane (commercially known as Cambridge filter pad) and a jet-impaction method were analyzed and compared. In addition smoke particulate samples were aged either at ambient temperature or at 195 K. X-ray Absorption Near-Edge Structure spectroscopy results revealed that the cut tobacco powder and cigarette ash contained almost exclusively AsV. The smoke particulate samples however contained a mixture of AsIII and AsV. The AsV in the smoke particulate was reduced to AsIII upon aging. Stabilizing the smoke particulate matter at 195 K by solid CO2 slowed down this aging reaction and revealed a higher percentage of AsV. This behavior is consistent with the redox properties of the arsenic species and the smoke particulate matrix.

  16. Forest of absorption lines in quasar spectra and the structure of the Universe

    The problem of the ''forest'' at absorption lines in the spectra of quasars is discussed in the frame of the A-theory of formation and evolution of the structure of the Universe. It is assumed that the hidden mass is connected with neutrino like particles (possibly instable) with a rest mass of the order of 60-100 eV. An observational test for the hypothesis proposed is discussed

  17. The 16th International Conference on X-ray Absorption Fine Structure (XAFS16)

    Grunwaldt, J.-D.; Hagelstein, M.; Rothe, J.

    2016-05-01

    This preface of the proceedings volume of the 16th International Conference on X- ray Absorption Fine Structure (XAFS16) gives a glance on the five days of cutting-edge X-ray science which were held in Karlsruhe, Germany, August 23 - 28, 2015. In addition, several satellite meetings took place in Hamburg, Berlin and Stuttgart, a Sino-German workshop, three data analysis tutorials as well as special symposia on industrial catalysis and XFELs were held at the conference venue.

  18. X-ray absorption study of the CuO sub 2 plane in Nd sub 2 sub - sub x Ce sub x CuO sub 4 sub - subdelta

    Ignatov, A Y; Chernov, V A; Ivanov, A A

    2000-01-01

    The local structure of the CuO sub 2 planes in Nd sub 2 sub - sub x Ce sub x CuO sub 4 sub - subdelta (x=0, 0.15; delta approx 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 CuO sub 2 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 CuO sub 2 planes.

  19. A new analysis of fine-structure constant measurements and modelling errors from quasar absorption lines

    Wilczynska, Michael R; King, Julian A; Murphy, Michael T; Bainbridge, Matthew B; Flambaum, Victor V

    2015-01-01

    We present an analysis of 23 absorption systems along the lines of sight towards 18 quasars in the redshift range of $0.4 \\leq z_{abs} \\leq 2.3$ observed on the Very Large Telescope (VLT) using the Ultraviolet and Visual Echelle Spectrograph (UVES). Considering both statistical and systematic error contributions we find a robust estimate of the weighted mean deviation of the fine-structure constant from its current, laboratory value of $\\Delta\\alpha/\\alpha=\\left(0.22\\pm0.23\\right)\\times10^{-5}$, consistent with the dipole variation reported in Webb et al. and King et al. This paper also examines modelling methodologies and systematic effects. In particular we focus on the consequences of fitting quasar absorption systems with too few absorbing components and of selectively fitting only the stronger components in an absorption complex. We show that using insufficient continuum regions around an absorption complex causes a significant increase in the scatter of a sample of $\\Delta\\alpha/\\alpha$ measurements, th...

  20. Atomic calculations and search for variation of the fine-structure constant in quasar absorption spectra

    Dzuba, V. A.; Flambaum, V. V.

    A brief review of the search for variation of the fine structure constant in quasar absorption spectra is presented. Special consideration is given to the role of atomic calculations in the analysis of the observed data. A range of methods which allow to perform calculations for atoms or ions with different electron structure and which cover practically all periodic table of elements is discussed. Critical compilation of the results of the calculations as well as a review of the most recent results of the analysis are presented.

  1. Atomic calculations and search for variation of the fine structure constant in quasar absorption spectra

    Dzuba, V A

    2008-01-01

    A brief review of the search for variation of the fine structure constant in quasar absorption spectra is presented. Special consideration is given to the role of atomic calculations in the analysis of the observed data. A range of methods which allow to perform calculations for atoms or ions with different electron structure and which cover practically all periodic table of elements is discussed. Critical compilation of the results of the calculations as well as a review of the most recent results of the analysis are presented.

  2. Multi-state analysis of the OCS ultraviolet absorption including vibrational structure

    Schmidt, Johan Albrecht; Johnson, Matthew Stanley; McBane, G.C.; Schinke, R.

    2012-01-01

    The first absorption band of OCS (carbonyl sulfide) is analyzed using potential energy surfaces and transition dipole moment functions of the lowest four singlet and the lowest four triplet states. Excitation of the 2 (1)A' state is predominant except at very low photon energies. It is shown that...... the vibrational structures in the center of the band are due to excitation of the 2 (3)A'' triplet state, whereas the structures at very low energies are caused by bending excitation in the potential wells of states 2 (1)A' and 1 (1)A''....

  3. Ab initio simulation of effects of structural singularities in aerogel absorption potential

    In the present work simulation of Van der Waals potential between helium atom and part of silica aerogel strand by means of ab initio methods was performed. Cell with alpha quartz structure was used as building block of aerogel strand, because it is the most stable structure at low temperature, and only the surface layer of aerogel has been considered. For modeling absorption potential field in plane, summation of potential from individual building blocks has been provided. Two dimensional Van der Waals energy field was calculated for different geometries of aerogel strands. A rather deep potential well has been found in the corner formed due to aerogel strand crossing.

  4. Structural changes of Gd thin films and islands during hydrogen absorption

    We report on the effects of hydrogen absorption in Gadolinium Systems by using scanning tunneling microscopy (STM) and spectroscopy (STS). Offering low amounts of hydrogen (1-2 L) to thin films results in the adsorption on the surface. Adsorbed hydrogen changes the electronic structure of the affected areas due to supression of the surface state of Gd (0001). After the subsequent diffusion of hydrogen into the underlying layer the surface state reappears. This can be observed using STS and STM. This change in the electronic structure causes a voltage dependent corrugation which changes sign at 0.8 V. It was observed that the inversion of the corrugation for islands occurs at higher voltages. For higher dosage (>50 L) not only the electronic structure is affected but also the topographic structure. As a result we found small circular islands (diameter 6-8 nm) and ramp-like structures exhibiting the height of one atomic step. The topographic change of the surface can be ascribed to hydride formation (GdH2) in the thin film. This obsevation will be compared to the behavior of islands during hydrogen absorption.

  5. Electronic structure of barium strontium titanate by soft-x-ray absorption spectroscopy

    Uehara, Y. [Mitsubishi Electric Co., Hyogo (Japan); Underwood, J.H.; Gullikson, E.M.; Perera, R.C.C. [Ernest Orlando Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    Perovskite-type titanates, such as Strontium Titanate (STO), Barium Titanate (BTO), and Lead Titanate (PTO) have been widely studied because they show good electric and optical properties. In recent years, thin films of Barium Strontium Titanate (BST) have been paid much attention as dielectrics of dynamic random access memory (DRAM) capacitors. BST is a better insulator with a higher dielectric constant than STO and can be controlled in a paraelectric phase with an appropriate ratio of Ba/Sr composition, however, few studies have been done on the electronic structure of the material. Studies of the electronic structure of such materials can be beneficial, both for fundamental physics research and for improving technological applications. BTO is a famous ferroelectric material with a tetragonal structure, in which Ti and Ba atoms are slightly displaced from the lattice points. On the other hand, BST keeps a paraelectric phase, which means that the atoms are still at the cubic lattice points. It should be of great interest to see how this difference of the local structure around Ti atoms between BTO and BST effects the electronic structure of these two materials. In this report, the authors present the Ti L{sub 2,3} absorption spectra of STO, BTO, and BST measured with very high accuracy in energy of the absorption features.

  6. Polarized X-ray absorption spectroscopy of single-crystal Mn(V) complexes relevant to the oxygen-evolving complex of photosystem II

    Yano, Junko; Robblee, John; Pushkar, Yulia; Marcus, Matthew A; Bendix, Jesper; Workman, José M; Collins, Terrence J; Solomon, Edward I; George, Serena Debeer; Yachandra, Vittal K

    2007-01-01

    High-valent Mn-oxo species have been suggested to have a catalytically important role in the water splitting reaction which occurs in the Photosystem II membrane protein. In this study, five- and six-coordinate mononuclear Mn(V) compounds were investigated by polarized X-ray absorption spectroscopy...... in order to understand the electronic structure and spectroscopic characteristics of high-valent Mn species. Single crystals of the Mn(V)-nitrido and Mn(V)-oxo compounds were aligned along selected molecular vectors with respect to the X-ray polarization vector using X-ray diffraction. The local...... electronic structure of the metal site was then studied by measuring the polarization dependence of X-ray absorption near-edge spectroscopy (XANES) pre-edge spectra (1s to 3d transition) and comparing with the results of density functional theory (DFT) calculations. The Mn(V)-nitrido compound, in which the...

  7. X-ray Absorption Spectra Analysis for the Investigation of the Retardation Mechanism of Iodine Migration by the Silver Ion Added to Bentonite

    Most of iodine was captured by the block when NaI solution flowed through a bentonite block sorbed silver to retard the migration of iodine released from high-level radioactive wastes. In order to understand in detail the mechanism for the retardation of the iodine by the silver ion, X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectra of the silver sorbed bentonite before and after the contact with iodide were compared with those of AgO, Ag2O and AgI as references. This examination suggests that the silver ion sorbed on the bentonite is desorbed, and then it retards the migration of iodine by forming the cluster of AgI precipitate

  8. Si K Edge Structure and Variability in Galactic X-Ray Binaries

    Schulz, Norbert S; Canizares, Claude R

    2016-01-01

    We survey the Si K edge structure in various absorbed Galactic low-mass X-ray binaries (LMXBs) to study states of silicon in the inter- and circum-stellar medium. The bulk of these LMXBs lie toward the Galactic bulge region and all have column densities above $10^{22}$ cm$^{-2}$. The observations were performed with the \\emph{Chandra} High Energy Transmission Grating Spectrometer. The Si K edge in all sources appears at an energy value of 1844$\\pm$0.001 eV. The edge exhibits significant substructure which can be described by a near edge absorption feature at 1849$\\pm$0.002 eV and a far edge absorption feature at 1865$\\pm$0.002 eV. Both of these absorption features appear variable with equivalent widths up to several m\\AA. We can describe the edge structure with several components: multiple edge functions, near edge absorption excesses from silicates in dust form, signatures from X-ray scattering optical depths, and a variable warm absorber from ionized atomic silicon. The measured optical depths of the edges ...

  9. Novel TRIP-steel/Mg-PSZ composite-open cell foam structures for energy absorption

    Aneziris, Christos G.; Berek, Harry; Hasterok, Manuel [Institute of Ceramic, Glass and Construction Materials, Technische Universitaet Bergakademie Freiberg (Germany); Biermann, Horst; Wolf, Stefan; Krueger, Lutz [Institute of Materials Engineering, Technische Universitaet Bergakademie Freiberg (Germany)

    2010-03-15

    Porous materials have received extensive attention for energy absorption in the last years. In terms of this study austenitic TRIP-steel/Mg-PSZ composite-open cell foam structures are formed based on replicas using open-celled polyurethane foam as a skeleton with and without a supporting dense face (jacket) coating. Their compression strength as well as their specific energy absorption SEA has been registered as a function of the compressive strain. The zirconia addition has reinforced the composite material with the face coating up to a compressive strain of 50%. The stress-induced martensitic transformation of partially stabilized zirconia phases has been investigated as a function of the compressive strain by EBSD. The zirconia phase transformation is triggered already at low compressive strains below 2%. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  10. Absorption and eigenmode calculation for one-dimensional periodic metallic structures using the hydrodynamic approximation

    Yanai, Avner; Mortensen, N. Asger; Levy, Uriel

    2013-01-01

    We develop a modal method that solves Maxwell's equations in the presence of the linearized hydrodynamic correction. Using this approach, it is now possible to calculate the full diffraction for structures with a period of the order of the plasma wavelength, including not only the transverse but...... examination of the propagation constants of these modes reveals that the absorption peaks and dips are directly related to the direction of phase propagation of the longitudinal modes. Furthermore, we formulate a variant of the plane wave expansion method, and use it to calculate the dispersion diagram of...... also the longitudinal modes appearing above the plasma frequency. As an example for using this method we solve the diffraction of a plane wave near the plasma frequency from a bimetallic layer, modeled as a continuous variation of the plasma frequency. We observe absorption oscillations around the...

  11. Theoretical calculations of X-ray absorption spectra of a copper mixed ligand complex using computer code FEFF9

    The terms X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) refer, respectively, to the structure in the X-ray absorption spectrum at low and high energies relative to the absorption edge. Routine analysis of EXAFS experiments generally makes use of simplified models and several many-body parameters, e.g. mean free paths, many-body amplitude factors, and Debye-Waller factors, as incorporated in EXAFS analysis software packages like IFEFFIT which includes Artemis. Similar considerations apply to XANES, where the agreement between theory and experiment is often less satisfactory. The recently available computer code FEFF9 uses the real-space Green's function (RSGF) approach to calculate dielectric response over a broad spectrum including the dominant low-energy region. This code includes improved treatments of many-body effects such as inelastic losses, core-hole effects, vibrational amplitudes, and the extension to full spectrum calculations of optical constants including solid state effects. In the present work, using FEFF9, we have calculated the X-ray absorption spectrum at the K-edge of copper in a complex, viz., aqua (diethylenetriamine) (isonicotinato) copper(II), the crystal structure of which is unknown. The theoretical spectrum has been compared with the experimental spectrum, recorded by us at the XAFS beamline 11.1 at ELETTRA synchrotron source, Italy, in both XANES and EXAFS regions.

  12. Study of the local distortions of the perovskite system La1-xSrxCoO3 (0≤x≤0.35) using the extended x-ray absorption fine structure technique

    Jiang, Y.; Bridges, F.; Sundaram, N.; Belanger, D. P.; Anderson, I. E.; Mitchell, J. F.; Zheng, H.

    2009-10-01

    We present a temperature-dependent extended x-ray absorption fine structure (EXAFS)/x-ray absorption near edge structure (XANES) investigation of La1-xSrxCoO3 (LSCO) over a wide doping concentration range (0≤x≤0.35) . Five of the samples are nanoparticles ( x=0.15 , 0.20, 0.25, 0.30, and 0.35) and four are bulk powders ( x=0 , 0.15, 0.20, and 0.30). From the EXAFS analysis, we find that the Co-O bonds are well ordered for both bulk and nanoparticle materials and there is no clear evidence for a Jahn-Teller (JT) distortion in the LSCO system (either static or dynamic). The distortion of the Co-O bond with increasing T , parameterized by the width of the pair distribution function (PDF), σ(T) , can easily be modeled using a correlated Debye model with a high correlated Debye temperature ˜800K . There is also no evidence for a step in plots of σ2 vs T . In addition, the very small nonthermal contribution to σ2 for the Co-O (PDF), σstatic2 , sets an upper limit on the extent of any Jahn-Teller distortion at low T . These experiments are inconsistent with the existence of a significant fraction of Co sites with an intermediate spin (IS) state, for which there is a JT active eg electron on the Co atoms. We cannot, however, exclude the possibility of a tiny fraction of sites having a JT distortion or some other (non-JT active) means of producing an IS state. The bulk samples are well ordered out to at least the third neighbors (Co-Co) while the nanoparticles show increased disorder and a reduction in coordination for Co-Co. XANES data are also presented, and, for both bulk and nanoparticle samples, there is essentially no edge shift with increasing Sr concentration. Bond-valence sums also indicate no change in effective Co valence. These results indicate that when holes are introduced via Sr doping, they have little Co(3d) character and the Co configuration remains close to 3d6 ; we argue that the holes have mostly O(2p) character and are localized more on the O

  13. X-ray absorption studies of gamma irradiated Nd doped phosphate glass

    This paper presents the X-ray absorption near edge structure (XANES) studies of Nd doped phosphate glasses before and after gamma irradiation. The intensity and location of LIII edge white line peak of Nd changes depending on its concentration as well as on the ratio of O/Nd in the glass matrix. The decrease in the peak intensity of white line after gamma irradiation indicates towards reduction of Nd3+ to Nd2+ in the glass matrix, which increases with an increase in the doses of gamma irradiation. Similarity in the XANES spectra of Nd doped phosphate glasses and Nd2O3 suggests that coordination geometry around Nd3+ in glass samples may be identical to that of Nd2O3

  14. X-ray absorption studies of gamma irradiated Nd doped phosphate glass

    Rai, V. N., E-mail: vnrai@rrcat.gov.in [Indus Synchrotron Utilization Division, Raja Ramanna Centre for Advanced Technology, Indore-452013 (India); Rajput, Parasmani; Jha, S. N.; Bhattacharyya, D. [Atomic & Molecular Physics Division, Bhabha Atomic Research Centre, Mumbai-400085 (India)

    2015-06-24

    This paper presents the X-ray absorption near edge structure (XANES) studies of Nd doped phosphate glasses before and after gamma irradiation. The intensity and location of L{sub III} edge white line peak of Nd changes depending on its concentration as well as on the ratio of O/Nd in the glass matrix. The decrease in the peak intensity of white line after gamma irradiation indicates towards reduction of Nd{sup 3+} to Nd{sup 2+} in the glass matrix, which increases with an increase in the doses of gamma irradiation. Similarity in the XANES spectra of Nd doped phosphate glasses and Nd{sub 2}O{sub 3} suggests that coordination geometry around Nd{sup 3+} in glass samples may be identical to that of Nd{sub 2}O{sub 3}.

  15. Auto-oligomerization and hydration of pyrrole revealed by x-ray absorption spectroscopy

    Near edge x-ray absorption fine structure spectra have been measured at the carbon and nitrogen K-edges of the prototypical aromatic molecule, pyrrole, both in the gas phase and when solvated in water, and compared with spectra simulated using a combination of classical molecular dynamics and first principles density functional theory in the excited state core hole approximation. The excellent agreement enabled detailed assignments. Pyrrole is highly reactive, particularly in water, and reaction products formed by the auto-oligomerization of pyrrole are identified. The solvated spectra have been measured at two different temperatures, indicating that the final states remain largely unaffected by both hydration and temperature. This is somewhat unexpected, since the nitrogen in pyrrole can donate a hydrogen bond to water.

  16. Auto-oligomerization and hydration of pyrrole revealed by x-ray absorption spectroscopy

    Advanced Light Source; Schwartz, Craig P.; Uejio, Janel S.; Duffin, Andrew M.; England, Alice H.; Prendergast, David; Saykally, Richard J

    2009-05-29

    Near edge x-ray absorption fine structure (NEXAFS) spectra have been measured at the carbon and nitrogen K-edges of the prototypical aromatic molecule, pyrrole, both in the gas phase and when solvated in water, and compared with spectra simulated using a combination of classical molecular dynamics and first principles density functional theory in the excited state core hole approximation. The excellent agreement enabled detailed assignments. Pyrrole is highly reactive, particularly in water, and reaction products formed by the auto-oligomerization of pyrrole are identified. The solvated spectra have been measured at two different temperatures, indicating that the final states remain largely unaffected by both hydration and temperature. This is somewhat unexpected, since the nitrogen in pyrrole can donate a hydrogen bond to water.

  17. Investigation of the Structural Stability of Ion-Implanted Gd2Ti2-xSnxO7 Pyrochlore-Type Oxides by Glancing Angle X-ray Absorption Spectroscopy

    Aluri, Esther Rani; Hayes, John R.; Walker, James D.S.; Grosvenor, Andrew P. (Saskatchewan)

    2016-03-24

    Rare-earth titanate and stannate pyrochlore-type oxides have been investigated in the past for the sequestration of nuclear waste elements because of their resistance to radiation-induced structural damage. In order to enhance this property, it is necessary to understand the effect of radioactive decay of the incorporated actinide elements on the local chemical environment. In this study, Gd2Ti2–xSnxO7 materials have been implanted with Au– ions to simulate radiation-induced structural damage. Glancing angle X-ray absorption near-edge spectroscopy (GA-XANES), glancing angle X-ray absorption fine structure (GA-EXAFS) analysis, and powder X-ray diffraction have been used to investigate changes in the local coordination environment of the metal atoms in the damaged surface layer. Examination of GA-XANES/EXAFS spectra from the implanted Gd2Ti2–xSnxO7 materials collected at various glancing angles allowed for an investigation of how the local coordination environment around the absorbing atoms changed at different depths in the damaged surface layer. This study has shown the usefulness of GA-XANES to the examination of ion-implanted materials and has suggested that Gd2Ti2–xSnxO7 becomes more susceptible to ion-beam-induced structural damage with increasing Sn concentration.

  18. Further evidence for a variable fine-structure constant from Keck/HIRES QSO absorption spectra

    Murphy, M T; Flambaum, V V

    2003-01-01

    [Abridged] We previously presented evidence for a varying fine-structure constant, alpha, in two independent samples of Keck/HIRES QSO spectra. Here we present a detailed many-multiplet analysis of a third Keck/HIRES sample containing 78 absorption systems. We also re-analyse the previous samples, providing a total of 128 absorption systems over the redshift range 0.2absorption clouds. Assuming that da/a=0 at z_abs=0, the da...

  19. Plasmonic Structure Integrated Single-Photon Detector Configurations to Improve Absorptance and Polarization Contrast

    Mária Csete

    2015-02-01

    Full Text Available 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-orientation (γ = 90°/0° azimuthal angle and the highest polarization contrast is attained in S-orientation of all devices. Common nanophotonical origin of absorptance enhancement is collective resonance on nanocavity gratings with different profiles, which is promoted by coupling between localized modes in quarter-wavelength metal-insulator-metal nanocavities and laterally synchronized Brewster-Zenneck-type surface waves in integrated SNSPDs possessing a three-quarter-wavelength-scaled periodicity. The spectral sensitivity and dispersion characteristics reveal that device design specific optimal configurations exist.

  20. Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

    Transparent glasses were synthesized in the NaPO3-BaF2-WO3 ternary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten LI and LIII absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network. XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO6) and that these glasses are free of tungstate tetrahedra (WO4). In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO6 octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify 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 (30% molar) due to the formation of WO6 clusters

  1. Exergy and Structural Analysis of an Absorption Cooling Cycle and the Effect of Efficiency Parameters

    Miquel Nogués

    2005-12-01

    Full Text Available

    Absorption cycles are an alternative to compression cycles in cooling and refrigeration applications. Our analysis of an absorption cycle is based on the exergy and the structural analysis. Once the exergy analysis has been achieved, the coefficients of structural bonds (CSBs of the main heat and mass exchangers can be determined by a structural analysis. The CSBs show how the modification of the irreversibility of one component, by means of a variation of its efficiency, affects the whole cycle. It will be wise to put much of the design effort in improving the efficiency of a component, knowing that a slight decrease of the irreversibility of that component, thanks to a higher efficiency, results in an important improvement in the total irreversibility of the cycle. This methodology is applied to a single effect ammonia-water absorption cooling cycle. We also study how the selection of efficiency parameters affects the results comparing CSBs of heat exchangers obtained from the minimum temperature differences or the UA-values.

    Results show that the UA is a more suitable parameter than the minimum temperature difference. Concerning the CSB values, we obtain very high values for the refrigerant heat exchanger. Values above one are also observed for the absorber, condenser and generator.

    Lower values are found for the generator and the solution heat exchanger. A more detailed analysis should investigate the dependence of the CSB values on the range of efficiencies. As a further step, these results could be used in the thermoeconomic analysis and economical optimization.

  2. Oscillations of light absorption in 2D macroporous silicon structures with surface nanocoatings

    Karachevtseva, L., E-mail: lakar@isp.kiev.ua [V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, 41 Nauki Pr., 03028 Kyiv (Ukraine); Kuchmii, S. [L.V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Nauki Pr., 03028 Kyiv (Ukraine); Lytvynenko, O.; Sizov, F.; Stronska, O. [V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, 41 Nauki Pr., 03028 Kyiv (Ukraine); Stroyuk, A. [L.V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Nauki Pr., 03028 Kyiv (Ukraine)

    2011-02-01

    We investigated the near-IR light absorption oscillations in 2D macroporous silicon structures with microporous silicon layers and CdTe, ZnO surface nanocrystals. The electro-optical effect was taken into account within the strong electric field approximation. Well-separated oscillations were observed in the spectral ranges of the surface bonds of macroporous silicon structures with surface nanocrystals. The model of the resonant electron scattering on impurity states in electric field of heterojunction 'silicon-nanocoating' on macropore surface as well as realization of Wannier-Stark effect on the randomly distributed surface bonds were considered. The Wannier-Stark ladders are not broken by impurities because of the longer scattering lifetime as compared with the period of electron oscillations in an external electric field, in all spectral regions considered for macroporous silicon structures with CdTe and ZnO surface nanocrystals.

  3. Oscillations of light absorption in 2D macroporous silicon structures with surface nanocoatings

    We investigated the near-IR light absorption oscillations in 2D macroporous silicon structures with microporous silicon layers and CdTe, ZnO surface nanocrystals. The electro-optical effect was taken into account within the strong electric field approximation. Well-separated oscillations were observed in the spectral ranges of the surface bonds of macroporous silicon structures with surface nanocrystals. The model of the resonant electron scattering on impurity states in electric field of heterojunction 'silicon-nanocoating' on macropore surface as well as realization of Wannier-Stark effect on the randomly distributed surface bonds were considered. The Wannier-Stark ladders are not broken by impurities because of the longer scattering lifetime as compared with the period of electron oscillations in an external electric field, in all spectral regions considered for macroporous silicon structures with CdTe and ZnO surface nanocrystals.

  4. Oscillations of light absorption in 2D macroporous silicon structures with surface nanocoatings

    Karachevtseva, L.; Kuchmii, S.; Lytvynenko, O.; Sizov, F.; Stronska, O.; Stroyuk, A.

    2011-02-01

    We investigated the near-IR light absorption oscillations in 2D macroporous silicon structures with microporous silicon layers and CdTe, ZnO surface nanocrystals. The electro-optical effect was taken into account within the strong electric field approximation. Well-separated oscillations were observed in the spectral ranges of the surface bonds of macroporous silicon structures with surface nanocrystals. The model of the resonant electron scattering on impurity states in electric field of heterojunction “silicon-nanocoating” on macropore surface as well as realization of Wannier-Stark effect on the randomly distributed surface bonds were considered. The Wannier-Stark ladders are not broken by impurities because of the longer scattering lifetime as compared with the period of electron oscillations in an external electric field, in all spectral regions considered for macroporous silicon structures with CdTe and ZnO surface nanocrystals.

  5. Structure-activity relationships of heterogeneous catalysts from time-resolved X-ray absorption spectroscopy

    Knowing the composition and the evolution of the bulk structure of a heterogeneous catalyst under working conditions (in situ) is a pre-requisite for understanding structure-activity relationships. X-ray absorption spectroscopy can be employed to study a catalytically active material in situ. In addition to steady-state investigations, the technique permits experiments with a time-resolution in the sub-second range to elucidate the solid-state kinetics of the reactions involved. Combined with mass spectrometry, the evolution of the short-range order structure of a heterogeneous catalyst, the average valence of the constituent metals, and the phase composition can be obtained. Here we present results obtained from time-resolved studies on the reduction of MoO3 in propene and in propene and oxygen

  6. Structural analysis of amorphous and hydrogen absorption alloys by neutron diffraction

    Structural studies of amorphous alloys and hydrogen absorption amorphous alloys by taking advantage of neutron and X-ray diffractions and using the reverse Monte Carlo (RMC) modeling for getting information of the three dimensional atom configuration are reviewed. Voronoi analysis of the RMC models is powerful to elucidate the structural origin of the stability of amorphous state, since Ni-Zr amorphous alloys are unstable in comparison with Cu-Zr ones. The polyhedra around Ni atoms are dominated by trigonal prism-like polyhedra. In contrast, icosahedron-like polyhedra are preferred for Cu. The Ni-Zr amorphous alloys have been reported to stabilize by adding Al. The Voronoi analysis informs us that trigonal prism-like polyhedra decreased in number by adding Al to the Ni-Zr system. On the contrary, the number of icosahedron-like polyhedra was found to increase. The results apparently indicate that the icosahedron-like polyhedra play an important role to stabilize the amorphous state. Moreover, neutron diffraction is a powerful tool to clarify the location of hydrogen atoms in the hydrogen absorption materials. For TbFe2D3.8 and TbNi2D2.4 amorphous alloys, the RMC model structure based on the diffraction data teach us that about 98% of hydrogen atoms occupy tetrahedral sites formed by metal atoms and stabilize the amorphous state. (author)

  7. Effect of Ti–Zn substitution on structural, magnetic and microwave absorption characteristics of strontium hexaferrite

    Baniasadi, Aminreza, E-mail: aminreza.baniasadi@yahoo.com [Department of Materials Science and Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Ghasemi, Ali [Materials Engineering Department, Malek Ashtar University of Technology, Shahin Shahr (Iran, Islamic Republic of); Nemati, Ali; Azami Ghadikolaei, Milad [Department of Materials Science and Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Paimozd, Ebrahim [Materials Engineering Department, Malek Ashtar University of Technology, Shahin Shahr (Iran, Islamic Republic of)

    2014-01-15

    Highlights: • M{sub s}, as well as H{sub c}, decreased with substitution of Ti–Zn ions in place of ferric. • Microwave absorption properties improved with increasing dopant content. • A composite with x = 2.5 has shown a minimum RL of −36.13 dB at 13.43 GHz. • A composite with x = 2.5 exhibited the widest bandwidth relative to other composites. -- Abstract: SrFe{sub 12−x}Ti{sub x/2}Zn{sub x/2}O{sub 19} (x = 0–2.5) powders were synthesized by use of chlorides through co-precipitation method. The obtained powders were then milled by high energy ball mill to crash hard agglomerates and achieve nanoparticles. In order to evaluate microwave absorption versus frequency, composites including ferrite, as a filler, and matrix of polyvinylchloride (PVC) with weight ratio of 70% ferrite were prepared. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), vibrating sample magnetometer (VSM) and vector network analyzer (VNA) were employed to study the structural, magnetic and microwave absorption properties of samples. The XRD patterns showed that the hexagonal single phase were obtained only if x ⩽ 2. FE-SEM micrographs indicated that the particle sizes were almost less than 40 nm. With increasing amount of dopant from x = 0 to x = 2.5, the saturation magnetization and coercivity decreased from 56 emu/g and 1350 Oe to 16 emu/g and 88 Oe, respectively. The maximum loss of electromagnetic waves was −36.13 dB obtained by ferrite with maximum amount of substitution. The obtained results indicated that the proposed composites can be introduced as electromagnetic wave absorption materials.

  8. Effect of Ti–Zn substitution on structural, magnetic and microwave absorption characteristics of strontium hexaferrite

    Highlights: • Ms, as well as Hc, decreased with substitution of Ti–Zn ions in place of ferric. • Microwave absorption properties improved with increasing dopant content. • A composite with x = 2.5 has shown a minimum RL of −36.13 dB at 13.43 GHz. • A composite with x = 2.5 exhibited the widest bandwidth relative to other composites. -- Abstract: SrFe12−xTix/2Znx/2O19 (x = 0–2.5) powders were synthesized by use of chlorides through co-precipitation method. The obtained powders were then milled by high energy ball mill to crash hard agglomerates and achieve nanoparticles. In order to evaluate microwave absorption versus frequency, composites including ferrite, as a filler, and matrix of polyvinylchloride (PVC) with weight ratio of 70% ferrite were prepared. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), vibrating sample magnetometer (VSM) and vector network analyzer (VNA) were employed to study the structural, magnetic and microwave absorption properties of samples. The XRD patterns showed that the hexagonal single phase were obtained only if x ⩽ 2. FE-SEM micrographs indicated that the particle sizes were almost less than 40 nm. With increasing amount of dopant from x = 0 to x = 2.5, the saturation magnetization and coercivity decreased from 56 emu/g and 1350 Oe to 16 emu/g and 88 Oe, respectively. The maximum loss of electromagnetic waves was −36.13 dB obtained by ferrite with maximum amount of substitution. The obtained results indicated that the proposed composites can be introduced as electromagnetic wave absorption materials

  9. Probing the Inner Structure of Polar Broad Absorption-Line Quasars

    Ghosh, Kajal

    2008-10-01

    We have discovered a sample of polar broad absorption-line quasars (BALQSOs). We know their inclination angles with reasonable certainty. Thus, these are the ideal objects to probe their inner structure through the X-ray studies. However, to date, we do not have a reasonably good signal-to-noise ratio X-ray spectrum of any of these objects. Here, we propose deep XMM-Newton observations of four polar BALQSOs to study the physical processes responsible for the X-ray emission, distribution of BAL clouds, wind driven mechanism, jet entrainment, etc. Finally, all these results will be used to constrain our time-dependent hydrodynamical simulations.

  10. A new analysis of fine-structure constant measurements and modelling errors from quasar absorption lines

    Wilczynska, Michael R.; Webb, John K.; King, Julian A.; Murphy, Michael T.; Bainbridge, Matthew B.; Flambaum, Victor V.

    2015-01-01

    We present an analysis of 23 absorption systems along the lines of sight towards 18 quasars in the redshift range of $0.4 \\leq z_{abs} \\leq 2.3$ observed on the Very Large Telescope (VLT) using the Ultraviolet and Visual Echelle Spectrograph (UVES). Considering both statistical and systematic error contributions we find a robust estimate of the weighted mean deviation of the fine-structure constant from its current, laboratory value of $\\Delta\\alpha/\\alpha=\\left(0.22\\pm0.23\\right)\\times10^{-5...

  11. X-ray absorption fine structure spectroscopy studies of thiol-capped copper nanoparticles

    Monodisperse Copper nanoparticles with controllable sizes of 0.6 and 1.8nm were synthesized via modifying Brust-Schiffrin two-phase method. This route involves a slow reduction of [TOA]2[CuBr4] precursor in toluene, with particles sizes rationally controlled by the S/Cu ratio. Size-dependent inter-atomic distance contraction in the thiol-capped copper nanoparticles was investigated by Extended X-ray Absorption Fine Structure (EXAFS). The analysis revealed a shortened Cu-Cu inter-atomic distance, indicating strong surface interaction, in accord with the larger effect expected for ultrasmall particals (<2nm).

  12. Energetics, structures, vibrational frequencies, vibrational absorption, vibrational circular dichroism and Raman intensities of Leu-enkephalin

    Jalkanen, Karl J.

    2003-01-01

    Here we present several low energy conformers of Leu-enkephalin (LeuE) calculated with the density functional theory using the Becke 3LYP hybrid functional and the 6-31G* basis set. The structures, conformational energies, vibrational frequencies, vibrational absorption (VA) intensities......, vibrational circular dichroism (VCD) intensities and Raman scattering intensities are reported for the conformers of LeuE which are expected to be populated at room temperature. The species of LeuE-present in non-polar solvents is the neutral non-ionic species with the NH2 and CO2H groups, in contrast to the...

  13. Optical Absorption, Stability and Structure of NpO2+ Complexes with Dicarboxylic Acids

    Complexation of NpO2+ with oxalic acid (OX),2,2'-oxydiacetic acid (ODA), 2,2'-iminodiacetic acid (IDA) and 2,2'-thiodiacetic acid (TDA), has been studied using spectrophotometry in1 M NaClO4. Both the position and the intensity of the absorption band of NpO2+ at 980 nm are affected by the formation of NpO2+/dicarboxylate complexes, providing useful information on the complexation strength, the coordination mode and the structure of the complexes

  14. Local structure of Ba(1-x)Sr(x)TiO3 and BaTi(1-y)Zr(y)O3 nanocrystals probed by X-ray absorption and X-ray total scattering.

    Rabuffetti, Federico A; Brutchey, Richard L

    2013-12-23

    The effect of isovalent chemical substitution on the magnitude and coherence length of local ferroelectric distortions present in sub-20 nm Ba(1-x)Sr(x)TiO3 (x = 0.0, 0.30, 0.50, 1.0) and BaTi(1-y)Zr(y)O3 (y = 0.0, 0.15, 0.50, 1.0) nanocrystals synthesized at room temperature is investigated using X-ray absorption near edge structure (XANES) and pair distribution function analysis of X-ray total scattering data (PDF). Although the average crystal structure of the nanocrystals is adequately described by a centrosymmetric, cubic Pm3m space group, local ferroelectric distortions due to the displacement of the titanium atom from the center of the perovskite lattice are observed for all compositions, except BaZrO3. The symmetry of the ferroelectric distortions is adequately described by a tetragonal P4mm space group. The magnitude of the local displacements of the titanium atom in BaTiO3 nanocrystals is comparable to that observed in single crystals and bulk ceramics, but the coherence length of their ferroelectric coupling is much shorter (≤20 Å). Substitution of Sr(2+) for Ba(2+) and of Zr(4+) for Ti(4+) induces a tetragonal-to-cubic transition of the room temperature local crystal structure, analogous to that observed for single crystals and bulk ceramics at similar compositions. This transition is driven by a reduction of the magnitude of the local displacements of the titanium atom and/or of the coherence length of their ferroelectric coupling. Replacing 50% of Ba(2+) with Sr(2+) slightly reduces the magnitude of the titanium displacement, but the coherence length is not affected. In contrast, replacing 15% of the ferroelectrically active Ti(4+) with Zr(4+) leads to a significant reduction of the coherence length. Deviations from the ideal solid solution behavior are observed in BaTi(1-y)Zr(y)O3 nanocrystals and are attributed to an inhomogeneous distribution of the barium atoms in the nanocrystal. Composition-structure relationships derived for Ba(1-x)Sr(x)TiO3

  15. An energy dispersive x-ray absorption spectroscopy beamline, X6A, at NSLS

    An energy dispersive x-ray absorption spectroscopy instrument has been built at the X6A beam port of the x-ray ring at the National Synchrotron Light Source (NSLS). This instrument allows the collection of extended x-ray-absorption fine structure and/or x-ray absorption near-edge structure spectra for many elements on the millisecond time scale. The beamline employs a four-point crystal bender and a rectangular Si 220 crystal to access incident energies between 6.5 and 21 keV. Because the polychromator focuses the synchrotron beam to a narrow 100-μm line, this experimental apparatus is ideal for x-ray absorption spectroscopy experiments in special environments such as at high pressures, for in situ experiments, and/or for very small samples. In this manuscript we will describe the instrument design and present data with which to evaluate the instrument. This beamline is available through the NSLS user proposal system

  16. Constraining the Variation of the Fine-structure Constant with Observations of Narrow Quasar Absorption Lines

    Songaila, A.; Cowie, L. L.

    2014-10-01

    The unequivocal demonstration of temporal or spatial variability in a fundamental constant of nature would be of enormous significance. Recent attempts to measure the variability of the fine-structure constant α over cosmological time, using high-resolution spectra of high-redshift quasars observed with 10 m class telescopes, have produced conflicting results. We use the many multiplet (MM) method with Mg II and Fe II lines on very high signal-to-noise, high-resolution (R = 72, 000) Keck HIRES spectra of eight narrow quasar absorption systems. We consider both systematic uncertainties in spectrograph wavelength calibration and also velocity offsets introduced by complex velocity structure in even apparently simple and weak narrow lines and analyze their effect on claimed variations in α. We find no significant change in α, Δα/α = (0.43 ± 0.34) × 10-5, in the redshift range z = 0.7-1.5, where this includes both statistical and systematic errors. We also show that the scatter in measurements of Δα/α arising from absorption line structure can be considerably larger than assigned statistical errors even for apparently simple and narrow absorption systems. We find a null result of Δα/α = (- 0.59 ± 0.55) × 10-5 in a system at z = 1.7382 using lines of Cr II, Zn II, and Mn II, whereas using Cr II and Zn II lines in a system at z = 1.6614 we find a systematic velocity trend that, if interpreted as a shift in α, would correspond to Δα/α = (1.88 ± 0.47) × 10-5, where both results include both statistical and systematic errors. This latter result is almost certainly caused by varying ionic abundances in subcomponents of the line: using Mn II, Ni II, and Cr II in the analysis changes the result to Δα/α = (- 0.47 ± 0.53) × 10-5. Combining the Mg II and Fe II results with estimates based on Mn II, Ni II, and Cr II gives Δα/α = (- 0.01 ± 0.26) × 10-5. We conclude that spectroscopic measurements of quasar absorption lines are not yet capable of

  17. Constraining the variation of the fine-structure constant with observations of narrow quasar absorption lines

    Songaila, A.; Cowie, L. L., E-mail: acowie@ifa.hawaii.edu [Institute for Astronomy, University of Hawaii, 2680 Woodlawn Drive, Honolulu, HI 96822 (United States)

    2014-10-01

    The unequivocal demonstration of temporal or spatial variability in a fundamental constant of nature would be of enormous significance. Recent attempts to measure the variability of the fine-structure constant α over cosmological time, using high-resolution spectra of high-redshift quasars observed with 10 m class telescopes, have produced conflicting results. We use the many multiplet (MM) method with Mg II and Fe II lines on very high signal-to-noise, high-resolution (R = 72, 000) Keck HIRES spectra of eight narrow quasar absorption systems. We consider both systematic uncertainties in spectrograph wavelength calibration and also velocity offsets introduced by complex velocity structure in even apparently simple and weak narrow lines and analyze their effect on claimed variations in α. We find no significant change in α, Δα/α = (0.43 ± 0.34) × 10{sup –5}, in the redshift range z = 0.7-1.5, where this includes both statistical and systematic errors. We also show that the scatter in measurements of Δα/α arising from absorption line structure can be considerably larger than assigned statistical errors even for apparently simple and narrow absorption systems. We find a null result of Δα/α = (– 0.59 ± 0.55) × 10{sup –5} in a system at z = 1.7382 using lines of Cr II, Zn II, and Mn II, whereas using Cr II and Zn II lines in a system at z = 1.6614 we find a systematic velocity trend that, if interpreted as a shift in α, would correspond to Δα/α = (1.88 ± 0.47) × 10{sup –5}, where both results include both statistical and systematic errors. This latter result is almost certainly caused by varying ionic abundances in subcomponents of the line: using Mn II, Ni II, and Cr II in the analysis changes the result to Δα/α = (– 0.47 ± 0.53) × 10{sup –5}. Combining the Mg II and Fe II results with estimates based on Mn II, Ni II, and Cr II gives Δα/α = (– 0.01 ± 0.26) × 10{sup –5}. We conclude that spectroscopic measurements of

  18. Constraining the variation of the fine-structure constant with observations of narrow quasar absorption lines

    The unequivocal demonstration of temporal or spatial variability in a fundamental constant of nature would be of enormous significance. Recent attempts to measure the variability of the fine-structure constant α over cosmological time, using high-resolution spectra of high-redshift quasars observed with 10 m class telescopes, have produced conflicting results. We use the many multiplet (MM) method with Mg II and Fe II lines on very high signal-to-noise, high-resolution (R = 72, 000) Keck HIRES spectra of eight narrow quasar absorption systems. We consider both systematic uncertainties in spectrograph wavelength calibration and also velocity offsets introduced by complex velocity structure in even apparently simple and weak narrow lines and analyze their effect on claimed variations in α. We find no significant change in α, Δα/α = (0.43 ± 0.34) × 10–5, in the redshift range z = 0.7-1.5, where this includes both statistical and systematic errors. We also show that the scatter in measurements of Δα/α arising from absorption line structure can be considerably larger than assigned statistical errors even for apparently simple and narrow absorption systems. We find a null result of Δα/α = (– 0.59 ± 0.55) × 10–5 in a system at z = 1.7382 using lines of Cr II, Zn II, and Mn II, whereas using Cr II and Zn II lines in a system at z = 1.6614 we find a systematic velocity trend that, if interpreted as a shift in α, would correspond to Δα/α = (1.88 ± 0.47) × 10–5, where both results include both statistical and systematic errors. This latter result is almost certainly caused by varying ionic abundances in subcomponents of the line: using Mn II, Ni II, and Cr II in the analysis changes the result to Δα/α = (– 0.47 ± 0.53) × 10–5. Combining the Mg II and Fe II results with estimates based on Mn II, Ni II, and Cr II gives Δα/α = (– 0.01 ± 0.26) × 10–5. We conclude that spectroscopic measurements of quasar absorption lines are not yet

  19. EVALUATION OF THE STRUCTURAL FUNDS ABSORPTION RATE BY MEANS OF THE HERMIN MODEL

    Opritescu Elena Madalina

    2012-07-01

    Full Text Available The main objective of this article is to highlight the main method that could quantify the impact of the structural funds on the Gross Domestic Product. I also presented the regional disparities situation and the European funds absorption rate. The HERMIN model has been designed considering the evolution of macro-variables throughout transition and pre-accession process, as well as out of the need to analyze the gradual alignment of Romania’s economic policies to those of EU. The fact that, initially, the HERMIN model was designed for the European Union’s less developed economies represented the cornerstone in choosing it, as it was the case for Romania, too. However, the quantitative evaluation must always be accompanied by a qualitative evaluation, in order to comprise factors which cannot be measured by the econometrical modeling. For this purpose, when the results of econometrical model based evaluation are used, it is important to be aware of the fact that models simplify reality, no matter the impressive mathematical calculations they employ. Also, we must not omit the fact that Romania’s major development needs and the current economic context imperatively demand a high as possible level of structural funds absorption, as well as their efficient use, meant to generate a significant impact at a national, regional and local level. One of the main instruments employed to sustain economic growth, while also reducing disparities between regions is represented by the structural funds. These funds, consisting in financial contributions of the member states, according to their level of development, are redistributed in compliance with an extremely complex regulating and procedural frame, to those EU states of regions which are fallen behind from a social and economical development perspective Nevertheless, when absorption capacity of a member state is evaluated, the used percentage from the allocated funds is not the only

  20. First principle studies on the electronic structures and absorption spectra in KMgF{sub 3} crystal with fluorine vacancy

    Cheng Fang [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Liu Tingyu, E-mail: liutyyxj@163.co [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Zhang Qiren; Qiao Hailin; Zhou Xiuwen [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China)

    2010-08-01

    The experiments indicate that the perfect KMgF{sub 3} crystal has no absorption in the visible range, however the electron irradiation induces a complex absorption spectrum. The absorption spectra can be decomposed by five Gaussian bands peaking at 2.5 eV (488 nm), 3.4 eV (359 nm), 4.2 eV (295 nm), 4.6 eV (270 nm) and 5.2 eV (239 nm), respectively. The purpose of this paper is to seek the origins of the absorption bands. The electronic structures and absorption spectra either for the perfect KMgF{sub 3} or for KMgF{sub 3}: V{sub F}{sup +} with electrical neutrality have been studied by using density functional theory code CASTEP with the lattice structure optimized. The calculation results predicate that KMgF{sub 3}: V{sub F}{sup +} also exhibits five absorption bands caused by the existence of the fluorine ion vacancy V{sub F}{sup +} and the five absorption bands well coincide with the experimental results. It is believable that the five absorption bands are related to V{sub F}{sup +} in KMgF{sub 3} crystal produced by the electron irradiation.

  1. First principle studies on the electronic structures and absorption spectra in KMgF 3 crystal with fluorine vacancy

    Cheng, Fang; Liu, Tingyu; Zhang, Qiren; Qiao, Hailin; Zhou, Xiuwen

    2010-08-01

    The experiments indicate that the perfect KMgF 3 crystal has no absorption in the visible range, however the electron irradiation induces a complex absorption spectrum. The absorption spectra can be decomposed by five Gaussian bands peaking at 2.5 eV (488 nm), 3.4 eV (359 nm), 4.2 eV (295 nm), 4.6 eV (270 nm) and 5.2 eV (239 nm), respectively. The purpose of this paper is to seek the origins of the absorption bands. The electronic structures and absorption spectra either for the perfect KMgF 3 or for KMgF 3: VF+ with electrical neutrality have been studied by using density functional theory code CASTEP with the lattice structure optimized. The calculation results predicate that KMgF 3: VF+ also exhibits five absorption bands caused by the existence of the fluorine ion vacancy VF+ and the five absorption bands well coincide with the experimental results. It is believable that the five absorption bands are related to VF+ in KMgF 3 crystal produced by the electron irradiation.

  2. Investigation on the temperature-dependence of absorption properties of solar cells with micro-structured surfaces

    2010-01-01

    The temperature of a solar cell will increase when it is exposed to the sunlight,which results in variations of optical parameters and thermal expansion coefficient of the cell,thus affecting its spectral absorption feature.This paper is aimed to investigate the effects of temperature on the absorption property of solar cells with micro-structured surfaces.By taking hemispherical, cylindrical and spherical surfaces as models,numerical computation is conducted to obtain spectral distribution of absorptance of such surfaces with different structural parameters by means of the finite difference time domain(FDTD)method.Furthermore,the effects of material properties and structural period on the absorption property are also investigated.

  3. X-ray absorption spectroscopy investigation of structurally modified lithium niobate crystals

    Vitova, Tonya

    2008-02-15

    The type and concentration of impurity centers in different valence states are crucial for tuning the photorefractive properties of doped Lithium Niobate (LN) crystals. X-ray Absorption Spectroscopy (XAS) is an appropriate tool for studying the local structure of impurity centers. XAS combined with absorption in UV/VIS/IR and High Resolution X-ray Emission Spectroscopy (HRXES) provide information about the valence state of the dopant ions in as-grown, reduced or oxidized doped LN crystals. Cu (Cu{sup 1+} and Cu{sup 2+}) and Fe (Fe{sup 2+} and Fe{sup 3+}) atoms are found in two different valence states, whereas there are indications for a third Mn valency, in addition to Mn{sup 2+} and Mn{sup 3+} in manganese-doped LN crystals. One of the charge compensation mechanisms during reduction of copper- doped LN crystals is outgassing of oxygen atoms. Cu ions in the reduced crystals have at least two different site symmetries: twofold (Cu{sup 1+}) and sixfold (Cu{sup 2+}) coordinated by O atoms. Fe and Mn atoms are coordinated by six O atoms. Cu and Fe ions are found to occupy only Li sites, whereas Mn ions are also incorporated into Li and Nb sites. The refractive index change in LN crystals irradiated with {sup 3}He{sup 2+} ions is caused by structurally disordered centers, where Nb atoms are displaced from normal crystallographic sites and Li or/and O vacancies are present. (orig.)

  4. X-ray absorption spectroscopy investigation of structurally modified lithium niobate crystals

    The type and concentration of impurity centers in different valence states are crucial for tuning the photorefractive properties of doped Lithium Niobate (LN) crystals. X-ray Absorption Spectroscopy (XAS) is an appropriate tool for studying the local structure of impurity centers. XAS combined with absorption in UV/VIS/IR and High Resolution X-ray Emission Spectroscopy (HRXES) provide information about the valence state of the dopant ions in as-grown, reduced or oxidized doped LN crystals. Cu (Cu1+ and Cu2+) and Fe (Fe2+ and Fe3+) atoms are found in two different valence states, whereas there are indications for a third Mn valency, in addition to Mn2+ and Mn3+ in manganese-doped LN crystals. One of the charge compensation mechanisms during reduction of copper- doped LN crystals is outgassing of oxygen atoms. Cu ions in the reduced crystals have at least two different site symmetries: twofold (Cu1+) and sixfold (Cu2+) coordinated by O atoms. Fe and Mn atoms are coordinated by six O atoms. Cu and Fe ions are found to occupy only Li sites, whereas Mn ions are also incorporated into Li and Nb sites. The refractive index change in LN crystals irradiated with 3He2+ ions is caused by structurally disordered centers, where Nb atoms are displaced from normal crystallographic sites and Li or/and O vacancies are present. (orig.)

  5. Fullerene-Based Photoactive Layers for Heterojunction Solar Cells: Structure, Absorption Spectra and Charge Transfer Process

    Yuanzuo Li

    2014-12-01

    Full Text Available The electronic structure and optical absorption spectra of polymer APFO3, [70]PCBM/APFO3 and [60]PCBM/APFO3, were studied with density functional theory (DFT, and the vertical excitation energies were calculated within the framework of the time-dependent DFT (TD-DFT. Visualized charge difference density analysis can be used to label the charge density redistribution for individual fullerene and fullerene/polymer complexes. The results of current work indicate that there is a difference between [60]PCBM and [70]PCBM, and a new charge transfer process is observed. Meanwhile, for the fullerene/polymer complex, all calculations of the twenty excited states were analyzed to reveal all possible charge transfer processes in depth. We also estimated the electronic coupling matrix, reorganization and Gibbs free energy to further calculate the rates of the charge transfer and the recombination. Our results give a clear picture of the structure, absorption spectra, charge transfer (CT process and its influencing factors, and provide a theoretical guideline for designing further photoactive layers of solar cells.

  6. Temperature dependence of aggregated structure of β-carotene by absorption spectral experiment and simulation.

    Lu, Liping; Wu, Jie; Wei, Liangshu; Wu, Fang

    2016-12-01

    β-carotene can self-assemble to form J- or H-type aggregate in hydrophilic environments, which is crucial for the proper functioning of biological system. Although several ways controlling the formation of the two types of aggregate in hydrated ethanol have been investigated in recent years, our study provided another way to control whether J- or H- β-carotene was formed and presented a method to investigate the aggregated structure. For this purpose, the aggregates of β-carotene formed at different temperatures were studied by UV-Vis spectra and a computational method based on Frenkel exciton was applied to simulate the absorption spectra to obtain the aggregated structure of the β-carotene. The analysis showed that β-carotene formed weakly coupled H-aggregate at 15°C in 1:1 ethanol-water solvent, and with the increase of temperature it tended to form J-type of aggregate. The absorption spectral simulation based on one-dimensional Frenkel exciton model revealed that good fit with the experiment was obtained with distance between neighbor molecules r=0.82nm, disorder of the system D=1500cm(-1) for H-type and r=1.04nm, D=1800cm(-1) for J-type. PMID:27348046

  7. Structures and optical absorption of Bi2OS2 and LaOBiS2

    Miura, Akira; Mizuguchi, Yoshikazu; Takei, Takahiro; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro; Tadanaga, Kiyoharu

    2016-02-01

    The band gaps of isostructural Bi2OS2 and LaOBiS2 were examined using optical absorption and discussed with the band structures calculated based on the crystal structures determined using synchrotron X-ray diffraction. The Bi 6p and S 3p orbitals in the Bi-S plane were computationally predicted to constitute the bands near the Fermi level. The optical reflectance spectra of Bi2OS2 and LaOBiS2 showed optical band gaps of ~1.0 eV, which were close to the computationally calculated direct band gaps of ~0.8 eV. Our results show that Bi2OS2 and LaOBiS2 are semiconductors containing direct band gaps of 0.8-1.0 eV, and they are suggested to be candidates for optoelectronic materials in the near-infrared region without highly toxic elements.

  8. High-sensitivity x-ray absorption fine structure investigation of arsenic shallow implant in silicon

    High-sensitivity fluorescence-yield x-ray absorption fine structure spectroscopy (XAFS) has been investigated to characterize the local structure around arsenic shallow implant in silicon. Fluorescence-yield XAFS experiments were performed using a high-brilliance synchrotron radiation beam from an in-vacuum-type undulator in a third-generation light source. In addition to investigating the efficiency of high-brilliance undulator x-rays during the fluorescence-yield XAFS measurements, we compared the analytical performance of both the wavelength dispersive spectrometer (WDS) and the energy dispersive spectrometer (EDS) based on the silicon drift detector (SDD). It was confirmed that the WDS reduces the influence of scattering background due to the high spectral resolution. Another advantage of the WDS is high counting rate measurements. It was found that fluorescence-yield XAFS using undulator x-rays combined with the WDS permits superior sensitivity measurements.

  9. Fine Structure of the R Absorption Lines of Cr3+ in Antiferromagnetic Dysprosium Aluminum Garnet

    Aoyagi, Kiyoshi; Kajiura, Masako; Sugano, Satoru

    1981-11-01

    The absorption spectrum of a Cr3+ ion in an antiferromagnetic disprosium aluminum garnet with the Néel temperature TN of 2.5 K, is measured in the red region between 1.7 K and 4.2 K. It is shown that the fine structure of the R1 and R2 lines at 1.7 K can be explained by using an effective Hamiltonian for the t2g3 2E excited state of Cr3+ in the surrounding of the ordered Dy3+ spins. The gross feature of the observed temperature dependence of the fine structure is shown to be reproduced by assuming appropriate exchange interactions of Cr3+ with Dy3+.

  10. Structure-induced resonant tail-state regime absorption in polymer: fullerene bulk-heterojunction solar cells

    Pfadler, Thomas; Kiel, Thomas; Stärk, Martin; Werra, Julia F. M.; Matyssek, Christian; Sommer, Daniel; Boneberg, Johannes; Busch, Kurt; Weickert, Jonas; Schmidt-Mende, Lukas

    2016-05-01

    In this work, we present resonant tail-state regime absorption enhanced organic photovoltaics. We combine periodically structured TiO2 bottom electrodes with P3HT-PCBM bulk-heterojunction solar cells in an inverted device configuration. The wavelength-scale patterns are transferred to the electron-selective bottom electrodes via direct laser interference patterning, a fast method compatible with roll-to-roll processing. Spectroscopic and optoelectronic device measurements suggest polarization-dependent absorption enhancement along with photocurrent generation unambiguously originating from the population of tail states. We discuss the effects underlying these absorption patterns with the help of electromagnetic simulations using the discontinuous Galerkin time domain method. For this, we focus on the total absorption spectra along with spatially resolved power loss densities. Our simulations stress the tunability of the absorption resonances towards arbitrary wavelength regions.

  11. New data on the structure of uranium monocarbide

    Uranium monocarbide (UC) or ternary alloys are considered to be possible candidates for future nuclear fuels. Although the crystallographic and electronic structure of UC has been addressed in past investigations, discrepancies in the literature data have fostered a new investigation of the UC phase. We report here a reinvestigation of the UC phase by complementary X-ray spectroscopy and quantum chemical calculations. A combination of X-ray powder diffraction and extended X-ray absorption fine structure analysis at the uranium LIII edge led to the crystallographic determination of the UC phase of the NaCl type. For electronic structure investigation, a combination of uranium X-ray absorption near-edge spectroscopy at the LIII edge and at the NIV, NV edges with quantum chemical calculations allowed us to define the evolution of the metal charge in comparison with metallic uranium on the one hand and uranium dioxide on the other hand. (authors)

  12. The local structure of transition metal doped semiconducting boron carbides

    Liu Jing; Dowben, P A [Department of Physics and Astronomy and the Nebraska Center for Materials and Nanoscience, Behlen Laboratory of Physics, University of Nebraska-Lincoln, PO Box 880111, Lincoln, NE 68588-0111 (United States); Luo Guangfu; Mei Waining [Department of Physics, University of Nebraska at Omaha, Omaha, NE 68182-0266 (United States); Kizilkaya, Orhan [J. Bennett Johnston Sr. Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Hwy., Baton Rouge LA 70806 (United States); Shepherd, Eric D; Brand, J I [College of Engineering, and the Nebraska Center for Materials and Nanoscience, N209 Walter Scott Engineering Center, 17th and Vine Streets, University of Nebraska-Lincoln, Lincoln, NE 68588-0511 (United States)

    2010-03-03

    Transition metal doped boron carbides produced by plasma enhanced chemical vapour deposition of orthocarborane (closo-1,2-C{sub 2}B{sub 10}H{sub 12}) and 3d metal metallocenes were investigated by performing K-edge extended x-ray absorption fine structure and x-ray absorption near edge structure measurements. The 3d transition metal atom occupies one of the icosahedral boron or carbon atomic sites within the icosahedral cage. Good agreement was obtained between experiment and models for Mn, Fe and Co doping, based on the model structures of two adjoined vertex sharing carborane cages, each containing a transition metal. The local spin configurations of all the 3d transition metal doped boron carbides, Ti through Cu, are compared using cluster and/or icosahedral chain calculations, where the latter have periodic boundary conditions.

  13. X-ray diffraction and absorption spectroscopic studies of copper mixed ligand complexes with aminophenol as one of the ligands

    X-ray diffraction (XRD) and X-ray absorption spectroscopic (XAS) studies have been conducted on two copper complexes, i.e., copper macrocyclic complex of succinic acid and ortho aminophenol (complex-1) and copper macrocyclic complex of pthalic acid and ortho aminophenol (complex-2). The diffraction pattern of the complexes have been recorded using Rigaku RINT-2000 X-ray diffractometer equipped with rotating anode X-ray tube operated at 40 kV and 100 mA. The X-ray absorption spectra of the complexes have been recorded at the K-edge of copper on Cauchois type bent crystal spectrograph having radius 0.4 m employing a mica crystal, oriented to reflect from (100) planes, for dispersion. The X-ray absorption near edge structure (XANES) parameters, viz., chemical shift, energy position of the principal absorption maximum and edge-width have been determined and discussed. From the extended X-ray absorption fine structure (EXAFS) data, the bond lengths have been calculated using three methods, namely, Levy's method, Lytle, Sayers and Stern's (LSS) method and Fourier transformation method. The results obtained have been compared with each other and discussed.

  14. Light Absorption Enhancement of Silicon-Based Photovoltaic Devices with Multiple Bandgap Structures of Porous Silicon

    Kuen-Hsien Wu

    2015-09-01

    Full Text Available Porous-silicon (PS multi-layered structures with three stacked PS layers of different porosity were prepared on silicon (Si substrates by successively tuning the electrochemical-etching parameters in an anodization process. The three PS layers have different optical bandgap energy and construct a triple-layered PS (TLPS structure with multiple bandgap energy. Photovoltaic devices were fabricated by depositing aluminum electrodes of Schottky contacts on the surfaces of the developed TLPS structures. The TLPS-based devices exhibit broadband photoresponses within the spectrum of the solar irradiation and get high photocurrent for the incident light of a tungsten lamp. The improved spectral responses of devices are owing to the multi-bandgap structures of TLPS, which are designed with a layered configuration analog to a tandem cell for absorbing a wider energy range of the incidental sun light. The large photocurrent is mainly ascribed to an enhanced light-absorption ability as a result of applying nanoporous-Si thin films as the surface layers to absorb the short-wavelength light and to improve the Schottky contacts of devices. Experimental results reveal that the multi-bandgap PS structures produced from electrochemical-etching of Si wafers are potentially promising for development of highly efficient Si-based solar cells.

  15. Changes in chemical state and local structure of green rust by addition of copper sulphate ions

    Suzuki, S. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan)], E-mail: ssuzuki@tagen.tohoku.ac.jp; Shinoda, K. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Sato, M. [Synchrotron Radiation Research Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Fujimoto, S. [Osaka University, 1-1 Yamadaoka, Suita, Osaka, 565-0871 (Japan); Yamashita, M. [University of Hyogo, 1-3-3, Higashikawasaki-cho, Chuo-ku, Kobe-shi, Hyogo, 650-0044 (Japan); Konishi, H. [Japan Atomic Energy Agency, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Doi, T.; Kamimura, T. [Sumitomo Metal Industries Ltd. 1-10, Fuso-cho, Amagasaki, Hyogo, 660-0891 (Japan); Inoue, K.; Waseda, Y. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan)

    2008-06-15

    The X-ray absorption near edge structure (XANES), the extended X-ray absorption fine structure (EXAFS) and X-ray diffraction (XRD) measurements were used for characterising the effect of the addition of copper sulphate ions on the chemical state and local structure of hydrosulphate green rust (GR). Fe K edge XANES spectra showed that Fe(II) in GR was partially oxidised by the addition of the copper sulphate solution. Cu K edge XANES spectra showed that the copper sulphate ions in the GR suspension were reduced to zero charge copper. Radial structural functions indicated that the structure of GR comprised edge sharing of FeO{sub 6} octahedral units, which was changed by the oxidation of Fe(II). In addition, it was found that the GR was partially oxidised to {alpha}-FeOOH by the addition of copper ions.

  16. Atomic Transition Frequencies, Isotope Shifts, and Sensitivity to Variation of the Fine Structure Constant for Studies of Quasar Absorption Spectra

    Berengut, J. C.; Dzuba, V. A.; Flambaum, V. V.; King, J. A.; Kozlov, M. G.; Murphy, M. T.; Webb, J. K.

    Theories unifying gravity with other interactions suggest spatial and temporal variation of fundamental "constants" in the Universe. A change in the fine structure constant, α = {e}2/hslash c , could be detected via shifts in the frequencies of atomic transitions in quasar absorption systems. Recent studies using 140 absorption systems from the Keck telescope and 153 from the Very Large Telescope, suggest that α varies spatially (61). That is, in one direction on the sky α seems to have been smaller at the time of absorption, while in the opposite direction it seems to have been larger.

  17. Structural vs electronic origin of renormalized band widths in TTF-TCNQ: An angular dependent NEXAFS study

    Sing, M; Meyer, J; Hoinkis, M; Glawion, S; Blaha, P; Gavrila, G; Jacobsen, Claus Schelde; Claessen, R

    2007-01-01

    We have performed angle-dependent near-edge x-ray absorption fine structure measurements in the Auger electron yield mode on the correlated quasi-one-dimensional organic conductor tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) in order to determine the orientation of the molecules in the...... the one-dimensional Hubbard model. Thereby, recent theoretical results are corroborated which invoke long-range Coulomb repulsion as alternative explanation to understand the spectral dispersions of TTF-TCNQ quantitatively within an extended Hubbard model....

  18. Dynamical tuning between nearly perfect reflection, absorption, and transmission of light via graphene/dielectric structures

    Linder, Jacob

    2016-01-01

    Exerting well-defined control over the reflection $(R)$, absorption $(A)$, and transmission $(T)$ of electromagnetic waves is a key objective in quantum optics. To this end, one often utilizes hybrid structures comprised of elements with different optical properties in order to achieve features such as high $R$ or high $A$ for incident light. A desirable goal would be the possibility to tune between all three regimes of nearly perfect reflection, absorption, and transmission within the same device, thus swapping between the cases $R\\to 1$, $A\\to1$, and $T\\to1$ dynamically. We here show that a dielectric interfaced with a graphene layer on each side allows for precisely this: by tuning only the Fermi level of graphene, all three regimes can be reached in the THz regime and below. Moreover, we show that the inclusion of cylindrical defects in the system offers a different type of control of the scattering of electromagnetic waves by means of the graphene layers.

  19. STRUCTURAL AND COHESION FUNDS ABSORPTION DEGREE AS AT QUARTER I 2012

    Cristian Nicolae STOINA

    2012-04-01

    Full Text Available The requirements imposed by the EU, the mechanisms of the community policies, the European rules and standards are challenges that manufacturers, processors, retailers and decision makers of the Romanian economic environment must cope with. In this article the structural and cohesion funds absorption degree was analyzed on the major allocation axis: transportation, environment, regional infrastructure, human resources development, increasing economic competitiveness, administrative capacity building and technical assistance.The purpose of this paper is to attain clear conclusions, which in turn may guide us to making recommendations on the identification of weaknesses that prevent a better absorption of the funds and determination of counteracting measures for these deficiencies.Among the main findings worth mentioning is the fact that the mechanism allowing access to European fi nancing is a functional, stable and efficient one. Of course, its performance could be greatly enhanced if the producers, processors, retailers and decision makers of the Romanian economic environment, previously mentioned, would give more signifi cance to this opportunity that makes the Romanian economic development possible.

  20. Arecibo Multi-Epoch HI Absorption Measurements Against Pulsars: Tiny-Scale Atomic Structure

    Stanimirovic, S; Pei, Z; Tuttle, K; Green, J T

    2010-01-01

    We present results from multi-epoch neutral hydrogen (HI) absorption observations of six bright pulsars with the Arecibo telescope. Moving through the interstellar medium (ISM) with transverse velocities of 10--150 AU/yr, these pulsars have swept across 1--200 AU over the course of our experiment, allowing us to probe the existence and properties of the tiny scale atomic structure (TSAS) in the cold neutral medium (CNM). While most of the observed pulsars show no significant change in their HI absorption spectra, we have identified at least two clear TSAS-induced opacity variations in the direction of B1929+10. These observations require strong spatial inhomogeneities in either the TSAS clouds' physical properties themselves or else in the clouds' galactic distribution. While TSAS is occasionally detected on spatial scales down to 10 AU, it is too rare to be characterized by a spectrum of turbulent CNM fluctuations on scales of 10-1000 AU, as previously suggested by some work. In the direction of B1929+10, an...

  1. ARECIBO MULTI-EPOCH H I ABSORPTION MEASUREMENTS AGAINST PULSARS: TINY-SCALE ATOMIC STRUCTURE

    We present results from multi-epoch neutral hydrogen (H I) absorption observations of six bright pulsars with the Arecibo telescope. Moving through the interstellar medium (ISM) with transverse velocities of 10-150 AU yr-1, these pulsars have swept across 1-200 AU over the course of our experiment, allowing us to probe the existence and properties of the tiny-scale atomic structure (TSAS) in the cold neutral medium (CNM). While most of the observed pulsars show no significant change in their H I absorption spectra, we have identified at least two clear TSAS-induced opacity variations in the direction of B1929+10. These observations require strong spatial inhomogeneities in either the TSAS clouds' physical properties themselves or else in the clouds' galactic distribution. While TSAS is occasionally detected on spatial scales down to 10 AU, it is too rare to be characterized by a spectrum of turbulent CNM fluctuations on scales of 101-103 AU, as previously suggested by some work. In the direction of B1929+10, an apparent correlation between TSAS and interstellar clouds inside the warm Local Bubble (LB) indicates that TSAS may be tracing the fragmentation of the LB wall via hydrodynamic instabilities. While similar fragmentation events occur frequently throughout the ISM, the warm medium surrounding these cold cloudlets induces a natural selection effect wherein small TSAS clouds evaporate quickly and are rare, while large clouds survive longer and become a general property of the ISM.

  2. Quick scanning monochromator for millisecond in situ and in operando X-ray absorption spectroscopy.

    Müller, O; Lützenkirchen-Hecht, D; Frahm, R

    2015-09-01

    The design and capabilities of a novel Quick scanning Extended X-ray Absorption Fine Structure (QEXAFS) monochromator are presented. The oscillatory movement of the crystal stage is realized by means of a unique open-loop driving scheme operating a direct drive torque motor. The entire drive mechanics are installed inside of a goniometer located on the atmospheric side of the vacuum chamber. This design allows remote adjustment of the oscillation frequency and spectral range, giving complete control of QEXAFS measurements. It also features a real step-scanning mode, which operates without a control loop to prevent induced vibrations. Equipped with Si(111) and Si(311) crystals on a single stage, it facilitates an energy range from 4.0 keV to 43 keV. Extended X-ray absorption fine structure spectra up to k = 14.4 Å(-1) have been acquired within 17 ms and X-ray absorption near edge structure spectra covering more than 200 eV within 10 ms. The achieved data quality is excellent as shown by the presented measurements. PMID:26429455

  3. Quick scanning monochromator for millisecond in situ and in operando X-ray absorption spectroscopy

    Müller, O.; Lützenkirchen-Hecht, D.; Frahm, R.

    2015-09-01

    The design and capabilities of a novel Quick scanning Extended X-ray Absorption Fine Structure (QEXAFS) monochromator are presented. The oscillatory movement of the crystal stage is realized by means of a unique open-loop driving scheme operating a direct drive torque motor. The entire drive mechanics are installed inside of a goniometer located on the atmospheric side of the vacuum chamber. This design allows remote adjustment of the oscillation frequency and spectral range, giving complete control of QEXAFS measurements. It also features a real step-scanning mode, which operates without a control loop to prevent induced vibrations. Equipped with Si(111) and Si(311) crystals on a single stage, it facilitates an energy range from 4.0 keV to 43 keV. Extended X-ray absorption fine structure spectra up to k = 14.4 Å-1 have been acquired within 17 ms and X-ray absorption near edge structure spectra covering more than 200 eV within 10 ms. The achieved data quality is excellent as shown by the presented measurements.

  4. Infrared absorption by two dimensional holes in GaAs-(ALx Ga1-x)As quantum well structures

    The coefficient of infrared absorption by 2 D holes in GaAs-(ALx Ga1-x)As quantum well structures is calculated. The contributions of intra subband as well as inter subband transitions are taken into account. It is shown that, on the absorption spectrum there is a sharp peak related by inter subband transitions. With increasing of temperature this peak is not sharp. The obtained results are agreed with experiment data. (author). 7 refs., 6 figs

  5. Uniform Catalytic Site in Sn-beta Zeolite Determined using X-ray Absorption Fine Structure

    Bare,S.; Kelly, S.; Sinkler, W.; Low, J.; Modica, F.; Valencia, S.; Corma, A.; Nemeth, L.

    2005-01-01

    The Sn silicate zeolite, Sn-{beta}, has been shown to be an efficient, selective heterogeneous catalyst for Baeyer-Villiger oxidations. Using primarily a multishell fit to extended X-ray absorption fine structure (EXAFS) data, we show that the Sn does not randomly insert into the {beta}-zeolite structure but rather occupies identical, specific, crystallographic sites. These sites are the T5/T6 sites in the six-membered rings. Moreover, the Sn is substituted in pairs on opposite sides of these six-membered rings. We believe that it is the specific, uniform crystallographic location of the Sn in the crystal structure that leads to sites with uniform catalytic activity, and consequently to the high chemical selectivity demonstrated for this catalyst. This manifests itself in the almost enzyme-like selectivity of this catalyst in Baeyer-Villiger oxidations. This uniform site distribution of the Sn suggests that there is likely a symbiotic relationship between the structure-directing agent in the zeolite synthesis and the Sn heteroatoms during the framework formation.

  6. Effects of heat treatment on optical absorption properties of Ni-P/AAO nano-array composite structure

    Liu, Yi-Fan; Wang, Feng-Hua; Guo, Dong-Lai; Huang, Sheng-You; Zou, Xian-Wu [Wuhan University, Department of Physics, Wuhan (China); Sang, Jian-Ping [Wuhan University, Department of Physics, Wuhan (China); Jianghan University, Department of Physics, Wuhan (China)

    2009-11-15

    Ni-P/AAO nano-array composite structure assemblies with Ni and P grown in the pores of anodic aluminum oxide (AAO) membranes were prepared by electroless deposition. The results of SEM, TEM and SAED show that as-deposited Ni-P nanowires have an amorphous structure and a few nanocrystallites form after annealing. The optical absorption spectra reveal that, as the annealing temperature increases, the absorption band edge of the Ni-P/AAO composite structure is obviously blue shifted, which is attributed to a decrease of the internal pressure after heat treatment. Meanwhile, the annealed Ni-P/AAO nano-array composite structure exhibits the absorption behavior of a direct band gap semiconductor. Details of this behavior are discussed together with the implications for potential device applications. (orig.)

  7. Characteristic Functions Describing the Power Absorption Response of Periodic Structures to Partially Coherent Fields

    Craeye, Christophe; Thomas, Christopher N

    2014-01-01

    Many new types of sensing or imaging surfaces are based on periodic thin films. It is explained how the response of those surfaces to partially coherent fields can be fully characterized by a set of functions in the wavenumber spectrum domain. The theory is developed here for the case of 2D absorbers with TE illumination and arbitrary material properties in the plane of the problem, except for the resistivity which is assumed isotropic. Sum and difference coordinates in both spatial and spectral domains are conveniently used to represent the characteristic functions, which are specialized here to the case of periodic structures. Those functions can be either computed or obtained experimentally. Simulations rely on solvers based on periodic-boundary conditions, while experiments correspond to Energy Absorption Interferometry (EAI), already described in the literature. We derive rules for the convergence of the representation versus the number of characteristic functions used, as well as for the sampling to be ...

  8. Extended x-ray absorption fine structure investigation of annealed carbon expanded austenite

    Oddershede, Jette; Christiansen, Thomas L.; Somers, Marcel A. J.;

    2012-01-01

    Carbon expanded austenite synthesized through carburizing of austenitic stainless steel powder at 380°C was annealed at 470°C and investigated with extended X-ray absorption fine structure (EXAFS) and synchrotron powder diffraction (SPD). SPD showed that the samples consisted of carbon expanded...... austenite and Hägg carbide, Ξ-M5C2. EXAFS showed that the Cr atoms were mainly present in environments similar to the carbides Hägg Ξ-M5C2 and M23C6. The environments of the Fe and Ni atoms were concluded to be largely metallic austenite. Light optical micrograph of stainless steel AISI 316 gas......-carburized in a temperature regime around 470°C. The surface zone is converted into carbon expanded austenite; the high interstitial content of carbon dissolved in the surface results in highly favorable materials properties. In the present article the local atomic environment of (annealed) carbon expanded...

  9. Compressive behavior and energy absorption of metal porous polymer composite with interpenetrating network structure

    LIU Yu; GONG Xiao-lu

    2006-01-01

    Interpenetrating phase composites (IPCs) are a new class of composite materials with improved combinations of mechanical and physical properties. This study was performed on a new type of IPC called metal porous polymer composite (MPPC) with an interpenetrating network structure. Aluminum-polypropylene (Al-PE) and Aluminum-epoxy resin (Al-Ep) composites were produced by infiltrating the polymer in the aluminum foam. The composite microstructures were characterized using SEM observation. The compressive behavior and energy absorption characteristics of MPPC were investigated and compared with the aluminum foams. The compressive modulus of composite was compared with the VOIGT-REUSS bounds and HASHIN-SHTRIKMAN (H-S) bounds models. The experimental modulus of compressive tests falls well within the theoretical models.

  10. Reflection-extented-x-ray-absorption-fine-structure spectroscopy at the carbon K-edge

    The authors report an investigation of the carbon K-edge Reflection-Extended X-Ray Absorption Fine Structure (refl-EXAFS) spectra from graphite, diamond and glassy carbon. There is good phase shift transferability between the two well-known bonding types in diamond and graphite, provided that appropriate inner potential corrections to the K-edge energy are made. The model spectra from diamond and graphite were used to investigate the nature of glassy carbon. It was found that, for the particular form of glassy carbon used in this study, the bonding more closely resembled sp3 than sp2. This result is preliminary pending evaluation of the influence of surface oxygen

  11. Development of a two-dimensional imaging system of X-ray absorption fine structure.

    Katayama, Misaki; Sumiwaka, Koichi; Hayashi, Kazuhiro; Ozutsumi, Kazuhiko; Ohta, Toshiaki; Inada, Yasuhiro

    2012-09-01

    A two-dimensional imaging system of X-ray absorption fine structure (XAFS) has been developed at beamline BL-4 of the Synchrotron Radiation Center of Ritsumeikan University. The system mainly consists of an ionization chamber for I(0) measurement, a sample stage, and a two-dimensional complementary metal oxide semiconductor (CMOS) image sensor for measuring the transmitted X-ray intensity. The X-ray energy shift in the vertical direction, which originates from the vertical divergence of the X-ray beam on the monochromator surface, is corrected by considering the geometrical configuration of the monochromator. This energy correction improves the energy resolution of the XAFS spectrum because each pixel in the CMOS detector has a very small vertical acceptance of ∼0.5 µrad. A data analysis system has also been developed to automatically determine the energy of the absorption edge. This allows the chemical species to be mapped based on the XANES feature over a wide area of 4.8 mm (H) × 3.6 mm (V) with a resolution of 10 µm × 10 µm. The system has been applied to the chemical state mapping of the Mn species in a LiMn(2)O(4) cathode. The heterogeneous distribution of the Mn oxidation state is demonstrated and is considered to relate to the slow delocalization of Li(+)-defect sites in the spinel crystal structure. The two-dimensional-imaging XAFS system is expected to be a powerful tool for analyzing the spatial distributions of chemical species in many heterogeneous materials such as battery electrodes. PMID:22898951

  12. Characterization of the Electronic Structure of Silicon Nanoparticles Using X-ray Absorption and Emission

    Vaverka, April Susan Montoya [Univ.of California, Davis, CA (United States)

    2008-01-01

    Resolving open questions regarding transport in nanostructures can have a huge impact on a broad range of future technologies such as light harvesting for energy. Silicon has potential to be used in many of these applications. Understanding how the band edges of nanostructures move as a function of size, surface termination and assembly is of fundamental importance in understanding the transport properties of these materials. In this thesis work I have investigated the change in the electronic structure of silicon nanoparticle assemblies as the surface termination is changed. Nanoparticles are synthesized using a thermal evaporation technique and sizes are determined using atomic force microscopy (AFM). By passivating the particles with molecules containing alcohol groups we are able to modify the size dependent band edge shifts. Both the valence and conduction bands are measured using synchrotron based x-ray absorption spectroscopy (XAS) and soft x-ray fluorescence (SXF) techniques. Particles synthesized via recrystallization of amorphous silicon/SiO2 multilayers of thicknesses below 10 nm are also investigated using the synchrotron techniques. These samples also show quantum confinement effects but the electronic structure is different from those synthesized via evaporation methods. The total bandgap is determined for all samples measured. The origins of these differences in the electronic structures are discussed.

  13. Effect of Internal Heat Recovery in Ammonia-Water Absorption Cooling Cycles: Exergy and Structural Analysis

    Miquel Nogués

    2009-03-01

    Full Text Available First and second law analysis have been conducted for three low temperature driven ammonia-water absorption cooling cycles with increasing internal heat recovery. Based on the results of exergy analysis the structural analysis has been achieved. The obtained Coefficients of Structural Bonds (CSB consider how the irreversibility of the whole cycle is affected by a change in the irreversibility related to an efficiency improvement of a single component. Trends for the different configurations are similar, while quantitative differences among the main heat exchangers are considerable. The highest values of the CSB are found for the refrigerant heat exchanger. Also the evaporator, the condenser, the generator and the absorber show values higher than unity. The lowest CSB’s are obtained in the solution heat exchanger. In general, CSB’s decrease with increasing efficiency. That means that for very efficient heat exchangers, a further improvement looks less attractive. The dephlegmator is an exception as it shows a singularity of the CSB value due to its complex interactions with the other components. Once the CSB’s are obtained for the main components, they can be used in the structural method of the thermoeconomic optimisation. This method enables us to find the optimum design of a component in a straightforward calculation.

  14. Recovery of x-ray absorption spectral profile in etched TiO{sub 2} thin films

    Sano, Keiji; Niibe, Masahito, E-mail: niibe@lasti.u-hyogo.ac.jp [Laboratory of Advanced Science and Technology for Industry, University of Hyogo, Kamigoori, Hyogo 678-1205 (Japan); Kawakami, Retsuo [Institute of Socio-Techno Science Technology, The University of Tokushima, Tokushima, Tokushima 770-8506 (Japan); Nakano, Yoshitaka [Institute of Science and Technology Research, Chubu University, Kasugai, Aichi 487-8501 (Japan)

    2015-05-15

    Near edge x-ray absorption fine structure (NEXAFS) spectra of plasma-etched TiO{sub 2} thin films were observed using the total fluorescence yield method involving visible emission. The disrupted spectrum recovered its as-grown (nonetched) profile, upon soft x-ray (SX) irradiation. This recovery was investigated by ultraviolet (UV) irradiation, spatial distribution measurements, exposing recovered samples to air, and NEXAFS measurements of ultrafine TiO{sub 2} particles. The spectral profile recovered upon UV irradiation, and at sample positions outside of the SX irradiation site. The recovered spectral profiles were disrupted again, upon exposure to air. Nonetched ultrafine TiO{sub 2} particles also exhibited a disrupted spectral profile, which was recovered upon SX irradiation. The spectral recovery is explained by a model involving electrons trapped in oxygen vacancies generated by etching.

  15. Percutaneous absorption of herbicides derived from 2,4-dichlorophenoxyacid: structure-activity relationship.

    Beydon, Dominique; Payan, Jean-Paul; Ferrari, Elisabeth; Grandclaude, Marie-Christine

    2014-08-01

    Ethyl to octyl esters of 2,4-dichlorophenoxy-acetic acids (2,4DAA), 2,4-dichlorophenoxy-propionic acids (2,4DPA) or 2,4-dichlorophenoxy-butyric acids (2,4DBA) are present in the most commonly used herbicides. Their use involves a significant risk of skin exposure, but little is known about the percutaneous flux of these substances. Studies have shown that percutaneous transition of esters may be dependent on their hydrolysis by esterases present in the skin. In this study, we describe ex vivo percutaneous absorption of seven pure esters (methyl to decyl) with a 2,4DA structure for rats (n=6) and humans (n=7). Esters were applied at 50 μL cm(-2) to dermatomed skin (approximately 0.5 mm thick) for 24 h. The enzymatic constants for hydrolysis of each ester by skin esterases were determined in vitro using skin homogenates from both species. Structure-activity relationships linking the evolution of the ex vivo percutaneous flux of esters and the 2,4D structure with enzymatic (Vmax; Km) and/or physical parameters (molecular weight, molecular volume, size of the ester, log(kow)) were examined to develop a good flux estimation model. Although the percutaneous penetration of all of the esters of the 2,4D family are "esterase-dependent", the decreasing linear relationship between percutaneous penetration and hyrophobicity defined by the logarithm for the octanol-water partition coefficient (log(kow)) is the most pertinent model for estimating the percutaneous absorption of esters for both species. The mean flux of the free acid production by the esterases of the skin is not the limiting factor for percutaneous penetration. The rate of hydrolysis of the esters in the skin decreases linearly with log(kow), which would suggest that either the solubility of the esters in the zones of the skin that are rich in esterases or the accessibility to the active sites of the enzyme is the key factor. The structure-activity relationship resulting from this study makes it possible, in

  16. Hydrogen absorption kinetics and structural properties of Mg85Ni10Ca5 and Mg90Ni10

    Mg85Ni10Ca5 and Mg90Ni10 were prepared by melting mixtures of the elements in mild steel crucibles and pouring them into copper molds. Hydrogen absorption kinetics and structural properties of the alloys were characterized by the volumetric method using a Sievert's apparatus, X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The crystallite size of Mg in Mg85Ni10Ca5, which is evaluated by XRD peak broadening, is about 50% smaller than that in Mg90Ni10. In addition, the nanometer-scale structure composed of Mg, Mg2Ni, Mg2Ca was observed in Mg85Ni10Ca5. Mg85Ni10Ca5 shows better hydrogen absorption kinetics than Mg90Ni10 in the temperature range of room temperature to 573 K. The better absorption kinetics of Mg85Ni10Ca5 is mainly attributed to the nanometer-scale structure

  17. Time-resolved pump-probe X-ray absorption fine structure spectroscopy of Gaq3

    Gallium(tris-8-hydroxyquinoline) (Gaq3) belongs to a class of metal organic compounds, used as electron transport layer and emissive layer in organic light emitting diodes. Many research activities have concentrated on the optical and electronic properties, especially of the homologue molecule aluminum(tris-8-hydroxyquinoline) (Alq3). Knowledge of the first excited state S1 structure of these molecules could provide deeper insight into the processes involved into the operation of electronic devices, such as OLEDs and, hence, it could further improve their efficiency and optical properties. Until now the excited state structure could not be determined experimentally. Most of the information about this structure mainly arises from theoretical calculations. X-ray absorption fine structure (XAFS) spectroscopy is a well developed technique to determine both, the electronic and the geometric properties of a sample. The connection of ultrashort pulsed X-ray sources with a pulsed laser system offers the possibility to use XAFS as a tool for studying the transient changes of a sample induced by a laser pulse. In the framework of this thesis a new setup for time-resolved pump-probe X-ray absorption spectroscopy at PETRA III beamline P11 was developed for measuring samples in liquid form. In this setup the sample is pumped into its photo-excited state by a femtosecond laser pump pulse with 343 nm wavelength and after a certain time delay probed by an X-ray probe pulse. In this way the first excited singlet state S1 of Gaq3 dissolved in benzyl alcohol was analyzed. A structural model for the excited state structure of the Gaq3 molecule based on the several times reproduced results of the XAFS experiments is proposed. According to this model it was found that the Ga-NA bond length is elongated, while the Ga-OA bond length is shortened upon photoexcitation. The dynamics of the structural changes were not the focus of this thesis. Nevertheless the excited state lifetime of Gaq3

  18. Effect of amorphous evolution on structure and absorption properties of FeSiCr alloy powders

    The master alloys of Fe87.5−xSi13.5Crx (x=0, 4, 8, 12 at%) were prepared in vacuum induction melting furnace. Corresponding powder samples were obtained by 60 h ball milling of the crushed master alloys, and studied by morphological, microstructural, electromagnetic and microwave absorption tests in the frequency range from 0.5 to 18 GHz. The powders were characterized by a particle size less than 1 μm and a grain size less than 100 nm. In the cases of x≥8, Fe3Si phase with D03-type structure was observed, and the powders became amorphous completely. A crystallization temperature of 685 K was found for x=8. Coercivity force and saturation magnetization of the powders decreased with the increasing of Cr content. As an electromagnetic wave absorbing material, the minimum reflectivity was −15.5 dB at 8.5 GHz and the absorption band was broad for x=8 powders. - Highlights: ► When Cr is 8 at%, after 60 h milling, D03 superlattice appeared. And exothermic peak appears at 685 K. ► With increasing Cr content, Ms decreases from 145 to 99 emu/g; μ″ is larger than the others at low frequency. ► The minimum reflectivity is −15.5 dB at 8.5 GHz for Cr content is 8 at% when thickness is 2 mm. ► The amorphous Fe78.5Si13.5Cr8 alloy can be applied as electromagnetic wave absorber

  19. Does the fine structure constant vary? A third quasar absorption sample consistent with varying alpha

    Webb, J K; Flambaum, V V; Curran, S J

    2003-01-01

    We report preliminary results from a third sample of quasar absorption line spectra from the Keck telescope which has been studied to search for any possible variation of the fine structure constant, alpha. This third sample, which is larger than the sum of the two previously published samples, shows the same effect, and also gives, as do the previous two samples, a significant result. The combined sample yields a highly significant effect, da/a = (alpha_z - alpha_0)/alpha_0 = -0.57 +/- 0.10 x 10^{-5}, averaged over the redshift range 0.2 < z < 3.7. We include a brief discussion of small-scale kinematic structure in quasar absorbing clouds. However, kinematics are unlikely to impact significantly on the averaged non-zero da/a above, and we have so far been unable to identify any systematic effect which can explain it. New measurements of quasar spectra obtained using independent instrumentation and telescopes are required to properly check the Keck results.

  20. The parsec-scale structure of radio-loud broad absorption line quasars

    Bruni, G; Mack, K -H; Montenegro-Montes, F M; González-Serrano, J I; Holt, J; Jiménez-Luján, F

    2013-01-01

    Broad Absorption Line Quasars (BAL QSOs) belong to a class of objects not well-understood as yet. Their UV spectra show BALs in the blue wings of the UV resonance lines, due to ionized gas with outflow velocities up to 0.2 c. They can have radio emission difficult to characterize, and that needs to be studied at various wavelengths and resolutions. We aim at studying the pc-scale properties of their synchrotron emission, and in particular at determining their core properties. We performed observations in Very Long Baseline Interferometry (VLBI) technique, using both the European VLBI Network (EVN) at 5 GHz, and the Very Long Baseline Array (VLBA) at 5 and 8.4 GHz to map the pc-scale structure of the brightest radio-loud objects of our sample, allowing a proper morphological interpretation. A variety of morphologies have been found: 9 BAL QSOs on a total of 11 observed sources have a resolved structure. Core-jet, double and symmetric objects are present, suggesting different orientations. In some cases the sou...

  1. The Compact Structure of Radio-Loud Broad Absorption Line Quasars

    Liu, Y; Wang, T G; Xie, F G

    2008-01-01

    We present the results of EVN+MERLIN VLBI polarization observations of 8 Broad Absorption Line (BAL) quasars at 1.6 GHz, including 4 LoBALs and 4 HiBALs with either steep or flat spectra on VLA scales. Only one steep-spectrum source, J1122+3124, shows two-sided structure on the scale of 2 kpc. The other four steep-spectrum sources and three flat-spectrum sources display either an unresolved image or a core-jet structure on scales of less than three hundred parsecs. In all cases the marginally resolved core is the dominant radio component. Linear polarization in the cores has been detected in the range of a few to 10 percent. Polarization, together with high brightness temperatures (from 2*10^9-5*10^10 K), suggest a synchrotron origin for the radio emission. There is no apparent difference in the radio orphologies or polarization between low-ionization and high-ionization BAL QSOs nor between flat- and steep-spectrum sources. We discuss the orientation of BAL QSOs with both flat and steep spectra, and consider...

  2. The compact structure of radio-loud broad absorption line quasars

    Liu, Y.; Jiang, D. R.; Wang, T. G.; Xie, F. G.

    2008-11-01

    We present the results of EVN+MERLIN very long baseline interferometry (VLBI) polarization observations of eight broad absorption line (BAL) quasars at 1.6 GHz, including four low-ionization BAL quasars (LoBALs) and four high-ionization BAL quasars (HiBALs) with either steep or flat spectra on Very Large Array (VLA) scales. Only one steep-spectrum source, J1122+3124, shows two-sided structure on the scale of 2 kpc. The other four steep-spectrum sources and three flat-spectrum sources display either an unresolved image or a core-jet structure on scales of less than 300 pc. In all cases, the marginally resolved core is the dominant radio component. Linear polarization in the cores has been detected in the range of a few to 10 per cent. Polarization, together with high brightness temperatures (from 2 × 109 to 5 × 1010K), suggests a synchrotron origin for the radio emission. There is no apparent difference in the radio morphologies or polarization between low-ionization and high-ionization BAL quasi-stellar objects (QSOs) or between flat- and steep-spectrum sources. We discuss the orientation of BAL QSOs with both flat and steep spectra, and consider a possible evolutionary scenario for BAL QSOs. In this scenario, BAL QSOs are probably a young population of radio sources that are compact steep spectrum or GHz peaked radio source analogues at the low end of radio power.

  3. Electronic structures of silicon monoxide film probed by X-ray absorption spectroscopy

    Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie

    2013-06-01

    Electronic structures of thin films of silicon monoxides (SiO) deposited on a solid surface have been in-situ investigated by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS). As a substrate, a highly oriented pyrolytic graphite (HOPG) was used because the hybridization between molecules and substrate can be excluded due to the inertness of the surface. For thin films with less than monolayer, XPS spectrum showed that the binding energy of the Si 1s is located just between those of the elemental silicon (Si0) and SiO2 (Si4 +). The result indicates that the stable divalent silicon surely exists in the deposited SiO layer. For the Si K-edge XAFS spectrum of the SiO thin film, the energy of the core-to-valence resonance peak is also located between those of the elemental silicon (Si0) and SiO2 (Si4 +). The polarization dependence of the Si K-edge XAFS spectra for the SiO film revealed that the SiO molecules are well-ordered and almost perpendicularly oriented on HOPG surface. The XAFS results also support the existence of the silicon divalent states in the deposited SiO films. The obtained well-ordered SiO films with divalent silicon will become an excellent starting material for the synthesis of low-dimensional SiOx films.

  4. Ab-initio multiplet calculations of Fe-L2,3 X-ray absorption spectra in LiFePO4 and FePO4

    Soft X-ray absorption near-edge structures (XANES) at the L2,3-edges of transition metal has been widely used for investigating the chemical reactions during charge-discharge cycles in the cathode materials of lithium ion batteries. In order to extract the information about the electronic structures from the experimental results, however, a theoretical tool that can deal with the strong electronic correlations between 2p and 3d electrons is necessary. In this study, the ab-initio multiplet method based on the relativistic configuration interaction (CI) method has been applied to the calculations of Fe-L2,3 XANES of LiFePO4 and FePO4. Experimental XANES spectra were quantitatively reproduced by this method. The effects of local symmetries around Fe ions to the spectral shapes were also discussed. (author)

  5. Electronic charge transfer in cobalt doped fullerene thin films and effect of energetic ion impacts by x-ray absorption spectroscopy

    We report on the electronic charge transfer in cobalt doped fullerene thin films by means of near-edge x-ray-absorption fine structure (NEXAFS) spectroscopy measurement. Co-doped fullerene films were prepared by co-deposition technique and subjected to energetic ion irradiation (120 MeV Au) for possibly alignment or interconnect of randomly distributed metal particles. Polarization dependent NEXAFS spectra revealed the alignment of Co and C atoms along the irradiated ionic path. The structural changes in Co-doped as-deposited and ion irradiated fullerene films were investigated by means of Raman spectroscopy measurements. Downshift of pentagonal pinch mode Ag(2) in Raman spectroscopy indicated the electronic charge transfer from Co atom to fullerene molecules, which is further confirmed by NEXAFS at C K-edge for Co-doped fullerene films.

  6. Electron and proton absorption calculations for a graphite/epoxy composite model. [large space structures

    Long, E. R., Jr.

    1979-01-01

    The Bethe-Bloch stopping power relations for inelastic collisions were used to determine the absorption of electron and proton energy in cured neat epoxy resin and the absorption of electron energy in a graphite/epoxy composite. Absorption of electron energy due to bremsstrahlung was determined. Electron energies from 0.2 to 4.0 MeV and proton energies from 0.3 to 1.75 MeV were used. Monoenergetic electron energy absorption profiles for models of pure graphite, cured neat epoxy resin, and graphite/epoxy composites are reported. A relation is determined for depth of uniform energy absorption in a composite as a function of fiber volume fraction and initial electron energy. Monoenergetic proton energy absorption profiles are reported for the neat resin model. A relation for total proton penetration in the epoxy resin as a function of initial proton energy is determined. Electron energy absorption in the composite due to bremsstrahlung is reported. Electron and proton energy absorption profiles in cured neat epoxy resin are reported for environments approximating geosynchronous earth orbit.

  7. Si K Edge Structure and Variability in Galactic X-Ray Binaries

    Schulz, Norbert S.; Corrales, Lia; Canizares, Claude R.

    2016-08-01

    We survey the Si K edge structure in various absorbed Galactic low-mass X-ray binaries (LMXBs) to study states of silicon in the inter- and circum-stellar medium. The bulk of these LMXBs lie toward the Galactic bulge region and all have column densities above 1022 cm‑2. The observations were performed using the Chandra High Energy Transmission Grating Spectrometer. The Si K edge in all sources appears at an energy value of 1844 ± 0.001 eV. The edge exhibits significant substructure that can be described by a near edge absorption feature at 1849 ± 0.002 eV and a far edge absorption feature at 1865 ± 0.002 eV. Both of these absorption features appear variable with equivalent widths up to several mÅ. We can describe the edge structure using several components: multiple edge functions, near edge absorption excesses from silicates in dust form, signatures from X-ray scattering optical depths, and a variable warm absorber from ionized atomic silicon. The measured optical depths of the edges indicate much higher values than expected from atomic silicon cross sections and interstellar medium abundances, and they appear consistent with predictions from silicate X-ray absorption and scattering. A comparison with models also indicates a preference for larger dust grain sizes. In many cases, we identify Si xiii resonance absorption and determine ionization parameters between log ξ = 1.8 and 2.8 and turbulent velocities between 300 and 1000 km s‑1. This places the warm absorber in close vicinity of the X-ray binaries. In some data, we observe a weak edge at 1.840 keV, potentially from a lesser contribution of neutral atomic silicon.

  8. Structure of absorption and luminescence centers in potassium and cesium haloid salts with impurities of thetraedrical anions

    Interrelation between vibronic srtucture of luminescence spectra, structure of IR absorption spectra and local symmetry of impurity molecular anions CrO42-, MoO42-, ReO4- in crystals of haloid salts of potassium and cesium is established

  9. Constraining the Variation of the Fine Structure Constant with Observations of Narrow Quasar Absorption Lines

    Songaila, A

    2014-01-01

    The unequivocal demonstration of temporal or spatial variability in a fundamental constant of nature would be of enormous significance. Recent attempts to measure the variability of the fine structure constant, alpha, over cosmological time, using high resolution spectra of high redshift quasars observed with 10m class telescopes, have produced conflicting results. We used the Many Multiplet (MM) method with Mg II and Fe II lines on very high signal-to-noise, high resolution (R = 72,000) Keck HIRES spectra of eight narrow quasar absorption systems and show, using careful wavelength calibrations, that the systematic wavelength errors are too large for previous observations to have had the sensitivity to detect such variation using this technique. We find no significant change in alpha, Delta(alpha)/alpha =(0.00 +/- 0.24) x 10^(-5), in the redshift range z=0.7-1.5. We also show that the scatter in measurements of Delta(alpha)/alpha arising from line selection can be considerably larger than assigned statistical...

  10. The Impact of EU Structural Fund Support and Problems of its Absorption

    Daiva Jurevičienė

    2013-06-01

    Full Text Available Targeted allocation of EU support in Lithuania can help resolving a number of problems and achieving significant results in a variety of areas. However, rush to absorb support may lead to a little, zero or even negative impact on national economy. In addition, EU support opportunities may distort investment motivation. This paper deals with issues related to the impact of EU support and problems of its absorption. The impact of EU support on the national economy has been established in three areas: attraction of foreign direct investment state investments into capital formation, and experience of companies, which are EU support beneficiaries. The paper proposes using regression analysis in search and evaluation of relations while obtaining more information about programmes, priorities and the impact of structural support on different indicators. In addition, it focuses on ascertaining the effectiveness of governmental and company spending. Furthermore, as companies – EU support beneficiaries – are engaged in different economic activities, their experience cannot be ascertained from statistical data; consequently, findings of an expert survey are presented to demonstrate the experience acquired by business companies as well as problems they face. Limitation of research was a short period of time to evaluate (only four years of the current funding period

  11. Speciation of copper in a range of food types by X-ray absorption spectroscopy.

    Ceko, Melanie J; Aitken, Jade B; Harris, Hugh H

    2014-12-01

    Copper (Cu) is an essential element and the effects of diets deficient in it are well established. However, the effects of long-term high copper intake are less clear. The chemical form of copper from food sources and its resultant bioavailability is a potentially important factor in its biological activity. X-ray Absorption Near-Edge Structure (XANES) was used to determine the chemical forms of Cu in a range of foods that would make significant contributions to total copper absorption in a standard diet, as well as a chlorinated tap water sample. Analysis of the Cu K-edge XANES spectra suggested that Cu existed in both Cu(I) and Cu(II) forms, with the following five model compounds: Cu(I) acetate; Cu(II) acetate; Cu(I)-glutathione; Cu(I)-cysteine; and, Cu(II)-histidine being fitted to the sample spectra. This research suggested that the absorption of dietary copper could vary markedly dependent on the types of food consumed and the different bioavailability of the Cu species they contain. PMID:24996304

  12. A surface extended X-ray absorption fine structure study of tellurium adsorbed onto Si(100)

    Burgess, S. R.; Cowie, B. C. C.; Wilks, S. P.; Dunstan, P. R.; Dunscombe, C. J.; Williams, R. H.

    1996-09-01

    The adsorption of tellurium on Si(100) has been studied using surface extended X-ray adsorption fine structure (SEXAFS) and X-ray standing wave spectroscopy (XSW). This particular system is of interest due to its potential applicability in the surfactant aided growth of CdHgTeCdTeSi(100) based infra-red detectors. The Te/Si(100) structure was generated by depositing a thick layer (˜ 100 Å) of CdTe onto a clean Si (2 × 1) double domain surface, and annealing the sample to 350°C. This resulted is a ˜ 1 ML Te terminated surface where the (2 × 1) reconstruction was lost in favour of a (1 × 1) symmetry. X-ray absorption of the Te L 3 edge ( E = 4341 eV), with a photon energy range of 4440-4700 eV, was probed using a total yield detection scheme. The SEXAFS results indicated that the Te atoms sat in 2-fold bridge sites directly above a fourth layer Si atom. The corresponding bond length was measured to be 2.52 ± 0.05 Å. The XSW measurements of the (400) reflection gave a coherent position of 1.63 ± 0.03 Å and a coherent fraction of 0.65. This is consistent with the breaking of the SiSi dimers and thus could be an example of the phenomena of adsorbate-induced dereconstruction of the surface. These results are compared with those of Bennet et al. who examined a similar system using soft X-ray photoemission (SXPS) and the STM study of Yoshikawa et al.

  13. Energetics, structures, vibrational frequencies, vibrational absorption, vibrational circular dichroism and Raman intensities of Leu-enkephalin

    Here we present several low energy conformers of Leu-enkephalin (LeuE) calculated with the density functional theory using the Becke 3LYP hybrid functional and the 6-31G* basis set. The structures, conformational energies, vibrational frequencies, vibrational absorption (VA) intensities, vibrational circular dichroism (VCD) intensities and Raman scattering intensities are reported for the conformers of LeuE which are expected to be populated at room temperature. The species of LeuE present in non-polar solvents is the neutral non-ionic species with the NH2 and CO2H groups, in contrast to the zwitterionic neutral species with the NH3+ and CO2- groups which predominates in aqueous solution and in the crystal. All of our attempts to find the zwitterionic species in the isolated state failed, with the result that a hydrogen atom from the positively charged N-terminus ammonium group transferred either to one of the oxygens of the carboxylate group of the C-terminus or to the oxygen of the amide group of one of the other residues. Hence we conclude that the zwitterionic species of LeuE is not stable in the isolated state. Spectral simulations of the species expected to be found in the isolated state can be compared to the measured VA, VCD and Raman spectra of LeuE in non-polar solvents to identify which conformer or conformers of LeuE are present in these media. Characteristic features in the VCD spectra are more sensitive to conformational changes than those in either the VA or Raman spectra, similar to the characteristic features in electronic circular dichroism spectra with respect to those in the UV-vis electronic absorption spectra. Finally, we have also attempted to stabilize the zwitterionic species by treating the aqueous environment by using a continuum solvent approach, the Onsager model. Here we found that the zwitterionic species is now stable. The neutral species in an aqueous environment was also modelled by the continuum solvent approaches to determine the

  14. X-ray absorption studies of La/sub 2-x/Sr/sub x/CuO/sub 4/ and Y/sub 1-x/Pr/sub x/Ba/sub 2/Cu/sub 3/O/sub 7-δ/

    The question of valence of Cu and rare-earth atoms in the newly discovered oxide superconductors with high transition temperatures is crucial to the understanding of their electronic structure. The authors have measured the X-Ray Absorption Near Edge Structure (XANES) of Cu K transition and Pr L/sub III/ transition to obtain information on the valence of Cu, ad Pr in La/sub 2-x/Sr/sub x/CuO/sub 4/ and Y/sub 1-x/Pr/sub x/Ba/sub 2/Cu/sub 3/O/sub 7-δ/. The authors present the experimental results, compare them with calculations of absorption cross-section for model atomic clusters, and discuss the valence of Cu as a function of oxygen concentration

  15. Fine structures in the optical absorption spectra of photochemical silver in silver halides? A call for further research

    Georgiev, Mladen

    2007-01-01

    A survey is presented of the work done so far to check earlier claims that a fine structure may be observed to occur under certain circumstances in the impurity spectral range of the optical absorption spectra of silver halides following photostimulation in the intrinsic range. This structure, associated with the photochemical formation of silver specks, has been questioned over the years. We now weigh carefully the experimental evidence on the silver halides against a background of similar d...

  16. Biomedical applications of X-ray absorption and vibrational spectroscopic microscopies in obtaining structural information from complex systems

    Aitken, Jade B.; Carter, Elizabeth A. [School of Chemistry, University of Sydney, NSW 2006 (Australia); Eastgate, Harold [Eastmac Pty Ltd, 8 Cassinia Close, Knoxfield, Vic 3180 (Australia); Hackett, Mark J.; Harris, Hugh H.; Levina, Aviva [School of Chemistry, University of Sydney, NSW 2006 (Australia); Lee, Y.-C.; Chen, C.-I. [National Synchrotron Radiation Research Centre, No. 101 Hsin-Ann Road, Hsinchu 30076, Taiwan (China); Lai, Barry; Vogt, Stefan [X-ray Science Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Lay, Peter A., E-mail: p.lay@chem.usyd.edu.a [School of Chemistry, University of Sydney, NSW 2006 (Australia)

    2010-02-15

    Protein crystallography and NMR spectroscopy took decades to emerge as routine techniques in structural biology. X-ray absorption spectroscopy now has reached a similar stage of maturity for obtaining complementary local structural information around metals in metalloproteins. However, the relatively recent emergence of X-ray and vibrational spectroscopic microprobes that build on these techniques has enabled the structural information obtained from the 'mature' techniques on isolated biomolecules to be translated into in situ structural information from inhomogeneous complex systems, such as whole cells and tissues.

  17. Hydrothermal synthesis, X-ray absorption and luminescence properties of Tb3+ doped LaPO4

    Tb3+ activated LaPO4 nano-phosphors have been prepared by a hydrothermal method. Luminescence spectra in VUV–vis range as well as fluorescence decays were studied for bulk and nano-phosphors. Bulk sample exhibits a relatively fast decay time. The 5D3 emissions from Tb3+ ions increase under X-ray excitation in comparison with that under ultraviolet light excitation. X-ray absorption near-edge structure (XANES) was employed to study the chemical environment and energy transfer efficiency to optical emission. XANES results across different element absorption edges indicate that the chemical environment does not change significantly, only oxygen contributes to luminescence negatively. - Highlights: • Nanorods LaPO4 with different sizes are prepared with hydrothermal method. • Luminescence properties of bulk and nano LaPO4:Tb samples are compared. • La, Tb and P contribute to luminescence positively at the measured absorption edges. • At oxygen absorption edges, quantum efficiency of optical emission decreases

  18. Hydrothermal synthesis, X-ray absorption and luminescence properties of Tb{sup 3+} doped LaPO{sub 4}

    Hou, Dejian [MOE Laboratory of Bioinorganic and Synthetic Chemistry, KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275 (China); Department of Chemistry, The University of Western Ontario, London, Ontario, Canada N6A 5B7 (Canada); Guo, Xiaoxuan [Department of Chemistry, The University of Western Ontario, London, Ontario, Canada N6A 5B7 (Canada); Liu, Chunmeng [MOE Laboratory of Bioinorganic and Synthetic Chemistry, KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275 (China); Sham, Tsun-Kong, E-mail: tsham@uwo.ca [Department of Chemistry, The University of Western Ontario, London, Ontario, Canada N6A 5B7 (Canada); Liang, Hongbin, E-mail: cesbin@mail.sysu.edu.cn [MOE Laboratory of Bioinorganic and Synthetic Chemistry, KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275 (China); Gao, Jing; Sun, Xuhui [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Materials Laboratory (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China); Zhang, Bingbing; Zhan, Fei; Huan, Yan; Tao, Ye [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100039 (China)

    2015-09-15

    Tb{sup 3+} activated LaPO{sub 4} nano-phosphors have been prepared by a hydrothermal method. Luminescence spectra in VUV–vis range as well as fluorescence decays were studied for bulk and nano-phosphors. Bulk sample exhibits a relatively fast decay time. The {sup 5}D{sub 3} emissions from Tb{sup 3+} ions increase under X-ray excitation in comparison with that under ultraviolet light excitation. X-ray absorption near-edge structure (XANES) was employed to study the chemical environment and energy transfer efficiency to optical emission. XANES results across different element absorption edges indicate that the chemical environment does not change significantly, only oxygen contributes to luminescence negatively. - Highlights: • Nanorods LaPO{sub 4} with different sizes are prepared with hydrothermal method. • Luminescence properties of bulk and nano LaPO{sub 4}:Tb samples are compared. • La, Tb and P contribute to luminescence positively at the measured absorption edges. • At oxygen absorption edges, quantum efficiency of optical emission decreases.

  19. An X-ray absorption spectroscopy study of the inversion degree in zinc ferrite nanocrystals dispersed on a highly porous silica aerogel matrix.

    Carta, D; Marras, C; Loche, D; Mountjoy, G; Ahmed, S I; Corrias, A

    2013-02-01

    The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO(2) aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn(2+) ions are at the tetrahedral sites and trivalent Fe(3+) ions occupy octahedral sites (normal spinel). When particle size decreases, Zn(2+) ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix. PMID:23406136

  20. Pressure-induced changes in the structural and absorption properties of crystalline 5-nitramino-3,4-dinitropyrazole

    Dong Xiang; Qiong Wu; Zhichao Liu; Weihua Zhu; Heming Xiao

    2015-10-01

    Periodic density functional theory with dispersion correction (DFT-D) was used to study the structural, electronic, and absorption properties of crystalline 5-nitramino-3, 4-dinitropyrazole (NADNP) under hydrostatic compression of 0-140 GPa. The results indicate that the PBE-G06 is the best functional for studying NADNP. As the pressure increases, the lattice of parameters, band gap, density of states and absorption spectra change regularly except for 126 GPa, where NADNP begins to decompose and form a new bond. An analysis of the band gap and density of states indicates that NADNP becomes more and more sensitive under compression. The absorption spectra show that NADNP has relatively high optical activity with increasing pressure.

  1. Phonon assisted free carrier magneto-absorption in quantum well structures

    The theory of free-carrier absorption is developed for quasi-two-dimensional quantum well in a quantizing magnetic field for the case where the carriers are scattered by polar optical phonons, piezoelectric phonons and nonpolar optical phonons and the radiation field is polarized perpendicular to the plane of the layer. The free-carrier absorption coefficients found for the case nondegenrate electron gas. For polar and nonpolar optical phonons the free-carrier absorption coefficient oscillates as a functions of the magnetic field and photon frequency with resonance occuringwhere are the cyclotron, photon and phonon frequency, respectively. For elastic scattering with piezoelectric phonons resonance's are expected. The obtained results are compared with those of the theory of free-carrier absorption in the absence of magnetic field

  2. Structural reconstruction of the catalytic center of LiPDF through multiple scattering calculation with MXAN

    Peptide deformylase (PDF, EC 3.5.1.27) is essential for the normal growth of eubacterium but not for mammalians. Recently, PDF has been studied as a target for new antibiotics. In this paper, X-ray absorption spectroscopy was employed to determine the local structure around the zinc ion of PDF from Leptospira Interrogans in dry powder, because it is very difficult to obtain the crystallized sample of LiPDF. We performed X-ray absorption near edge structure (XANES) calculation and reconstructed successfully the local geometry of the active center, and the results from calculations show that a water molecule (Wat1) has moved towards the zinc ion and lies in the distance range to coordinate with the zinc ion weakly. In addition, the sensitivity of theoretical spectra to the different ligand bodies was evaluated in terms of goodness-of-fit

  3. Structural reconstruction of the catalytic center of LiPDF through multiple scattering calculation with MXAN

    Guo Xiaoyun [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China); School of Life Science, Key Laboratory of Structural Biology, University of Science and Technology of China, 230026 Hefei, Anhui (China); Chu Wangsheng [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China); Department of Physics, University of Science and Technology of China, 230026 Hefei, Anhui (China); Ma Sixuan [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China); Gong Weimin [National Laboratory of Biomacromolecules, Institute of Biophysics, Chinese Academy of Sciences, 100101 Beijing (China); Benfatto, Maurizio [Instituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, 00044 Frascati (Italy); Hu Tiandou [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China); Xie Yaning [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China); Wu Ziyu [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China) and Instituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, 00044 Frascati (Italy)]. E-mail: wuzy@mail.ihep.ac.cn

    2006-11-15

    Peptide deformylase (PDF, EC 3.5.1.27) is essential for the normal growth of eubacterium but not for mammalians. Recently, PDF has been studied as a target for new antibiotics. In this paper, X-ray absorption spectroscopy was employed to determine the local structure around the zinc ion of PDF from Leptospira Interrogans in dry powder, because it is very difficult to obtain the crystallized sample of LiPDF. We performed X-ray absorption near edge structure (XANES) calculation and reconstructed successfully the local geometry of the active center, and the results from calculations show that a water molecule (Wat1) has moved towards the zinc ion and lies in the distance range to coordinate with the zinc ion weakly. In addition, the sensitivity of theoretical spectra to the different ligand bodies was evaluated in terms of goodness-of-fit.

  4. Sulfur K-edge absorption spectroscopy on selected biological systems

    Sulfur is an essential element in organisms. In this thesis investigations of sulfur compounds in selected biological systems by XANES (X-ray Absorption Near Edge Structure) spectroscopy are reported. XANES spectroscopy at the sulfur K-edge provides an excellent tool to gain information about the local environments of sulfur atoms in intact biological samples - no extraction processes are required. Spatially resolved measurements using a Kirkpatrick-Baez mirror focusing system were carried out to investigate the infection of wheat leaves by rust fungi. The results give information about changes in the sulfur metabolism of the host induced by the parasite and about the extension of the infection into visibly uninfected plant tissue. Furthermore, XANES spectra of microbial mats from sulfidic caves were measured. These mats are dominated by microbial groups involved in cycling sulfur. Additionally, the influence of sulfate deprivation and H2S exposure on sulfur compounds in onion was investigated. To gain an insight into the thermal degradation of organic material the influence of roasting of sulfur compounds in coffee beans was studied. (orig.)

  5. Experimental and theoretical study of electronic structure of aluminum in extreme conditions with X-ray absorption spectroscopy

    Matter in extreme conditions belongs to Warm Dense Matter regime which lays between dense plasma regime and condensed matter. This regime is still not well known, indeed it is very complex to generate such plasma in the laboratory to get experimental data and validate models. The goal of this thesis is to study electronic structure of aluminum in extreme conditions with X-ray absorption spectroscopy. Experimentally aluminum has reached high densities and high temperatures, up to now unexplored. An X-ray source has also been generated to probe highly compressed aluminum. Two spectrometers have recorded aluminum absorption spectra and aluminum density and temperature conditions have been deduced thanks to optical diagnostics. Experimental spectra have been compared to ab initio spectra, calculated in the same conditions. The theoretical goal was to validate the calculation method in high densities and high temperatures regime with the study of K-edge absorption modifications. We also used absorption spectra to study the metal-non metal transition which takes place at low density (density ≤ solid density). This transition could be study with electronic structure modifications of the system. (author)

  6. The influence of multiscale fillers reinforcement into impact resistance and energy absorption properties of polyamide 6 and polypropylene nanocomposite structures

    Highlights: ► Significant improvement in PA composites impact resistance performance. ► Decrease in energy absorption capabilities of PP, this phenomenon is explained. ► Positive effects on mechanical and interphase properties of the matrix material. ► Transition from brittle to ductile fracture mode established. ► Two different toughening mechanisms were observed and explained. - Abstract: Three-phase composites (thermoplastic polymer, glass-fibres and nano-particles) were investigated as an alternative to two-phase (polymer and glass-fibres) composites. The effect of matrix and reinforcement material on the energy absorption capabilities of composite structures was studied in details in this paper. Dynamic and quasi-static axial collapse of conical structures was conducted using a high energy drop tower, as well as Instron universal testing machine. The impact event was recorded using a high-speed camera and the fracture surface was investigated with scanning electron microscopy (SEM). Attention was directed towards the relation between micro and macro fracture process with crack propagation mechanism and energy absorbed by the structure. The obtained results indicated an important influence of filler and matrix material on the energy absorption capabilities of the polymer composites. A significant increase in specific energy absorption (SEA) was observed in polyamide 6 (PA6) reinforced with nano-silica particles and glass-spheres, whereas addition of montmorillonite (MMT) caused a decrease in that property. On the other hand, very little influence of the secondary reinforcement on the energy absorption capabilities of polypropylene (PP) composites was found

  7. The parsec-scale structure of radio-loud broad absorption line quasars

    Bruni, G.; Dallacasa, D.; Mack, K.-H.; Montenegro-Montes, F. M.; González-Serrano, J. I.; Holt, J.; Jiménez-Luján, F.

    2013-06-01

    Context. Broad absorption line quasars (BAL QSOs) belong to a class of objects not well-understood as yet. Their UV spectra show BALs in the blue wings of the UV resonance lines, owing to ionized gas with outflow velocities up to 0.2 c. They can have radio emission that is difficult to characterize and that needs to be studied at various wavelengths and resolutions. Aims: We aim to study the pc-scale properties of their synchrotron emission and, in particular, to determine their core properties. Methods: We performed observations in the Very Long Baseline Interferometry (VLBI) technique, using both the European VLBI Network (EVN) at 5 GHz, and the Very Long Baseline Array (VLBA) at 5 and 8.4 GHz to map the pc-scale structure of the brightest radio-loud objects of our sample, allowing a proper morphological interpretation. Results: A variety of morphologies have been found: 9 BAL QSOs on a total of 11 observed sources have a resolved structure. Core-jet, double, and symmetric objects are present, suggesting different orientations. In some cases the sources can be young GPS or CSS. The projected linear size of the sources, also considering observations from our previous work for the same objects, can vary from tens of pc to hundreds of kpc. In some cases, a diffuse emission can be supposed from the missing flux-density with respect to previous lower resolution observations. Finally, the magnetic field strength does not significantly differ from the values found in the literature for radio sources with similar sizes. Conclusions: These results are not easily interpreted with the youth scenario for BAL QSOs, in which they are generally compact objects still expelling a dust cocoon. The variety of orientations, morphologies, and extensions found are presumably related to different possible angles for the BAL producing outflows, with respect to the jet axis. Moreover, the phenomenon could be present in various phases of the QSO evolution. Table 3 is available in

  8. Watching coherent molecular structural dynamics during photoreaction: beyond kinetic description

    Lemke, Henrik T; Hartsock, Robert; van Driel, Tim Brandt; Chollet, Matthieu; Glownia, J M; Song, Sanghoon; Zhu, Diling; Pace, Elisabetta; Nielsen, Martin M; Benfatto, Maurizio; Gaffney, Kelly J; Collet, Eric; Cammarata, Marco

    2015-01-01

    A deep understanding of molecular photo-transformations occurring is challenging because of the complex interaction between electronic and nuclear structure. The initially excited electronic energy dissipates into electronic and structural reconfigurations often in less than a billionth of a second. Molecular dynamics induced by photoexcitation have been very successfully studied with femtosecond optical spectroscopies, but electronic and nuclear dynamics are often very difficult to disentangle. X-ray based spectroscopies can reduce the ambiguity between theoretical models and experimental data, but it is only with the recent development of bright ultrafast X-ray sources, that key information during transient molecular processes can be obtained on their intrinsic timescale. We use Free Electron Laser (FEL) based time-resolved X-ray Absorption Near Edge Structure (XANES) measurements around the Iron K-edge of a spin crossover prototypical compound. We reveal its transformation from the ligand-located electroni...

  9. Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy

    Graphical abstract: - Highlights: • Immobility and transformation of As on different Eh soils were investigated. • μ-XRF, XANES, and XPS were used to gain As distribution and speciation in soil. • Sorption capacity of As on anaerobic soil was much higher than that on oxic soil. • Fe oxides reductive dissolution is a key factor for As sorption and transformation. - Abstract: The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils

  10. Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy

    Fan, Jian-Xin [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); School of River and Ocean Engineering, Chongqing Jiaotong University, Chongqing 400074 (China); Wang, Yu-Jun, E-mail: yjwang@issas.ac.cn [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Liu, Cun [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Wang, Li-Hua; Yang, Ke [Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of sciences, Shanghai 201204 (China); Zhou, Dong-Mei, E-mail: dmzhou@issas.ac.cn [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Li, Wei; Sparks, Donald L. [Environmental Soil Chemistry Group, Delaware Environmental Institute and Department of Plant and Soil Sciences, University of Delaware, Newark, DE 19717-1303 United States (United States)

    2014-08-30

    Graphical abstract: - Highlights: • Immobility and transformation of As on different Eh soils were investigated. • μ-XRF, XANES, and XPS were used to gain As distribution and speciation in soil. • Sorption capacity of As on anaerobic soil was much higher than that on oxic soil. • Fe oxides reductive dissolution is a key factor for As sorption and transformation. - Abstract: The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils.

  11. Local structure of Th complexes on montmorillonite clay mineral determined by extended X-ray absorption fine structure (EXAFS) spectroscopy

    The research at the Waste Management Laboratory, PSI, concentrates on the understanding of safety relevant mechanisms and processes that govern the release of radionuclides from waste matrices, and their transport through engineered barrier systems and the surrounding geosphere. For this reason, detailed sorption studies of radionuclides in clay and cement systems are conducted. The studies are combined with extended X-ray absorption fine structure (EXAFS) spectroscopy measurements in order to understand the sorption mechanisms at an atomic level. In this manuscript, a case study of Th(IV) uptake on montmorillonite is presented. EXAFS samples were prepared by incubating a montmorillonite suspension with Th for seven days at pH = 5 (Thinitial: 4.3 x 10-5 to 4 x 10-4 M). The resulting Th loadings on the clay varied between 14 and 166 μmol/g. LIII-Th EXAFS spectra of Th-treated montmorillonite were measured at the Rossendorf Beamline at the European Synchrotron Radiation Facility. Data analysis revealed the presence of two O shells at 2.27 angstrom and 2.45 angstrom in all samples. The spectra at low Th uptake suggest the presence of Si/A1 and Th backscattering atoms at distances of 3.85 angstrom and 3.77 angstrom respectively. The presence of a Th-Si/A1 backscattering pair suggests that Th is bound to Si tetrahedra by a double corner-sharing manner. At higher Th uptake, however, the spectrum shows a strong similarity with the spectrum of amorphous Th(OH)4 and suggests that Th is predominately present as a newly formed Th(OH)4-like phase. (authors)

  12. Supporting Structure of the LSD Wave in an Energy Absorption Perspective

    In Repetitively Pulsed (RP) Laser Propulsion, laser energy irradiated to a vehicle is converted to blast wave enthalpy during the Laser Supported Detonation (LSD) regime. Based on the measured post-LSD electron number density profiles by two-wavelength Mach Zehnder interferometer in a line-focusing optics, electron temperature and absorption coefficient were estimated assuming Local Thermal Equilibrium. A 10J/pulse CO2 laser was used. As a result, laser absorption was found completed in the layer between the shock wave and the electron density peak. Although the LSD-termination timing was not clear from the shock-front/ionization-front separation in the shadowgraph images, there observed drastic changes in the absorption layer thickness from 0.2 mm to 0.5 mm and in the peak heating rate from 12-17x1013 kW/m3 to 5x1013 kW/m3 at the termination

  13. Absorption Capacity, Structural Similarity and Embodied Technology Spillovers in A ‘Macro’ Model: An Implementation within a CGE Framework

    Das, Gouranga; Powell, Alan A. L.

    2000-01-01

    In this paper, all technology transfers are embodied in trade flows within a three-region, one-traded-commodity version of the GTAP model. Exogenous Hicks-Neutral technical progress in one region can have uneven impacts on productivity elsewhere. Why? Destination regions’ ability to harness new technology depends on their absorptive capacity and the structural congruence of the source and destination. Together with trade volume, these two factors determine the recipient’s spillover coeffic...

  14. Absorption-line ''forest'' in quasar spectra, and the structure of the universe

    Doroshkevich, A.G.; Muket, J.P.

    1985-05-01

    The ''forest'' of absorption lines observed in the spectrum of distant quasars is interpreted in light of the adiabatic (pancake) theory for the origin and evolution of structure in the universe. The hidden mass might reside in neutrino-like particles (perhaps unstable) having a rest mass of about 60--100 eV. Opportunities for testing the hypothesis observationally are discussed.

  15. Controlling many-body effects in the midinfrared gain and THz absorption of quantum cascade laser structures

    Pereira Jr., M. F.; Lee, S. -C.; Wacker, A.

    2004-01-01

    A many-body theory based on nonequilibrium Green functions, in which transport and optics are treated on a microscopic quantum mechanical basis, is used to compute gain and absorption in the optical and THz regimes in quantum cascade laser structures. The relative importance of Coulomb interactions for different intersubband transitions depends strongly on the spatial overlap of the wavefunctions and the specific nonequilibrium populations within the subbands. The magnitude of the Coulomb eff...

  16. The electronic structure of homogeneous ferromagnetic (Ga, Mn)N epitaxial films

    Piskorska-Hommel, E., E-mail: e.piskorska@int.pan.wroc.pl [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Institute W. Trzebiatowski, Wroclaw (Poland); Institute of Solid State Physics, University of Bremen, Bremen (Germany); Winiarski, M. J. [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Institute W. Trzebiatowski, Wroclaw (Poland); Kunert, G.; Falta, J. [Institute of Solid State Physics, University of Bremen, Bremen (Germany); Demchenko, I. N. [Institute of Physic, Polish Academy of Sciences, Warsaw (Poland); Roshchupkina, O. D.; Grenzer, J. [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Ion Beam Physics and Materials Research, Bautzner Landstraße 400, 01328 Dresden (Germany); Hommel, D. [Institute of Solid State Physics, University of Bremen, Bremen (Germany); Wrocław Research Center EIT+ Sp. z o.o., Wroclaw (Poland); Experimental Physics, University of Wroclaw, Wroclaw (Poland); Holý, V. [Department of Condensed Matter Physics, Faculty of Mathematics and Physics, Charles University in Prague, Praha (Czech Republic)

    2015-02-14

    X-ray Absorption Fine Structure (XAFS) techniques, namely, X-ray Near Edge Structure (XANES), Extended XAFS (EXAFS), and Anomalous X-ray Diffraction (AXRD) were used to investigate the local atomic and electronic structure of (Ga, Mn)N magnetic layers with Mn concentrations of up to 10% grown by Molecular Beam Epitaxy. The XANES and AXRD analysis prove the Mn incorporation on substitutional GaN lattice sites. EXAFS results indicate the good quality of the structure under examination, although 0.5 nitride atom vacancies were found. The Wien2k code was applied to interpret the XANES spectra quantitatively, i.e., to determine the electronic structure of the Mn atoms. It was shown that accounting for the core-hole effect is necessary to reconstruct effectively the XANES spectra. Conducted charge density analysis based on DFT calculations identified the valency of Mn atom to be of 2.4+.

  17. Structural, absorption and fluorescence spectral analysis of Pr3+ ions doped zinc bismuth borate glasses

    Highlights: → 20ZnO.xBi2O3.(79.5-x)B2O3.0.5Pr6O11 (15 ≤ x ≤ 35) glasses were prepared by melt quench technique. → The Judd-Ofelt parameters Ωλ (λ = 2, 4, 6) and other radiative properties like radiative transition probability, radiative life time, branching ratio and stimulated emission cross-section of the prepared glasses have been calculated. → The branching ratio for 3P0 → 3F2 transition of Pr3+ doped glasses is 42% and the predicted spontaneous radiative transition probability rates are fairly high. - Abstract: Glasses having composition 20ZnO.xBi2O3.(79.5 - x)B2O3.0.5Pr6O11 were prepared by melt quench technique. The amorphous nature of the prepared glass samples was confirmed by X-ray diffraction. The spectroscopic properties of these glasses were investigated by recording optical absorption and fluorescence spectra. The structural investigations of the glasses were carried out by recording the IR spectra. The optical properties of Pr3+ ions doped zinc borate glasses with varying concentration of bismuth oxide have been studied. The Judd-Ofelt intensity parameters Ωλ (λ = 2, 4, 6) and other radiative properties like radiative transition probability, radiative life time, branching ratio and stimulated emission cross-section of the prepared glasses have been calculated. The variation of Ω2 with Bi2O3 content has been attributed to changes in the asymmetry of the ligand field at the rare earth ion site and to the changes in their rare earth oxygen (RE-O) covalency. The branching ratio for 3P0 → 3F2 transition is 42% and the predicted spontaneous radiative transition probability rates are fairly high (14,347-14,607 s-1). This is beneficial for lasing emission. The stimulated emission cross-section for all the emission bands has been calculated.

  18. Investigation of the structure of molecular complexes by X ray absorption and diffraction: application to the f compound family

    After having recalled that his research thesis was dealing with 4d transition elements while investigating niobium clusters reactivity, and having outlined that he is now interested in the investigation of 4f and 5f compound behaviour, notably by using X ray absorption spectroscopy, the author describes the experimental methods he implemented. Then, he discusses the stereo-chemical structure of molecular complexes, reports the use of X ray absorption and diffraction, discusses the generation of electronic functions of chi(k) and the adjustment of the chi(k) function through geometrical parameters. He also describes the simple diffusion approach, reports a multiple diffusion analysis. He outlines the peculiarity of heavy atoms because of relativistic effects. Then, he discusses the investigation of the electronic structure of molecular complexes by means of a stereo-chemical approach, with the determination of the absorption threshold and of the oxidation degree. He discusses the attempt of a semi-empirical approach of the stereo-chemical and electronic structure

  19. 21 centimeter HI absorption at z = 0.437 against the extended radio structure of 3c 196

    We report the detection of an absorption line at 988.7. MHz toward the quasar 3C 196. We identify this line as the lambda21 cm line of neutral atomic hydrogen seen at a redshift of z/sub abs/ = 0.4366. No optical absorption lines have been noted in the z/sub em/ = 0.871 quasar 3C 196 heretofore. All the radio emission of 3C 196 is contained in two thetaroughly-equal3'' extended lobes symmetrically placed (position angle approx.260) about the optical object. The optical QSO itself is an extremely weak, 0, that is in a direction perpendicular to the separation of the radio lobes. If this wisp is the disk of an intervening galaxy, then the H i absorption is direct evidence for absorption in a galactic halo. Puzzles abound; (1) If the optical wisp seen superposed on the QSO is an intervening galaxy then what aspects, if any, of the emission from 3C 196 are gravitational lens effects. (2) If the wisp is associated with the QSO, why is it radio quiet and why is it orthogonal to the extended radio structure of 3C 196. (3) Is it significant that z/sub abs/ is one-half z/sub em/ within the errors

  20. Mapping kiloparsec-scale structures in the extended HI disc of the galaxy UGC 00439 by HI 21-cm absorption

    Dutta, Rajeshwari; Srianand, Raghunathan; O'Meara, John

    2016-01-01

    We study the properties of HI gas in the outer regions (~2r_25) of a spiral galaxy, UGC 00439 (z = 0.01769), using HI 21-cm absorption towards different components of an extended background radio source, J0041$-$0043 (z = 1.679). The radio source exhibits a compact core coincident with the optical quasar and two lobes separated by ~7 kpc, all at an impact parameter ~25 kpc. The HI 21-cm absorption detected towards the southern lobe is found to extend over ~2 kpc^2. The absorbing gas shows sub-kpc-scale structures with the line-of-sight velocities dominated by turbulent motions. Much larger optical depth variations over 4-7 kpc-scale are revealed by the non-detection of HI 21-cm absorption towards the radio core and the northern lobe, and the detection of NaI and CaII absorption towards the quasar. This could reflect a patchy distribution of cold gas in the extended HI disc. We also detect HI 21-cm emission from UGC 00439 and two other galaxies within ~150 kpc to it, that probably form an interacting group. Ho...

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

    Kvashnina, Kristina O.; De Groot, Frank M F

    2014-01-01

    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

  2. Tailoring defect structure and optical absorption of porous anodic aluminum oxide membranes

    Defects influence the optical and electronic properties of nanostructured materials that may be relevant for applications. In self-organized anodic aluminum oxide (AAO) templates we have investigated the effect of annealing, doping and nanoscale metal deposition. Optical absorption spectroscopy has been used as a sensitive probe for the defect density in AAO templates. The electronic spectra are found to be dominated by bands which originate from oxygen-deficient color centers (F+, F and F2). In annealing studies, the integrated absorption of the bands changes non-monotonically with annealing temperature and annealing time. This demonstrates that the concentration of defects can be optimized to tailor the optical properties of the AAO. Metallic Au wires are deposited in the template to establish a plasmonic template or array. The investigations provide an interesting insight into the interplay of reactivity and diffusivity on nanoscales. - Highlights: ► Preparation of metal wire arrays in oxide templates with tailored plasmonic properties. ► Oxygen defects are characterized using optical absorption and fluorescence. ► Optical absorption spectra are assigned to energy levels of oxygen vacancies (color centers). ► Annealing and electrodeposition of Au wires minimize defects maintaining the morphology.

  3. Photonic band gap structures of obliquely incident electromagnetic wave propagation in a one-dimension absorptive plasma photonic crystal

    The photonic band gap structures of obliquely incident electromagnetic waves propagating in a one-dimension plasma photonic crystal with collision have been studied on the basis of electromagnetic theory and transfer matrix approach. The dispersion relations for both the transverse electric wave case and the transverse magnetic wave case are deduced. And the photonic band gap structures, with their function dependence on the microplasma layer density, microplasma width, collision frequency, background material dielectric constant, and incident angle, are computed. The results show that there exist two photonic band gap structures in an adsorptive plasma photonic crystal: one is a normal photonic band gap structure and the other is an absorption photonic band gap structure. Parameter dependence of the effects is calculated and discussed.

  4. Displacive phase-transition of cuprite Ag2O revealed by extended x-ray absorption fine structure

    Sanson, Andrea

    2016-08-01

    The low-temperature phase-transition of silver oxide (Ag2O) has been investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy as a function of temperature. The thermal evolution of the local structure around Ag atoms has been determined. In particular, below the phase-transition temperature at ∼35 K, a progressive splitting of the Ag-Ag next-nearest-neighbor distances is observed. This definitely supports the idea that the phase-transition of Ag2O is due to displacive disorder of the Ag atoms.

  5. The electronic structure of zirconium in hydrided and oxidized states

    Highlights: • XANES and XPS of zirconium in oxidized and hydrided states were studied. • The variations in the XANES spectra are explained with density functional theory. • Hydrogen preferentially bonds to specific oxygen sites in the monoclinic ZrO2. • The monoclinic ZrO2 offers the strongest barrier against hydriding attack. - Abstract: Valence band energy shifts for pure zirconium and a model zirconium alloy (Zircaloy-4) in oxidized and hydrided states have been investigated with X-ray photoelectron spectroscopy (XPS) and X-ray Absorption Near-Edge Structure (XANES) technique. With XANES, we show that O/H interactions in oxidized Zr can be detected in the near-edge region of O K. Using density functional theory (DFT) simulations, we have determined where H atoms bond in the monoclinic ZrO2 lattice. The preferred stoichiometry is ZrO2:H, but the O-H bond is weak; increasing H causes the H atoms to form H2 molecules rather than O-H bonds. These interactions cause energy shifts in the Zr 3d XPS spectra. The results illustrate the complex processes of hydrogen and oxygen interactions at the Zr surface

  6. The electronic structure of tungsten oxide thin films prepared by pulsed cathodic arc deposition and plasma-assisted pulsed magnetron sputtering

    Pulsed cathodic arc and pulsed magnetron sputtered WO3 thin films were investigated using electron microscopy. It was found that the cathodic arc deposited material consisted of the α-WO3 phase with a high degree of crystallinity. In contrast, the magnetron sputtered material was highly disordered making it difficult to determine its phase. Electron energy-loss spectroscopy was used to study the oxygen K edge of the films and it was found that the near-edge fine structures of films produced by the two deposition methods differed. The oxygen K-edge near-edge structures for various phases of WO3 were calculated using two different self-consistent methods. Each phase was found to exhibit a unique oxygen K edge, which would allow different phases of WO3 to be identified using x-ray absorption spectroscopy or electron energy-loss spectroscopy. Both calculation methods predicted an oxygen K edge for the γ-WO3 phase which compared well to previous x-ray absorption spectra. In addition, a close match was found between the oxygen K edges obtained experimentally from the cathodic arc deposited material and that calculated for the α-WO3 phase

  7. Origin of improved scintillation efficiency in (Lu,Gd).sub.3./sub.(Ga,Al).sub.5./sub.O.sub.12./sub.:Ce multicomponent garnets: an X-ray absorption near edge spectroscopy (XANES) study

    Wu, Y.; Luo, J.; Nikl, Martin; Ren, G.

    2014-01-01

    Roč. 2, č. 1 (2014), "012101-1"-"012101-8". ISSN 2166-532X R&D Projects: GA MŠk LH12185 Institutional support: RVO:68378271 Keywords : scintillator * multicomponent garnet * Ce 4+ * XANES Subject RIV: BM - Solid Matter Physics ; Magnetism

  8. Superparamagnetic nanoplatforms for theragnostic applications: a structural investigation

    Milosevic, Irena; Motte, Laurence; Saboungi, Marie-Louise; Aoun, Bachir; Li, Tao; Sun, Chengjun; Ren, Yang

    2014-03-01

    Magnetic nanoplatforms are being developed for use in bioassays, diagnosis, therapy and nano-organocatalysis. The nanoparticle has two essential roles: to act as a probe owing to its specific magnetic properties and to carry on its surface antitumoral molecules, precursor groups for the covalent coupling of biological recognition molecules, or small organic catalysts such as amino acids and alkaloids. The nanoplatforms consist of a superparamagnetic iron oxide core and different coatings for surface passivation and stabilization. We report recent results obtained at the Advanced Photon Source on three kinds of nanoplatforms, differing in their coating molecules: shape and size determination by small-angle X-ray scattering, distribution of valences and chemical environments of the iron ions deduced from X-ray absorption near-edge structure measurements, and atomic structures determined by x-ray diffraction.

  9. X-ray absorption Studies of Zinc species in Centella asiatica

    Dehipawala, Sunil; Cheung, Tak; Hogan, Clayton; Agoudavi, Yao; Dehipawala, Sumudu

    2013-03-01

    Zinc is a very important mineral present in a variety of vegetables. It is an essential element in cellular metabolism and several bodily functions. We used X-ray fluorescence, and X-ray Absorption near Edge structure(XANES) to study the amount of zinc present in several leafy vegetables as well as its chemical environment within the plant. Main absorption edge position of XANES is sensitive to the oxidation state of zinc and is useful when comparing the type of zinc present in different vegetables to the standard zinc present in supplements. Normalized main edge height is proportional to the amount of zinc present in the sample. Several leafy greens were used in this study, such as Spinacia oleracea, Basella alba, Brassica oleracea, Cardiospermum halicacabumand Centella asiatica. All of these plant leaves contained approximately the same amount of zinc in the leaf portion of the plant and a slightly lower amount in the stems, except Centella asiatica. Both leaves and stems of the plant Centella asiatica contained nearly two times the zinc compared to other plants. Further investigation of zinc's chemical environment within Centella asiatica could lead to a much more efficient dietary consumption of zinc. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886

  10. Structural elucidation of active layers in organic electronic devices via NEXAFS

    Loo, Y-L, E-mail: lloo@princeton.edu [Chemical and Biological Engineering Department, Princeton University, Princeton NJ 08544-5263 (United States)

    2010-11-15

    The electrically-active thin films within organic electronic devices are structurally complex; the details of which depend strongly on both inherent materials properties as well as processing history. Given structural heterogeneities within such electrically-active thin films can influence device characteristics dramatically, understanding - and ultimately, controlling - structural development is a necessary precursor to producing reliable and high-performance electronic devices. Highlighted herein are several examples from our laboratories in which synchrotron soft x-rays based near-edge x-ray absorption fine structure spectroscopy is used to elucidate (i) ensemble-average molecular orientation (ii) relative surface coverage and (iii) vertical compositional profile in such electrically-active thin films.

  11. Excitonic and vibronic structure of absorption spectra of Me-PTCDI and PTCDA crystals

    The excitonic and vibronic spectra (exciton + one quantum of intramolecular vibration) of Me-PTCDI and PTCDA crystals are studied in the case of strong mixing of a Frenkel exciton (FE) and charge-transfer excitons (CTEs). The linear optical susceptibility is calculated in the framework of dynamical theory of vibronic spectra. The absorption spectra of both crystals have been modelled. The positions, maximal values and integral intensity of the absorption peaks which correspond to the bound exciton-phonon states and to unbound (many-particle) states have been calculated using FE and CTEs's parameters of Me-PTCDI and PTCDA crystals. The calculated spectra show: (i) the possible recovering of excitonic and vibronic regions; (ii) bigger integral intensity of many-particle states in the case of weak exciton-phonon coupling; (iii) the dominant role of the bound states in the case of intermediate and strong exciton-phonon coupling

  12. Capturing molecular structural dynamics by 100 ps time-resolved X-ray absorption spectroscopy

    An experimental set-up for time-resolved X-ray absorption spectroscopy with 100 ps time resolution at beamline NW14A at the Photon Factory Advanced Ring is presented. An experimental set-up for time-resolved X-ray absorption spectroscopy with 100 ps time resolution at beamline NW14A at the Photon Factory Advanced Ring is presented. The X-ray positional active feedback to crystals in a monochromator combined with a figure-of-merit scan of the laser beam position has been utilized as an essential tool to stabilize the spatial overlap of the X-ray and laser beams at the sample position. As a typical example, a time-resolved XAFS measurement of a photo-induced spin crossover reaction of the tris(1,10-phenanthrorine)iron(II) complex in water is presented

  13. Proton emission from resonant laser absorption and self-focusing effects from hydrogenated structures

    Cutroneo, M.; Torrisi, L.; Margarone, Daniele; Picciotto, A.

    2013-01-01

    Roč. 272, May (2013), s. 50-54. ISSN 0169-4332 R&D Projects: GA MŠk EE.2.3.20.0087 Grant ostatní: OP VK 2 Laser Gen(XE) CZ.1.07/2.3.00/20.0087 Institutional support: RVO:68378271 Keywords : resonant absorption * self-focusing * Thomson parabola * spectrometer Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 2.538, year: 2013

  14. The effects of dust scattering on high-resolution X-ray absorption edge structure

    Corrales, L.; García, J.; Wilms, J.; Baganoff, F.

    2016-06-01

    High energy studies of astrophysical dust complement observations of dusty interstellar gas at other wavelengths. With high resolution X-ray spectroscopy, dust scattering significantly enhances the total extinction optical depth and alters the shape of photoelectric absorption edges. This effect is modulated by the dust grain size distribution, spatial location along the line of sight, and the imaging resolution of the X-ray telescope. At soft energies, the spectrum of scattered light is likely to have significant features at the 0.3 keV (C-K), 0.5 keV (O-K), and 0.7 keV (Fe-L) photoelectric absorption edges. This direct probe of ISM dust grain elements will be important for (i) understanding the relative abundances of graphitic grains or PAHs versus silicates, and (ii) measuring the depletion of gas phase elements into solid form. We focus in particular on the Fe-L edge, fitting a template for the total extinction to the high resolution spectrum of three X-ray binaries from the Chandra archive: GX 9+9, XTE J1817-330, and Cyg X-1. We discuss ways in which spectroscopy with XMM can yield insight into dust obscured objects such as stars, binaries, AGN, and foreground quasar absorption line systems.

  15. Subwavelength structure for sound absorption from graphene oxide-doped polyvinylpyrrolidone nanofibers

    Qamoshi, Khadijeh; Rasuli, Reza

    2016-09-01

    We study the sound absorption of the reinforced polyvinylpyrrolidone nanofibers with graphene oxide. It is shown that reinforced nanofibers can acquire impedance-matched surface to airborne sound at special frequencies. To obtain such surface, nanofibers were spun with polyvinylpyrrolidone polymer that was doped by graphene oxide with concentrations of 0, 6 and 12 wt%. It was found that fibers without graphene oxide were spun continuously and randomly, whereas by doping with graphene oxide, the mode of fibers is changed and some nodes form on the fibers coating. The sound absorption coefficient was measured by an impedance tube based on 105341-1 ISO standard. Measurements in the frequency range from 700 to 1600 Hz show that use of graphene oxide as a reinforcing phase increases sound absorption coefficient of the samples at a frequency ~1500 Hz up to ~40 %. Angular eigenfrequency and dissipation coefficient of the samples were obtained by impedance measurement for the prepared samples. Results show that doping the polymer with graphene oxide causes an increase in the angular eigenfrequency and the dissipation coefficient.

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

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

    2016-01-21

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

  17. Comparative analysis of the vibrational structure of the absorption spectra of acrolein in the excited ( S 1) electronic state

    Koroleva, L. A.; Tyulin, V. I.; Matveev, V. K.; Pentin, Yu. A.

    2012-04-01

    The assignments of absorption bands of the vibrational structure of the UV spectrum are compared with the assignments of bands obtained by the CRDS method in a supersonic jet from the time of laser radiation damping for the trans isomer of acrolein in the excited ( S 1) electronic state. The ν00 trans = 25861 cm-1 values and fundamental frequencies, including torsional vibration frequency, obtained by the two methods were found to coincide in the excited electronic state ( S 1) for this isomer. The assignments of several absorption bands of the vibrational structure of the spectrum obtained by the CRDS method were changed. Changes in the assignment of (0-v') transition bands of the torsional vibration of the trans isomer in the Deslandres table from the ν00 trans trans origin allowed the table to be extended to high quantum numbers v'. The torsional vibration frequencies up to v' = 5 were found to be close to the frequencies found by analyzing the vibrational structure of the UV spectrum and calculated quantum-mechanically. The coincidence of the barrier to internal rotation (the cis-trans transition) in the one-dimensional model with that calculated quantum-mechanically using the two-dimensional model corresponds to a planar structure of the acrolein molecule in the excited ( S 1) electronic state.

  18. Log spiral of revolution highly oriented pyrolytic graphite monochromator for fluorescence x-ray absorption edge fine structure

    We have constructed an x-ray monochromator based on a log spiral of revolution covered with highly oriented pyrolytic graphite. Such a monochromator is used for obtaining x-ray absorption edge fine structure by the fluorescence method, and is particularly useful for measuring the fine structure of dilute element A in a concentrated matrix of element B, where B is to the left of A in the Periodic Table. Using the log spiral monochromator, we measure good Cr x-ray fine structure in an alloy of 1% Cr in a V matrix, whereas the corresponding spectrum is severely distorted by the V background if nonmonochromatized fluorescence is used. We also obtain excellent rejection of Mn fluorescence relative to Cr fluorescence in a Cr80Mn20 alloy, and can tune the monochromator such that the entire Mn step height is significantly smaller than the Cr x-ray absorption edge fine structure oscillations for this system. (c) 2000 American Institute of Physics

  19. Structure and magnetism of Zn0.9Co0.1O DMS films prepared by chemical solution deposition method

    The Zn0.9Co0.1O films are fabricated by chemical solution deposition method. All the films have the ZnO wurtzite structure with a preferential orientation along the c-axis. The analysis of X-ray near-edge absorption spectroscopy and X-ray photoelectron spectroscopy indicates that the valence of Co is +2, and there are oxygen vacancies in Zn0.9Co0.1O films annealed in Ar atmosphere. Extended X-ray absorption fine structure results reveal that Co2+ ions have dissolved into ZnO and substituted for Zn2+ ions. Magnetization measurements show that the film annealed in Ar exhibits ferromagnetism which can be explained by the formation of bound magnetic polarons.

  20. Structured triacylglycerol containing behenic and oleic acids suppresses triacylglycerol absorption and prevents obesity in rats

    Takamatsu Kiyoharu

    2010-07-01

    Full Text Available Abstract Background Dietary 1(3-behenoyl-2,3(1-dioleoyl-rac-glycerol (BOO has been reported to inhibit pancreatic lipase activity in vitro and suppress postprandial hypertriacylglycerolemia in humans. In the present study, the anti-obesity activities of BOO and its inhibitory effects on lymphatic triacylglycerol (TAG absorption were investigated in rats. Methods In Experiment 1, rats were fed either BOO or soybean oil (SO diet for 6 weeks. In the BOO diet, 20% of SO was replaced with an experimental oil rich in BOO. In Experiments 2 and 3, rats cannulated in the thoracic duct were administered an emulsions containing trioleoylglycerol (OOO or an oil mixture (OOO:BOO, 9:1. Tri[1-14C]oleoylglycerol (14C-OOO was added to the emulsions administered in Experiment 3. Results No observable differences were detected in food intake or body weight gain between the BOO and SO groups in Experiment 1. Plasma and liver TAG concentrations and visceral fat weights were significantly lower in the BOO group than in the SO group. The apparent absorption rate of fat was significantly lower in the BOO group than in the SO group. In Experiment 2, the lymphatic recovery of oleic and behenic acids was significantly lower at 5 and 6 h after BOO administration than after OOO administration. In Experiment 3, the lymphatic recovery of 14C-OOO was significantly lower at 5 and 6 h after BOO administration than after OOO administration. Conclusions These results suggest that BOO prevents deposition of visceral fat and hepatic TAG by lowering and delaying intestinal absorption of TAG.

  1. Doublet structure in the absorption redshifts in the spectrum of PKS 0237-23

    The spectrum of the quasar PKS 0237-23 has been observed over the wavelength range lambdalambda3730-4300 at a resolution of 0.17 A with the University College London image photon counting system. A list of 75 absorption lines has been combined with a further 26 lines drawn from other sources and identified by computer using a procedure described by Bahcall. Two new redshift systems, a complex of redshifts near z/suba//subb//subs/=1.55 and a system at z/suba//subb//subs/=2.1758, were found. The systems z=1.51, 1.59, 1.65, and 1.67 discovered by earlier workers were all found to be double or multiple; in addition, the system z/suba//subb//subs/=1.36 may be double. A constant splitting, Δz=0.0012, between adjacent redshifts, corresponding to 141plus-or-minus9 km s-1 in velocity, occurs at least seven times. The origin of this splitting, which also occurs in the quasars Markarian 132 and Ton 1530, is not understood. It almost corresponds, however, to the splitting between Lα, lambda1215.67 and the nearby line lambda1215.14 of He II. This amounts to 130.8 km s-1. Most of the absorption lines are unresolved and have widths corresponding to velocity spreads of less than 50 km s-1 in the rest frames of the absorbing clouds. There is evidence for absorption line-locking involving superpositions of the lines of the C IV resonance doublet in nearby redshift systems

  2. Size-dependent absorption and defect states in CdSe nanocrystals in various multilayer structures.

    Nesheva, D; Levi, Z; Aneva, Z; Zrinscak, I; Main, C; Reynolds, S

    2002-12-01

    GeS2-CdSe superlattices and composite films are prepared by consecutive thermal evaporation of CdSe and GeS2 in vacuum. CdSe layer thickness varies between 1 and 10 nm, while the thickness of GeS2 layers is either equal (in superlattices) to or 20 times greater (in composite films) than that of CdSe layers. Standard spectral photocurrent measurements and various constant photocurrent methods are used to study optical absorption of all samples. An overall blueshift is observed with decreasing CdSe layer thickness of superlattices. This shift is related to a size-induced increase of the optical band gap of CdSe due to one-dimensional carrier confinement in the continuous nanocrystalline CdSe layers. A number of features are observed in the absorption spectra of composite films containing CdSe nanocrystals with average radii of approximately 2.5 and approximately 3.3 nm. They are discussed in terms of three-dimensional carrier confinement and are considered a manifestation of excited electron states in CdSe nanocrystals embedded in GeS2 thin film matrix. In addition to these discrete features, the exponential dependence of the optical absorption (Urbach) edge indicates a distribution of "valence band" tail states associated with disorder. Transient photoconductivity measurements made on similarly prepared SiOx-CdSe superlattices exhibit a rapid fall in photocurrent by a power law decay over several orders of magnitude of time, which is consistent with multi-pletrapping transport via an extensive distribution of deep defects. PMID:12908429

  3. Atomic transition frequencies, isotope shifts, and sensitivity to variation of the fine structure constant for studies of quasar absorption spectra

    Berengut, J C; Flambaum, V V; King, J A; Kozlov, M G; Murphy, M T; Webb, J K

    2010-01-01

    Theories unifying gravity with other interactions suggest spatial and temporal variation of fundamental "constants" in the Universe. A change in the fine structure constant, alpha, could be detected via shifts in the frequencies of atomic transitions in quasar absorption systems. Recent studies using 140 absorption systems from the Keck telescope and 153 from the Very Large Telescope, suggest that alpha varies spatially. That is, in one direction on the sky alpha seems to have been smaller at the time of absorption, while in the opposite direction it seems to have been larger. To continue this study we need accurate laboratory measurements of atomic transition frequencies. The aim of this paper is to provide a compilation of transitions of importance to the search for alpha variation. They are E1 transitions to the ground state in several different atoms and ions, with wavelengths ranging from around 900 - 6000 A, and require an accuracy of better than 10^{-4} A. We discuss isotope shift measurements that are...

  4. On variations in the fine-structure constant and limits on AGB pollution of quasar absorption systems

    Fenner, Y; Gibson, B K

    2005-01-01

    At redshifts z_abs < 2, quasar absorption-line constraints on space-time variations in the fine-structure constant, alpha, rely on the comparison of MgII and FeII transition wavelengths. One potentially important uncertainty is the relative abundance of Mg isotopes in the absorbers which, if different from solar, can cause spurious shifts in the measured wavelengths and, therefore, alpha. Here we explore chemical evolution models with enhanced populations of intermediate-mass (IM) stars which, in their asymptotic giant branch (AGB) phase, are thought to be the dominant factories for heavy Mg isotopes at the low metallicities typical of quasar absorption systems. By design, these models partially explain recent Keck/HIRES evidence for a smaller alpha in z_abs < 2 absorption clouds than on Earth. However, such models also over-produce N, violating observed abundance trends in high-z_abs damped Lyman-alpha systems (DLAs). Our results do not support the recent claim of Ashenfelter, Mathews & Olive (2004...

  5. Voyager 1 imaging and IRIS observations of Jovian methane absorption and thermal emission: Implications for cloud structure

    West, R. A.; Kupferman, P. N.; Hart, H.

    1984-01-01

    Images from three filters of the Voyager 1 wide angle camera are used to measure the continuum reflectivity and spectral gradient near 6000 A and the 6190 A band methane/continuum ratio for a variety of cloud features in Jupiter's atmosphere. The dark barge features in the North Equatorial Belt have anomalously strong positive continuum spectral gradients suggesting unique composition. Methane absorption is shown at unprecedented spatial scales for the Great Red Spot and its immediate environment, for a dark barge feature in the North Equatorial Belt, and for two hot spot and plume regions in the North Equatorial Belt. Methane absorption and five micrometer emission are correlated in the vicinity of the Great Red Spot but are anticorrelated in one of the plume hot spot regions. Methane absorption and simultaneous maps of five micrometer brightness temperature is quantitatively compared to realistic cloud structure models which include multiple scattering at five micrometer as well as in the visible. Variability in H2 quadrupole lines are also investigated.

  6. Voyager 1 imaging and IRIS observations of Jovian methane absorption and thermal emission - Implications for cloud structure

    West, R. A.; Kupferman, P. N.; Hart, H.

    1985-01-01

    Images from three filters of the Voyager 1 wide angle camera are used to measure the continuum reflectivity and spectral gradient near 6000 A and the 6190 A band methane/continuum ratio for a variety of cloud features in Jupiter's atmosphere. The dark barge features in the North Equatorial Belt have anomalously strong positive continuum spectral gradients suggesting unique composition. Methane absorption is shown at unprecedented spatial scales for the Great Red Spot and its immediate environment, for a dark barge feature in the North Equatorial Belt, and for two hot spot and plume regions in the North Equatorial Belt. Methane absorption and five micrometer emission are correlated in the vicinity of the Great Red Spot but are anticorrelated in one of the plume hot spot regions. Methane absorption and simultaneous maps of five micrometer brightness temperature are quantitatively compared to realistic cloud structure models which include multiple scattering at five micrometer as well as in the visible. Variability in H2 quadrupole lines are also investigated.

  7. The VLBI structure of radio-loud Broad Absorption Line quasars

    Liu, Y.; Jiang, D. R.; Gu, M.

    2016-02-01

    The nature and origin of Broad Absorption Line (BAL) quasars and their relationship to non-BAL quasars are an open question. The BAL quasars are probably normal quasars seen along a particular line of sight. Alternatively, they are young or recently refueled. The high resolution radio morphology of BAL quasars is very important to understand the radio properties of BAL quasars. We present VLBA observations at L and C bands for a sample of BAL quasars. The observations will help us to explore the VLBI radio properties, and distinguish the present models of explaining BAL phenomena.

  8. The energy absorption of damaged braided and non-crimp fibre composite material structures

    Bottome, Kristofer John

    2006-01-01

    The effects of pre-existing damage on the mode of failure and energy absorption characteristics of Non-Crimp Fabric (NCF) and biaxially braided tubular sections under axial loading were considered. Loading rate effects were incorporated by testing at quasi-static rates and impact rates up to 7ms-1 and the pre-existing damage was simulated through stress concentrations and out-of-plane impact damage. Circular and square geometries were tested, and a range of NCF and braided fibre architectures...

  9. Polarization-dependent X-ray-absorption spectroscopy of $RNi_{2} B_{2}$ C (R=Er $\\to$ Lu) Reduced Ni-3d occupancy in $YbNi_{2} B_{2} C$

    Mazumdar, C; Von Lips, H; Golden, M S; Fink, J; Canfield, P C; Kaindl, G

    2001-01-01

    We present here the results of polarization-dependent X-ray- absorption near-edge structure (XANES) studies at the B-K, C-K, and Ni-L/sub 3/ thresholds of single-crystalline borocarbide compounds RNi/sub 2/B/sub 2/C (with R=Er to Lu) using bulk-sensitive fluorescence yield technique. The Ni-L/sub 3/ XANES spectrum for YbNi /sub 2/B/sub 2/C with photon polarization parallel to the ab plane is significantly more intense than in analogous spectra of other members of this series. This indicates a reduced Ni-3d occupancy in the Ni /sub 2/B/sub 2/ layer in YbNi/sub 2/B/sub 2/C, a fact that might be responsible for the absence of superconductivity in this material. (26 refs).

  10. Ferrocene-Substituted Naphthalenediimide with Broad Absorption and Electron-Transport Properties in the Segregated-Stack Structure.

    Takai, Atsuro; Sakamaki, Daisuke; Seki, Shu; Matsushita, Yoshitaka; Takeuchi, Masayuki

    2016-05-23

    A new naphthalenediimide (NDI) molecule, where two ferrocene (Fc) units were directly attached to both imide nitrogens (Fc-NDI-Fc), was synthesized. The Fc units provide high crystallinity to Fc-NDI-Fc with good solubility to conventional organic solvents. The Fc units also work as electron-donating substituents, in contrast to the electron-deficient NDI unit, resulting in broad charge-transfer absorption of Fc-NDI-Fc from the UV region to 1500 nm in the solid state. The crystal structure analysis revealed that Fc-NDI-Fc formed a segregated-stack structure. The DFT calculation based on the crystal structure showed that the NDI π-orbitals extended over two axes. The extended π-network of the NDI units led to the electron-transport properties of Fc-NDI-Fc, which was confirmed using a flash-photolysis time-resolved microwave conductivity technique. PMID:27061109

  11. Optical and structural properties of plasma-treated Cordyceps bassiana spores as studied by circular dichroism, absorption, and fluorescence spectroscopy

    Lee, Geon Joon; Sim, Geon Bo; Choi, Eun Ha; Kwon, Young-Wan; Kim, Jun Young; Jang, Siun; Kim, Seong Hwan

    2015-01-01

    To understand the killing mechanism of fungal spores by plasma treatment, the optical, structural, and biological properties of the insect pathogenic fungus Cordyceps bassiana spores were studied. A nonthermal atmospheric-pressure plasma jet (APPJ) was used to treat the spores in aqueous solution. Optical emission spectra of the APPJ acquired in air indicated emission peaks corresponding to hydroxyl radicals and atomic oxygen. When the APPJ entered the aqueous solution, additional reactive species were derived from the interaction of plasma radicals with the aqueous solution. Fluorescence and absorption spectroscopy confirmed the generation of hydroxyl radicals and hydrogen peroxide in the plasma-activated water (PAW). Spore counting showed that plasma treatment significantly reduced spore viability. Absorption spectroscopy, circular dichroism (CD) spectroscopy, and agarose gel electrophoresis of the DNA extracted from plasma-treated spores showed a reduction in spore DNA content. The magnitude of the dip in the CD spectrum was lower in the plasma-treated spores than in the control, indicating that plasma treatment causes structural modifications and/or damage to cellular components. Tryptophan fluorescence intensity was lower in the plasma-treated spores than in the control, suggesting that plasma treatment modified cell wall proteins. Changes in spore viability and DNA content were attributed to structural modification of the cell wall by reactive species coming from the APPJ and the PAW. Our results provided evidence that the plasma radicals and the derived reactive species play critical roles in fungal spore inactivation.

  12. Optical and structural properties of plasma-treated Cordyceps bassiana spores as studied by circular dichroism, absorption, and fluorescence spectroscopy

    Lee, Geon Joon, E-mail: gjlee@kw.ac.kr; Sim, Geon Bo; Choi, Eun Ha [Plasma Bioscience Research Center/Department of Electrical and Biological Physics, Kwangwoon University, Seoul 139-701 (Korea, Republic of); Kwon, Young-Wan [KU-KIST Graduate School of Converging Science and Technology, Korea University, Seoul 136-701 (Korea, Republic of); Kim, Jun Young; Jang, Siun; Kim, Seong Hwan, E-mail: piceae@naver.com [Department of Microbiology and Institute of Basic Sciences, Dankook University, Cheonan 330-714 (Korea, Republic of)

    2015-01-14

    To understand the killing mechanism of fungal spores by plasma treatment, the optical, structural, and biological properties of the insect pathogenic fungus Cordyceps bassiana spores were studied. A nonthermal atmospheric-pressure plasma jet (APPJ) was used to treat the spores in aqueous solution. Optical emission spectra of the APPJ acquired in air indicated emission peaks corresponding to hydroxyl radicals and atomic oxygen. When the APPJ entered the aqueous solution, additional reactive species were derived from the interaction of plasma radicals with the aqueous solution. Fluorescence and absorption spectroscopy confirmed the generation of hydroxyl radicals and hydrogen peroxide in the plasma-activated water (PAW). Spore counting showed that plasma treatment significantly reduced spore viability. Absorption spectroscopy, circular dichroism (CD) spectroscopy, and agarose gel electrophoresis of the DNA extracted from plasma-treated spores showed a reduction in spore DNA content. The magnitude of the dip in the CD spectrum was lower in the plasma-treated spores than in the control, indicating that plasma treatment causes structural modifications and/or damage to cellular components. Tryptophan fluorescence intensity was lower in the plasma-treated spores than in the control, suggesting that plasma treatment modified cell wall proteins. Changes in spore viability and DNA content were attributed to structural modification of the cell wall by reactive species coming from the APPJ and the PAW. Our results provided evidence that the plasma radicals and the derived reactive species play critical roles in fungal spore inactivation.

  13. Structural study on Si O2 porous gels doped with copper ny using x-ray absorption spectroscopy

    Si O2 porous matrix were prepared by sol-gel method and doped with copper adding Cu Cl and Cu SO4. The samples were prepared in monolithic shape, were dried at 1100 deg C. The structural evolution of these gels was studied by X-ray Absorption Spectroscopy (EXAFs and Xanes). The obtained spectra show the formation of Cu O phase in the samples prepared from Cu Cl and treated at 900 and 1100 deg C. In the samples prepared from Cu SO4 occur the formation of Cu O at 900 deg C and Cu2 O at 1100 deg C. (author)

  14. Effect of two kinds of iron drops on the discoloration, atomic absorption and structural changes of primary teeth enamel

    Mehran M.; Jafari S; Mohammadi Bassir M.

    2009-01-01

    "nBackground and Aim: Black staining after taking iron drops on the primary teeth is always concern of parents. There is not an exact explanation for the mechanism of iron black staining. The purpose of this study was to compare tooth discolorations, atomic absorption and structural changes of primary teeth enamel caused by two kinds of iron drops[ Kharazmi(Iran) and Fer-in-sol(USA)]. "nMaterials and Methods: In this ex-vivo study, 93 sound primary teeth in normal color range were d...

  15. 100-picosecond time-resolved X-ray absorption fine structure of FeII(1,10-phenanthroline)3

    Studying photo-induced molecular dynamics in liquid with sub-nanosecond time-resolution and sub-Angstrom spatial resolution gives information for understanding fundamental chemical process in the photo-induced cooperative phenomena of molecular systems and also for developing new materials and devices. Here, we present time-resolved X-ray absorption fine structure on the spin-crossover complex FeII tris-(1,10-phenanthroline) dissolved in aqueous solution. We utilized femtosecond laser at 400nm pulse for excitation and 100ps X-ray pulse for probe.

  16. 100-picosecond time-resolved X-ray absorption fine structure of FeII(1,10-phenanthroline)3

    Sato, Tokushi; Nozawa, Shunsuke; Ichiyanagi, Kouhei; Tomita, Ayana; Ichikawa, Hirohiko; Chollet, Matthieu; Fujii, Hiroshi; Adachi, Shin-ichi; Koshihara, Shin-ya

    2009-02-01

    Studying photo-induced molecular dynamics in liquid with sub-nanosecond time-resolution and sub-Angstrom spatial resolution gives information for understanding fundamental chemical process in the photo-induced cooperative phenomena of molecular systems and also for developing new materials and devices. Here, we present time-resolved X-ray absorption fine structure on the spin-crossover complex FeII tris-(1,10-phenanthroline) dissolved in aqueous solution. We utilized femtosecond laser at 400nm pulse for excitation and 100ps X-ray pulse for probe.

  17. Branched isomeric 1,2,3-triazolium-based ionic liquids: new insight into structure-property relationships.

    Lartey, M; Meyer-Ilse, J; Watkins, J D; Roth, E A; Bowser, S; Kusuma, V A; Damodaran, K; Zhou, X; Haranczyk, M; Albenze, E; Luebke, D R; Hopkinson, D; Kortright, J B; Nulwala, H B

    2015-11-28

    A series of four isomeric 1,2,3-triazolium-based ionic liquids (ILs) with vary degree of branching were synthesized and characterized to investigate the effect of ion branching on thermal and physical properties of the resulting IL. It was found that increased branching led to a higher ionicity and higher viscosity. The thermal properties were also altered significantly and spectral changes in the near edge X-ray absorption fine structure (NEXAFS) spectra show that branching affects intermolecular interaction. While the ionicity and viscosity varying linearly with branching, the MDSC and NEXAFS measurements show that the cation shape has a stronger influence on the melting temperature and absorptive properties than the number of branched alkyl substituents. PMID:26486091

  18. The Sizes and Kinematic Structure of Absorption Systems Towards the Lensed Quasar APM08279+5255

    Ellison, S L; Pettini, M; Lewis, G F; Aracil, B; Petitjean, P; Srianand, R; Ellison, Sara L.; Ibata, Rodrigo; Pettini, Max; Lewis, Geraint F.; Aracil, Bastien; Petitjean, Patrick

    2003-01-01

    We have obtained spatially resolved spectra of the z=3.911 triply imaged QSO APM08279+5255 using the Space Telescope Imaging Spectrograph (STIS) on board the Hubble Space Telescope (HST). We study the line of sight equivalent width (EW) differences and velocity shear of high and low ionization absorbers (including a damped Lyman alpha [DLA] system identified in a spatially unresolved ground based spectrum) in the three lines of sight. We find that high ionization systems (primarily CIV absorbers) do not exhibit strong EW variations on scales 80%) over kpc scales. A minimum radius for strong (EW > 0.3 A) MgII systems of > 1.4 kpc is inferred from absorption coincidences in all lines of sight. For weak MgII absorbers (EW < 0.3 A), a maximum likelihood analysis indicates a most probable coherence scale of 2.0 kpc for a uniform spherical geometry, with 95% confidence limits ranging between 1.5 and 4.4 kpc. Finally, for systems with weak absorption that can be confidently converted to column densities, we find...

  19. Effect of damage on the energy absorption of prismatic thin-walled polymer composite structures

    Warrior, N.A.; Ribeaux, M. [School of Mechanical, Materials, Mfg. Engineering and Management, Univ. of Nottingham, Nottingham (United Kingdom)

    2003-07-01

    This paper investigates the effect of three types of simulated damage on the specific energy absorption (SEA) under axial crushing of square section E-glass/polyester composite tubes. Damage was simulated by through-drilled holes of various sizes, by delaminations of different sizes and by zones of out-of-plane impact damage created using a hemispherical tup driven at different energy levels. Also, in order to increase tolerance to out-of-plane impact damage, a thermoplastic interleaf was moulded into a number of samples. Tube samples were crushed axially at quasi-static (5 mm/min) and impact (5 ms{sup -1}) rates. SEA was seen to be strongly influenced by loading rate and significant reductions in SEA were seen as rate increased. Below a certain threshold damage level (or size) there was no effect on the SEA. Above this threshold, the damage triggered unstable failure - leading to greatly reduced energy absorption capability. The threshold level was seen to be dependent on damage type, damage level and test rate and a significant improvement in damage tolerance was seen as the loading rate increased. The SEA for thermoplastic interleaf samples was reduced, but became independent of rate. (orig.)

  20. Electronic Structure and Absorption Properties of Strongly Coupled Porphyrin-Perylene Arrays.

    High, Judah S; Virgil, Kyle A; Jakubikova, Elena

    2015-09-24

    Porphyrin-perylene arrays are ideal candidates for light-harvesting systems capable of panchromatic absorption. In this work, we employ density functional theory (DFT) and time-dependent DFT to investigate the unique UV-vis absorption properties exhibited by a series of ethynyl-linked porphyrin-perylene arrays that were previously synthesized and characterized spectroscopically [Chem. Commun. 2014, 50, 14512-5]. We find that the ethynyl linker is responsible for strong electronic coupling of porphyrin and perylene subunits in these systems. Additionally, these arrays exhibit a low barrier to rotation around the ethynyl linker (<1.4 kcal/mol per one perylene substituent), which results in a wide range of molecular conformations characterized by different porphyrin-perylene dihedral angles being accessible at room temperature. The best match between the calculated and experimental UV-vis spectra is obtained by averaging the calculated UV-vis spectra over the range of conformations defined by the porphyrin-perylene dihedral angles. Finally, our calculations suggest that the transitions in the lower energy region (550-750 nm) can be assigned to the excitations originating from the porphyrin subunit; the mid-energy region transitions (450-550 nm) are assigned to the perylene-centered excitations, while the high-energy transitions (350-450 nm) involve contributions from both porphyrin and perylene subunits. PMID:26322743

  1. PREFACE: The 15th International Conference on X-ray Absorption Fine Structure (XAFS15)

    Wu, Z. Y.

    2013-04-01

    The 15th International Conference on X-ray Absorption Fine Structure (XAFS15) was held on 22-28 July 2012 in Beijing, P. R. China. About 340 scientists from 34 countries attended this important international event. Main hall Figure 1. Main hall of XAFS15. The rapidly increasing application of XAFS to the study of a large variety of materials and the operation of the new SR source led to the first meeting of XAFS users in 1981 in England. Following that a further 14 International Conferences have been held. Comparing a breakdown of attendees according to their national origin, it is clear that participation is spreading to include attendees from more and more countries every year. The strategy of development in China of science and education is increasing quickly thanks to the large investment in scientific and technological research and infrastructure. There are three Synchrotron Radiation facilities in mainland China, Hefei Light Source (HLS) in the National Natural Science Foundation of China (NSRL), Beijing Synchrotron Radiation Facility (BSRF) in the Institute of High Energy Physics, and Shanghai Synchrotron Radiation Facility (SSRF) in the Shanghai Institute of Applied Physics. More than 10000 users and over 5000 proposals run at these facilities. Among them, many teams from the USA, Japan, German, Italy, Russia, and other countries. More than 3000 manuscript were published in SCI journals, including (incomplete) Science (7), Nature (10), Nature Series (7), PNAS (3), JACS (12), Angew. Chem. Int. Ed. (15), Nano Lett. (2), etc. In XAFS15, the participants contributed 18 plenary invited talks, 16 parallel invited talks, 136 oral presentations, 12 special talks, and 219 poster presentations. Wide communication was promoted in the conference halls, the classical banquet restaurant, and the Great Wall. Parallel hallCommunicationPoster room Figure 2. Parallel hallFigure 3. CommunicationFigure 4. Poster room This volume contains 136 invited and contributed papers

  2. Diameter-dependence of the electronic structures of the ZnO nanorods

    Full text: O K-, Zn L3- and K-edges x-ray absorption near-edge structure (XANES) spectra and scanning photoelectron microscopy (SPEM) spectra were measured for the ZnO nanorods with various diameters to study their electronic structures. Analysis of the XANES spectra revealed that charge transfer from the O 2p to Zn 3d states is enhanced with the decrease of the nanorod diameter. The charge transfer due to O 2p-Zn 3d hybridization is found to be compensated by the Zn 4p to O 2p charge transfer due to O 2p-Zn 4p rehybridization in consistence with the Zn 3d SPEM results. The valence-band photoemission spectra show changes in the electronic structures, especially near to the Fermi level, with the decrease of the nanorod diameter due to surface effect and/or local electrostatic polarization

  3. Potential antitumor gold drugs: DFT and XANES studies of local atomic and electronic structure

    Geometry structure optimization of the potential antitumor agent Au(bipy)(OH)2 was carried out by means of density functional theory simulations. The experimental Au L3-edge X-ray absorption near edge structure (XANES) spectrum of Au(bipy)(OH)2 was obtained. The theoretical Au L3-XANES spectra of the gold(III) complex Au(bipy)(OH)2 were simulated using both the self-consistent real-space full multiple scattering theory within the muffin-tin approximation for the potential shape and the full-potential finite difference method. The comparison of the theoretical spectra with the experimental XANES is discussed. The exact local atomic structure of gold complex Au(bipy)(OH)2 has been defined by two independent ab initio methods.

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

    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)2*1 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 to give a comprehensive description of the LuPc2 molecular electronic structure. The DFT calculations reveal the interaction of the two molecular rings with each other and with the metallic center forming new kinds of orbitals in between the phthalocyanine rings, which allows to better understand the experimentally obtained NEXAFS results. (authors)

  5. Island shape and electronic structure in diindenoperylene thin films deposited on Au(110) single crystals.

    Ciccullo, Francesca; Savu, Sabine A; Glaser, Mathias; Rocco, Maria Luiza M; Chassé, Thomas; Casu, M Benedetta

    2016-05-11

    We have investigated diindenoperylene (DIP) thin films deposited on Au(110) single crystals, by using a multi-technique approach based on X-ray photoemission spectroscopy (XPS), resonant photoemission spectroscopy (RPES), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, atomic force microscopy (AFM) and photoemission electron microscopy (PEEM). DIP molecules are physisorbed on gold, with image-charge screening playing the major role as an interface phenomenon. DIP thin films show Stranski-Krastanov growth mode and the structural herringbone arrangement mimics the arrangement found in DIP single crystals. These results are common with the (100) and (111) gold substrate geometries. On the contrary, the island aggregation is substrate geometry-dependent. This paves the way to exploit the degree of anisotropy in different lattice geometries as a tool for molecular patterning of inorganic surfaces, keeping the electronic structure preserved. PMID:27140434

  6. Structure and Orientation of the Mn4Ca Cluster in Plant Photosystem II Membranes Studied by Polarized Range-extended X-ray Absorption Spectroscopy*[S]♦

    Pushkar, Yulia; Yano, Junko; Glatzel, Pieter; Messinger, Johannes; Lewis, Azul; Sauer, Kenneth; Bergmann, Uwe; Yachandra, Vittal

    2006-01-01

    X-ray absorption spectroscopy has provided important insights into the structure and function of the Mn4Ca cluster in the oxygen-evolving complex of Photosystem II (PS II). The range of manganese extended x-ray absorption fine structure data collected from PSII until now has been, however, limited by the presence of iron in PS II. Using a crystal spectrometer with high energy resolution to detect solely the manganese Kα fluorescence, we are able to extend the extended x-ray absorption fine st...

  7. Pressure dependence of the local structure of iridium ditelluride across the structural phase transition

    Paris, E.; Joseph, B.; Iadecola, A.; Marini, C.; Ishii, H.; Kudo, K.; Pascarelli, S.; Nohara, M.; Mizokawa, T.; Saini, N. L.

    2016-04-01

    The local structure of IrTe2 has been studied by iridium L3-edge x-ray absorption spectroscopy (XAS) measurements as a function of pressure, performed at two temperatures (100 and 295 K) across the structural phase transition at ˜270 K. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectra show pressure-dependent anomalies, suggesting phase transitions that are characterized by different local atomic displacements. The high-temperature phase of IrTe2 (trigonal at 295 K) reveals a clear anomaly in the Ir-Te correlations at ˜4 GPa, while the low-temperature phase (at 100 K) shows a smaller change at ˜6 GPa, likely to be associated with transitions in lower-symmetry phases. XANES spectra, measuring higher-order atomic correlations, also show nonlinear pressure dependence in the local geometry at the anomalous pressures. These nonlinear changes suggest that IrTe2 goes through lower local symmetry phases with increasing pressure.

  8. Mechanisms of mercury removal by biochars produced from different feedstocks determined using X-ray absorption spectroscopy.

    Liu, Peng; Ptacek, Carol J; Blowes, David W; Landis, Richard C

    2016-05-01

    Thirty-six biochars produced from distinct feedstocks at different temperatures were evaluated for their potential to remove mercury (Hg) from aqueous solution at environmentally relevant concentrations. Concentrations of total Hg (THg) decreased by >90% in batch systems containing biochars produced at 600 and 700°C and by 40-90% for biochars produced at 300°C. Elevated concentrations of SO4(2-) (up to 1000mgL(-1)) were observed in solutions mixed with manure-based biochars. Sulfur X-ray absorption near edge structure (XANES) analyses indicate the presence of both reduced and oxidized S species in both unwashed and washed biochars. Sulfur XANES spectra obtained from biochars with adsorbed Hg were similar to those of washed biochars. Micro-X-ray fluorescence mapping results indicate that Hg was heterogeneously distributed across biochar particles. Extended X-ray absorption fine structure modeling indicates Hg was bound to S in biochars with high S content and to O and Cl in biochars with low S content. The predominant mechanisms of Hg removal are likely the formation of chemical bonds between Hg and various functional groups on the biochar. This investigation provides information on the effectiveness and mechanisms of Hg removal that is critical for evaluating biochar applications for stabilization of Hg in surface water, groundwater, soils, and sediments. PMID:26844404

  9. Local Structure and Electrical Performance of Pulsed Laser Deposited CdTe/CdS Thin-Film Solar Cells

    Nabizadeh, Arya; Lesinski, Darren; Cerqueira, Luis; Sahiner, Mehmet; Sahiner-Amscl Team

    2015-03-01

    The photovoltaic thin films of CdS/CdTe were prepared by pulsed laser deposition (PLD) on indium tin oxide (ITO) coated glass. The local structural variations in the thin films around Cd atom upon variations in the thin film growth parameters were investigated by X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure spectroscopy (EXAFS) and x-ray diffraction. X-ray absorption spectroscopy measurements were performed at the National Synchrotron Light Source of Brookhaven National Laboratory. The effect of the thicknesses of the CdS and CdTe layers, laser energy and the substrate temperature on the local crystal structure and coordination around the Cd atoms were investigated through quantitative multiple scattering analysis and modeling of the x-ray absorption spectroscopy data. The induced local structural modifications upon varying synthesis conditions are correlated with the electrical performance of these photovoltaic thin-films. The quantitative multiple scattering analyses and modeling of X-ray absorption spectroscopy data revealed the local environment around the Cd atoms are highly sensitive to thin film deposition parameters and the variations of the Cd local structure influences interface quality consequently, affect the electrical performance of these photovoltaic thin films. This work is supported by NSF Award #:DMI-0420952 and Research Corporation Award #:CC6405 and New Jersey Space Grant Consortium.

  10. Modeling of water absorption induced cracks in resin-based composite supported ceramic layer structures.

    Huang, Min; Thompson, V P; Rekow, E D; Soboyejo, W O

    2008-01-01

    Cracking patterns in the top ceramic layers of the modeled dental multilayers with polymer foundation are observed when they are immersed in water. This article developed a model to understand this cracking mechanism. When water diffuses into the polymer foundation of dental restorations, the foundation will expand; as a result, the stress will build up in the top ceramic layer because of the bending and stretching. A finite element model based on this mechanism is built to predict the stress build-up and the slow crack growth in the top ceramic layers during the water absorption. Our simulations show that the stress build-up by this mechanism is high enough to cause the cracking in the top ceramic layers and the cracking patterns predicted by our model are well consistent with those observed in experiments on glass/epoxy/polymer multilayers. The model is then used to discuss the life prediction of different dental ceramics. PMID:17497681

  11. Tri-layered composite plasmonic structure with a nanohole array for multiband enhanced absorption at visible to NIR frequencies: plasmonic and metamaterial resonances

    A tri-layered composite structure of gold/ZnS/gold, with the top gold layer patterned into a periodic array of circular holes, was fabricated by laser interference lithography and lift-off processes. This plasmonic composite absorbing structure showed a series of enhanced absorption peaks across the visible to NIR frequencies with an peak absorption exceeding 95% at 0.52 μm wavelength. These absorption peaks were reproduced in electromagnetic simulations of the structures. The peaks are shown to arise from the various resonances of the system: the localized surface plasmon resonances of the holes, the surface plasmon polaritons on the various interfaces and the shape dependent electromagnetic resonances of the holes. The measured angular dispersion of the absorption peaks indicated the SPP origin of the resonances while the computer simulations of the electromagnetic fields could be used to understand the nature of the localized resonances. (paper)

  12. Resonant absorption of ultrasonic waves in superconductors with moving vortex structure

    Equations describing interaction of ultrasonic waves with a moving vortex structure were derived. The addition to attenuation factor and relative change in velocity of longitudinal ultrasonic waves induced by the interaction were found. It proved that anomalous attenuation appears at a rate of the vortex structure movement V equal to half of velocity of the longitudinal ultrasonic wave propagating in the direction of the vortex structure movement. It is shown that in the vortex structure a slightly attenuating mode is present, its propagation rate 2V, which is responsible for the anomalous attenuation of longitudinal ultrasonic waves

  13. Fine structures in the optical absorption spectra of photochemical silver in silver halides? A call for further research

    Georgiev, Mladen

    2007-01-01

    A survey is presented of the work done so far to check earlier claims that a fine structure may be observed to occur under certain circumstances in the impurity spectral range of the optical absorption spectra of silver halides following photostimulation in the intrinsic range. This structure, associated with the photochemical formation of silver specks, has been questioned over the years. We now weigh carefully the experimental evidence on the silver halides against a background of similar data on the alkali halides, where competing processes run slower. We come to the conclusion that present day advances in experimental techniques may be quite adequate for providing a solid experimental basis to solve the problem unambiguously.

  14. Structural Characterization of 1,1,3,3-Tetramethylguanidinium Chloride Ionic Liquid by Reversible SO2 Gas Absorption

    Berg, Rolf W.; Harris, Pernille; Riisager, Anders;

    2013-01-01

    A unique new ionic liquid−gas adduct solid state compound formed between 1,1,3,3-tetramethylguanidinium chloride ([tmgH]Cl) and sulfur dioxide has been characterized by X-ray diffraction and Raman spectroscopy. The structure contains SO2 molecules of near normal structure kept at their positions...... by Cl−S interactions. The crystals belong in the orthorhombic system, space group Pbcn, with unit cell dimensions of a = 15.6908(10) Å, b = 9.3865(6) Å, and c = 14.1494(9) Å, angles α = β = γ = 90°, and Z = 8 at 120 K. The [tmgH]Cl has a very high absorption capacity of nearly 3 mol of SO2 per mol...

  15. Sensitivity of absorption spectra to surface segregation in InGaN/GaN quantum well structures

    We investigate the influence of the indium surface segregation on absorption spectra in InGaN/GaN quantum well structures having different indium amount. Results of the mathematical modeling show that such influence is more pronounced in quantum well structures with high indium amounts. The origin of this effect is related to the interplay between the indium surface segregation and internal electrostatic fields. Our theoretical analysis is performed using semiconductor Bloch equations within the Hartree-Fock approximation including into consideration excitonic effects. Results of the global sensitivity analysis evidence that the influence of the indium surface segregation is less than one order of magnitude in comparison with the impact of the quantum-well width and indium molar fraction. Also, the influence of the indium surface segregation is not the same for each interface of the quantum well

  16. Investigation of the structure and chemistry of surface layers on metals by x-ray absorption spectroscopy

    Most structural metals are very active chemically and without a passivating or protective layer would soon oxidize or corrode. The history of the industry is an attempt to minimize this process. The problem is becoming more acute, particularly in the aerospace industry, where the frames of many older airplanes are lasting longer than their outer skins. A more esoteric effect is the corrosion of metal surfaces in earth orbit by atomic oxygen. This paper is concerned with the structural and chemical characterization by x-ray absorption spectroscopy (XAS) of surface layers on aluminum alloys exposed to salt spray testing and with iron-based A-286 superalloy bolts exposed to atomic oxygen in a low earth orbit

  17. Effect of metal ion on the structure and function of LiPDF: The study of the fine structure around the metal site using XANES

    We used X-ray absorption near edge structure (XANES) spectroscopy to investigate the metal-dependent enzymatic activity of the peptide deformylase from Leptospira interrogans (LiPDF). Ab initio full multiple scattering calculations performed by MXAN are applied to obtain the local structure of the cobalt-containing LiPDF (Co-LiPDF) and zinc-containing LiPDF (Zn-LiPDF) around the metal sites in pH9.0 buffer solution. The result shows the cobalt-wat1 (the bond water molecule) distance of Co-LiPDF is 1.89 A, much shorter than that of Zn-LiPDF, 2.50 A. That is an essential factor for its low catalytic activity.

  18. Effect of metal ion on the structure and function of LiPDF: The study of the fine structure around the metal site using XANES

    Wang Yu [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Chu Wangsheng, E-mail: cws@ihep.ac.c [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Yang Feifei; Yu Meijuan; Zhao Haifeng [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Gong Weimin [National Laboratory of Biomacromolecules, Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101 (China); Dong Yuhui; Xie Yaning [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wu, Ziyu, E-mail: wuzy@ustc.edu.c [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

    2010-07-21

    We used X-ray absorption near edge structure (XANES) spectroscopy to investigate the metal-dependent enzymatic activity of the peptide deformylase from Leptospira interrogans (LiPDF). Ab initio full multiple scattering calculations performed by MXAN are applied to obtain the local structure of the cobalt-containing LiPDF (Co-LiPDF) and zinc-containing LiPDF (Zn-LiPDF) around the metal sites in pH9.0 buffer solution. The result shows the cobalt-wat1 (the bond water molecule) distance of Co-LiPDF is 1.89 A, much shorter than that of Zn-LiPDF, 2.50 A. That is an essential factor for its low catalytic activity.

  19. Differentiation of biological hydroxyapatite compounds by infrared spectroscopy, x-ray diffraction and extended x-ray absorption fine structure

    Chassot, E.; Oudadesse, H.; Irigaray, J.; Curis, E.; Bénazeth, S.; Nicolis, I.

    2001-12-01

    Pure hydroxyapatite (HAP) and HAP doped with 800 ppm of zinc were implanted in cortical bone of femur diaphysis of ovines [J. L. Irigaray et al., Mater. Clin. Appl. 28, 399 (1999)]. We observed that the doped HAP was better resorbed than pure HAP. The first hypothesis is that zinc acts as a stimulator on macrophage cells and improves quantity and quality of osteoblast cells. The second hypothesis is that zinc yields HAP structure that is better resorbed in biological field. For our experiment we used HAP doped with 3000 ppm of zinc in order to have a good sensitivity. In the present work, chemical studies by inductively coupled plasma absorption emission spectrometry, x ray diffraction, and infrared were carried out to determine the composition of major and trace elements in the doped hydroxyapatite, and the crystallographic structure. These studies can indicate possible modifications induced by the insertion of zinc. We used the extended x-ray absorption fine structure experimental station of LURE (Orsay, France) to try to clarify the atomic surroundings of zinc in doped HAP structure and transformations induced in initial lattice. Despite the low zinc concentration, we got good quality fluorescence mode spectra. These spectra showed medium range order of the material that is consistent with its crystalline form. To perform the analysis, we compared the result obtained with another models like β tricalcium phosphate and we created theoretical models of zinc in substitution of calcium in order to reproduce as well as possible the experimental spectrum. After this study, only two models are coherent with experimental spectrum, zinc in substitution of calcium in site I and zinc in the interstice between the two hydroxydes.

  20. Extended X-ray absorption fine structure of the [Fe]-hydrogenase Hmd active site

    Salomone-Stagni, Marco; Meyer-Klaucke, Wolfram [European Molecular Biology Laboratory (EMBL), Outstation Hamburg, Notkestr. 85, 22603 Hamburg (Germany); Vogt, Sonja; Shima, Seigo, E-mail: wolfram@embl-hamburg.d [Max-Planck-Institut fuer terrestrische Mikrobiologie, Karl-von-Frisch-Strasse, D-35043 Marburg (Germany)

    2009-11-15

    Hydrogenases are enzymes that catalyze the reversible oxidation of molecular hydrogen. Although their structure and catalytic mechanism are of considerable applied interest as models for the development of efficient catalysts for hydrogen fueled processes, the understanding of how hydrogenases react with H{sub 2} is only in its infancy. Two of the three known types of hydrogenases are iron-sulfur proteins that contain a dinuclear metal center, either [NiFe] or [FeFe]. In contrast, [Fe]-hydrogenase is the only mononuclear hydrogenase and thus a perfect system for studying the structural and electronic determinants of these enzymes. Here we summarize recent improvements in modeling based on the EXAFS signal and the geometric structure of this metalloenzyme in its as isolated or reconstituted form. The individual contributions to the EXAFS resulting in two different structural models are presented and discussed. Inspired by the new crystal structure, we show an advanced EXAFS model for the enzyme from Methanothermobacter marburgensis.

  1. Atomic resolution mapping of the excited-state electronic structure of Cu2O with time-resolved x-ray absorption spectroscopy

    Hillyard, P. W.; Kuchibhatla, S. V. N. T.; Glover, T. E.; Hertlein, M. P.; Huse, Nils; Nachimuthu, P.; Saraf, L. V.; Thevuthasan, S.; Gaffney, K. J.

    2010-05-02

    We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the O K-edge and the Cu L3-edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that the conduction-band and valence-band edges have very similar Cu 3d and O 2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the Cu L3- and O K-edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process.

  2. Small-scale structure in the interstellar medium: time-varying interstellar absorption towards {\\kappa} Velorum

    Smith, Keith T; Cordiner, Martin A; Sarre, Peter J; Smith, Arfon M; Bell, Tom A; Viti, Serena

    2012-01-01

    Ultra-high spectral resolution observations of time-varying interstellar absorption towards {\\kappa} Vel are reported, using the Ultra-High Resolution Facility on the Anglo-Australian Telescope. Detections of interstellar Ca I, Ca II, K I, Na I and CH are obtained, whilst an upper limit on the column density is reported for C_2. The results show continued increases in column densities of K I and Ca I since observations ~ 4 yr earlier, as the transverse motion of the star carried it ~ 10 AU perpendicular to the line of sight. Line profile models are fitted to the spectra and two main narrow components (A & B) are identified for all species except CH. The column density N(K I) is found to have increased by 82 +10-9 % between 1994 and 2006, whilst N(Ca I) is found to have increased by 32 +- 5 % over the shorter period of 2002-2006. The line widths are used to constrain the kinetic temperature to T_k,A 7 * 10^3 cm^-3 and n_B > 2 * 10^4 cm^-3. Calcium depletions are estimated from the Ca I / K I ratio. Compar...

  3. Nanostructured Palladium-Rhodium for Hydrogen Absorption: Processing, Structure, and Properties

    Yee, Joshua Keng

    Impetus to identify and implement alternatives to fossil fuels has driven research on several different energy sources. Use of hydrogen as a fuel has been of particular interest, due to its relative abundance and cleanliness as a fuel, amongst other desirable characteristics. However, one of the current challenges to using hydrogen is finding an effective and safe method to store it for later use. Metal hydrides have been proposed as possibilities for safe solid state storage of hydrogen. In the present thesis, cryomilled Pd-10%Rh was investigated as potential solid state storage material of hydrogen. Pd-10%Rh was first atomized, and then subsequently cryomilled. The cryomilled Pd-10%Rh was then examined using microstructural characterization techniques including optical microscopy, electron microscopy, and X-ray diffraction. Pd-10%Rh particles were significantly flattened, increasing the apparent surface area. Microstructural refinement was observed in the cryomilled Pd-10%Rh, generating grains at the nanometric scale through dislocation based activity. Hydrogen sorption properties were also characterized, generating both capacity as well as kinetics measurements. It was found that the microstructural refinement due to cryomilling did not play a significant role on hydrogen sorption properties until the smallest grain size (on the order of ~25 nm) was achieved. Additionally, the increased surface area and other changes in particle morphology were associated with cryomilling changed the kinetics of hydrogen absorption.

  4. Laboratory-based recording of holographic fine structure in X-ray absorption anisotropy using polycapillary optics

    Dabrowski, K.M. [Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Krakow (Poland); Korecki, P., E-mail: pawel.korecki@uj.edu.pl [Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Krakow (Poland)

    2012-08-15

    Highlights: Black-Right-Pointing-Pointer Holographic fine structures in X-ray absorption recorded using a tabletop setup. Black-Right-Pointing-Pointer Setup based on polycapillary collimating optics and an HOPG crystal. Black-Right-Pointing-Pointer Demonstration of element sensitivity by detection of X-ray fluorescence. Black-Right-Pointing-Pointer Potential of laboratory-based experiments for heavily doped crystals and thin films. - Abstract: A tabletop setup composed of a collimating polycapillary optics and a highly oriented pyrolytic graphite monochromator (HOPG) was characterized and used for recording two-dimensional maps of X-ray absorption anisotropy (XAA). XAA originates from interference of X-rays directly inside the sample. Depending on experimental conditions, fine structures in XAA can be interpreted in terms of X-ray holograms or X-ray standing waves and can be used for an element selective atomic-resolved structural analysis. The implementation of polycapillary optics resulted in a two-order of magnitude gain in the radiant intensity (photons/s/solid angle) as compared to a system without optics and enabled efficient recording of XAA with a resolution of 0.15 Degree-Sign for Mo K{alpha} radiation. Element sensitivity was demonstrated by acquisition of distinct XAA signals for Ga and As atoms in a GaAs (1 1 1) wafer by using X-ray fluorescence as a secondary signal. These results indicate the possibility of performing laboratory-based XAA experiments for heavily doped single crystals or thin films. So far, because of the weak holographic modulation of XAA, such experiments could be only performed using synchrotron radiation.

  5. Structural, electronic and magnetic properties of Er implanted ZnO thin films

    We report the structural, electronic and magnetic properties of Er implanted and annealed ZnO thin films. The effect of annealing in oxygen-deficient and oxygen-rich conditions was investigated. Rutherford backscattering spectrometry results revealed that the Er atoms are located at the implantation depth of around 13 nm, and annealing conditions had no adverse effect on the Er concentration in the layer. Raman spectroscopy results showed peak related to E2(high) mode of ZnO indicating enhanced crystalline quality of the Er implanted and annealed ZnO films. X-ray absorption near edge spectroscopy results demonstrated pre-edge features in O K-edge which are attributed to the structural defects in the films. Room temperature magnetic ordering was observed in Er implanted and annealed films, and is mainly assigned to the intrinsic defects in ZnO

  6. Structural, electronic and magnetic properties of Er implanted ZnO thin films

    Murmu, P. P.; Kennedy, J.; Ruck, B. J.; Leveneur, J.

    2015-09-01

    We report the structural, electronic and magnetic properties of Er implanted and annealed ZnO thin films. The effect of annealing in oxygen-deficient and oxygen-rich conditions was investigated. Rutherford backscattering spectrometry results revealed that the Er atoms are located at the implantation depth of around 13 nm, and annealing conditions had no adverse effect on the Er concentration in the layer. Raman spectroscopy results showed peak related to E2(high) mode of ZnO indicating enhanced crystalline quality of the Er implanted and annealed ZnO films. X-ray absorption near edge spectroscopy results demonstrated pre-edge features in O K-edge which are attributed to the structural defects in the films. Room temperature magnetic ordering was observed in Er implanted and annealed films, and is mainly assigned to the intrinsic defects in ZnO.

  7. Structural, electronic and magnetic properties of Er implanted ZnO thin films

    Murmu, P.P. [National Isotope Centre, GNS Science, PO Box 31312, Lower Hutt 5010 (New Zealand); The MacDiarmid Institute for Advanced Materials and Nanotechnology, PO Box 600, Wellington 6140 (New Zealand); Kennedy, J., E-mail: J.Kennedy@gns.cri.nz [National Isotope Centre, GNS Science, PO Box 31312, Lower Hutt 5010 (New Zealand); The MacDiarmid Institute for Advanced Materials and Nanotechnology, PO Box 600, Wellington 6140 (New Zealand); Ruck, B.J. [The MacDiarmid Institute for Advanced Materials and Nanotechnology, PO Box 600, Wellington 6140 (New Zealand); Leveneur, J. [National Isotope Centre, GNS Science, PO Box 31312, Lower Hutt 5010 (New Zealand)

    2015-09-15

    We report the structural, electronic and magnetic properties of Er implanted and annealed ZnO thin films. The effect of annealing in oxygen-deficient and oxygen-rich conditions was investigated. Rutherford backscattering spectrometry results revealed that the Er atoms are located at the implantation depth of around 13 nm, and annealing conditions had no adverse effect on the Er concentration in the layer. Raman spectroscopy results showed peak related to E{sub 2}(high) mode of ZnO indicating enhanced crystalline quality of the Er implanted and annealed ZnO films. X-ray absorption near edge spectroscopy results demonstrated pre-edge features in O K-edge which are attributed to the structural defects in the films. Room temperature magnetic ordering was observed in Er implanted and annealed films, and is mainly assigned to the intrinsic defects in ZnO.

  8. Photodegradation of the electronic structure of PCBM and C60 films in air

    Anselmo, Ana S.; Dzwilewski, Andrzej; Svensson, Krister; Moons, Ellen

    2016-05-01

    Fullerenes are common electron acceptors in organic solar cells. Here the photostability in air of the electronic structures of spin-coated PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) and evaporated C60 films are studied using ultraviolet photoelectron spectroscopy (UPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. After exposing these materials in air to simulated sunlight, the filled and empty molecular orbitals are strongly altered, indicating that the conjugated π-system of the C60-cage has degraded. Even a few minutes in normal lab light induces changes. These results stress the importance of protecting fullerene-based films from light and air during processing, operation, and storage.

  9. Electronic structure of RbCl and Rb2ZnCl4 in solid and liquid states: analysis of near structure of X-ray absorption

    The experimental absorption spectra for the Rb K-edge in the RbCl and Rb2ZnCl4 structures in the solid state and in the melt are obtained. The detailed analysis of the RbCl electron structure is carried out through the method of complete multiple scattering and good agreement with the experimental spectrum is obtained. The thin structure of free electron states in the conductivity zone of the studied compound is determined. It is shown that the rubidium nonoccupied states are in a significant degree hybridized with the Cl p-states in the conductivity band. It is established that the RbCl melt may be with sufficiently good approximation described on the basis of the cluster model with the Debye-Waller parameters σ2 = 0.3 A-2

  10. Effect of two kinds of iron drops on the discoloration, atomic absorption and structural changes of primary teeth enamel

    Mehran M.

    2009-03-01

    Full Text Available "nBackground and Aim: Black staining after taking iron drops on the primary teeth is always concern of parents. There is not an exact explanation for the mechanism of iron black staining. The purpose of this study was to compare tooth discolorations, atomic absorption and structural changes of primary teeth enamel caused by two kinds of iron drops[ Kharazmi(Iran and Fer-in-sol(USA]. "nMaterials and Methods: In this ex-vivo study, 93 sound primary teeth in normal color range were divided into five groups. Two groups of samples were immersed into the Artificial Caries Challenge(ACC for two weeks before getting exposured to iron drops: Group 1 Control(NS: sound enamel teeth which were kept in Normal Saline environment(NS(13teeth. Group 2 (NS-KH: NS, kharazmi iron drop (20 teeth. Group 3 (ACC-KH: ACC, Kharazmi iron drop (20teeth. Group 4 (NS-F-in-S: NS, Fer-in-Sol iron drop (20teeth. Group 5 (ACC-F-in-S: ACC, Fer-in-Sol iron drop. Visual tooth discolorations were determined by a specialist in operative dentistry who was not aware of experimental groups. The iron concentration was measured by ICP system (Vista-pro, Australia and the structural changes were studied by SEM (Philips, Netherland. The data of discoloration were studied with Kruskal-Wallis test and multiple comparison using Bonferroni type test, and with the data of atomic absorption were studied with oneway ANOVA test and Tukey HSD test. "nResults: The discoloration in the teeth immersed into the ACC (ACC-KH, ACC-F-in-S was more severe than the sound enamel surface (NS-KH, NS-F-IN-S (p<0.001 and Kharazmi iron drop caused more discoloration in the teeth immersed into the ACC (p=0.018. The teeth immersed into the ACC, absorbed more iron than the sound enamel surface (p<0.001 and also the teeth immersed into the ACC absorbed more Kharazmi iron drop (p<0.001. In the Scanning Electron Microscopy study, at low magnification in the sound teeth the perikymata was arranged regular. At low

  11. A different view of structure-making and structure-breaking in alkali halide aqueous solutions through x-ray absorption spectroscopy.

    Waluyo, Iradwikanari; Nordlund, Dennis; Bergmann, Uwe; Schlesinger, Daniel; Pettersson, Lars G M; Nilsson, Anders

    2014-06-28

    X-ray absorption spectroscopy measured in transmission mode was used to study the effect of alkali and halide ions on the hydrogen-bonding (H-bonding) network of water. Cl(-) and Br(-) are shown to have insignificant effect on the structure of water while I(-) locally weakens the H-bonding, as indicated by a sharp increase of the main-edge feature in the x-ray absorption spectra. All alkali cations act as structure-breakers in water, weakening the H-bonding network. The spectral changes are similar to spectra of high density ices where the 2nd shell has collapsed due to a break-down of the tetrahedral structures, although here, around the ions, the breakdown of the local tetrahedrality is rather due to non-directional H-bonding to the larger anions. In addition, results from temperature-dependent x-ray Raman scattering measurements of NaCl solution confirm the H-bond breaking effect of Na(+) and the effect on the liquid as similar to an increase in temperature. PMID:24985653

  12. Oxygen K-edge extended x-ray-absorption fine-structure studies of molecules containing oxygen and carbon atoms

    The absorption spectra of a group of selected molecules containing O: C bonds, carbon monoxide, carbon dioxide, carbonyl sulfide, acetone, ethanol, diethylether, tetrahydrofuran, and dioxane, have been recorded in a transmission mode in the energy region from 500 to 1000 eV. Earlier observation of extended x-ray-absorption fine structure (EXAFS) in some of these molecules is confirmed. A systematic analysis of the EXAFS spectra is performed. The results in both phase and amplitude show disagreement with the single-electron single-scattering theory with plane-wave approximation. The measured phase is systematically lower than the theory of Teo and Lee [J. Am. Chem. Soc. 101, 2815 (1979)] by about 0.7--1.5 rad, which may be significant in determining interatomic distances. The EXAFS amplitude function in the molecules containing oxygen-carbon single bonds also shows an appreciable deviation (decrease) in the first-neighbor backscattering from that predicted by theory and an increase in the second-neighbor backscattering at high-k values

  13. A Comparative Study of Molecular Structure, pKa, Lipophilicity, Solubility, Absorption and Polar Surface Area of Some Antiplatelet Drugs

    Milan Remko

    2016-03-01

    Full Text Available Theoretical chemistry methods have been used to study the molecular properties of antiplatelet agents (ticlopidine, clopidogrel, prasugrel, elinogrel, ticagrelor and cangrelor and several thiol-containing active metabolites. The geometries and energies of most stable conformers of these drugs have been computed at the Becke3LYP/6-311++G(d,p level of density functional theory. Computed dissociation constants show that the active metabolites of prodrugs (ticlopidine, clopidogrel and prasugrel and drugs elinogrel and cangrelor are completely ionized at pH 7.4. Both ticagrelor and its active metabolite are present at pH = 7.4 in neutral undissociated form. The thienopyridine prodrugs ticlopidine, clopidogrel and prasugrel are lipophilic and insoluble in water. Their lipophilicity is very high (about 2.5–3.5 logP values. The polar surface area, with regard to the structurally-heterogeneous character of these antiplatelet drugs, is from very large interval of values of 3–255 Å2. Thienopyridine prodrugs, like ticlopidine, clopidogrel and prasugrel, with the lowest polar surface area (PSA values, exhibit the largest absorption. A high value of polar surface area (PSA of cangrelor (255 Å2 results in substantial worsening of the absorption in comparison with thienopyridine drugs.

  14. Precise limits on cosmological variability of the fine-structure constant with zinc and chromium quasar absorption lines

    Murphy, Michael T; Prochaska, J Xavier

    2016-01-01

    The strongest transitions of Zn and CrII are the most sensitive to relative variations in the fine-structure constant ($\\Delta\\alpha/\\alpha$) among the transitions commonly observed in quasar absorption spectra. They also lie within just 40 \\AA\\ of each other (rest frame), so they are resistant to the main systematic error affecting most previous measurements of $\\Delta\\alpha/\\alpha$: long-range distortions of the wavelength calibration. While Zn and CrII absorption is normally very weak in quasar spectra, we obtained high signal-to-noise, high-resolution echelle spectra from the Keck and Very Large Telescopes of 9 rare systems where it is strong enough to constrain $\\Delta\\alpha/\\alpha$ from these species alone. These provide 12 independent measurements (3 quasars were observed with both telescopes) at redshifts 1.0--2.4, 11 of which pass stringent reliability criteria. These 11 are all consistent with $\\Delta\\alpha/\\alpha=0$ within their individual uncertainties of 3.5--13 parts per million (ppm), with a we...

  15. Probing local and electronic structure in Warm Dense Matter: single pulse synchrotron x-ray absorption spectroscopy on shocked Fe

    Torchio, Raffaella; Occelli, Florent; Mathon, Olivier; Sollier, Arnaud; Lescoute, Emilien; Videau, Laurent; Vinci, Tommaso; Benuzzi-Mounaix, Alessandra; Headspith, Jon; Helsby, William; Bland, Simon; Eakins, Daniel; Chapman, David; Pascarelli, Sakura; Loubeyre, Paul

    2016-06-01

    Understanding Warm Dense Matter (WDM), the state of planetary interiors, is a new frontier in scientific research. There exists very little experimental data probing WDM states at the atomic level to test current models and those performed up to now are limited in quality. Here, we report a proof-of-principle experiment that makes microscopic investigations of materials under dynamic compression easily accessible to users and with data quality close to that achievable at ambient. Using a single 100 ps synchrotron x-ray pulse, we have measured, by K-edge absorption spectroscopy, ns-lived equilibrium states of WDM Fe. Structural and electronic changes in Fe are clearly observed for the first time at such extreme conditions. The amplitude of the EXAFS oscillations persists up to 500 GPa and 17000 K, suggesting an enduring local order. Moreover, a discrepancy exists with respect to theoretical calculations in the value of the energy shift of the absorption onset and so this comparison should help to refine the approximations used in models.

  16. High-precision limit on variation in the fine-structure constant from a single quasar absorption system

    Kotuš, Srđan M; Carswell, Robert F

    2016-01-01

    The brightest southern quasar above redshift $z=1$, HE 0515$-$4414, with its strong intervening metal absorption-line system at $z_{abs}=1.1508$, provides a unique opportunity to precisely measure or limit relative variations in the fine-structure constant ($\\Delta\\alpha/\\alpha$). A variation of just $\\sim$3 parts per million (ppm) would produce detectable velocity shifts between its many strong metal transitions. Using new and archival observations from the Ultraviolet and Visual Echelle Spectrograph (UVES) we obtain an extremely high signal-to-noise ratio spectrum (peaking at S/N $\\approx250$ pix$^{-1}$). This provides the most precise measurement of $\\Delta\\alpha/\\alpha$ from a single absorption system to date, $\\Delta\\alpha/\\alpha=-1.42\\pm0.55_{\\rm stat}\\pm0.65_{\\rm sys}$ ppm, comparable with the precision from previous, large samples of $\\sim$150 absorbers. The largest systematic error in all (but one) previous similar measurements, including the large samples, was long-range distortions in the wavelengt...

  17. Interfacial engineering of optical absorption in epitaxial LaCrO3-SrTiO3 superlattices

    Comes, Ryan; Kaspar, Tiffany; Heald, Steve; Bowden, Mark; Chambers, Scott

    2015-03-01

    SrTiO3 (STO) is a wide-gap semiconductor well suited for photocatalytic H2 production due to the alignment of its band edges with the half-cell energies of the H2O redox reactions. However, the wide optical gap of STO (3.3 eV) makes the material an inefficient light absorber in the visible spectrum, preventing formation of electron-hole pairs needed for photocatalysis. Superlattice films comprised of alternating layers of band insulator SrTiO3 and Mott insulator LaCrO3 (LCO) have been theoretically predicted to offer intriguing optical properties due to the broken symmetry between the unoccupied Ti dxy and Ti dxz and dyz orbitals. In this work, we examine the properties of LCO-STO superlattices grown with various periodicities on (La,Sr)(Al,Ta)O3 (LSAT) (001) substrates using oxide molecular beam epitaxy. Films were characterized via in situ x-ray photoelectron spectroscopy to measure valence band structure and interfacial band bending. Polarized Ti and Cr K-edge x-ray absorption near edge spectroscopy was used to examine the bonding anisotropy. Spectroscopic ellipsometry measurements show the presence of interfacially-induced visible light absorption not found in either STO or LCO.

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

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

    2016-02-01

    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 metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

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

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

    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 metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge. PMID:26908198

  20. In situ examination of uranium contaminated soil particles by micro-X-ray absorption and micro-fluorescence spectroscopies

    Two complimentary spectroscopic techniques, X-ray absorption and fluorescence spectroscopy have been conducted at spatial scales of 1 to 25 μm on uranium contaminated soil sediments collected from two former nuclear materials processing facilities of the DOE: Fernald, OH and Savannah River Site, SC. A method of imbedding particles in a non-reactive Si polymer was developed such that individual particles could be examined before and after extraction with a wide range of chemicals typically used in sequential extraction techniques and others proposed for ex situ chemical intervention technologies. Using both the micro-X-ray fluorescence (XRF) and micro-X-ray Absorption Near Edge Structure (XANES) techniques, both elemental and oxidation state distribution maps were generated on individual particles before and following chemical extraction. XANES can determine the relative proportion of U(VI) and U(IV) in phases comprising individual particles before and after extraction and showed that greater than 85% of the uranium existed as hexavalent U(VI). Fluorescence spectra of contaminated particles containing mainly U(VI) revealed populations of uranyl hydroxide phases and demonstrated the relative efficacy and specificity of each extraction method. Correlation of XAS and fluorescence data at micron scales provides information of U oxidation state as well as chemical form in heterogeneous samples. (author)

  1. Structural characterization of vanadium oxide catalysts supported on nanostructured silica SBA-15 using X-ray absorption spectroscopy

    Walter Anke

    2010-02-01

    Full Text Available Abstract The local structure of vanadium oxide supported on nanostructured SiO2 (VxOy/SBA-15 was investigated by in situ X-ray absorption spectroscopy (XAS. Because the number of potential parameters in XAS data analysis often exceeds the number of "independent" parameters, evaluating the reliability and significance of a particular fitting procedure is mandatory. The number of independent parameters (Nyquist may not be sufficient. Hence, in addition to the number of independent parameters, a novel approach to evaluate the significance of structural fitting parameters in XAS data analysis is introduced. Three samples with different V loadings (i.e. 2.7 wt %, 5.4 wt %, and 10.8 wt % were employed. Thermal treatment in air at 623 K resulted in characteristic structural changes of the V oxide species. Independent of the V loading, the local structure around V centers in dehydrated VxOy/SBA-15 corresponded to an ordered arrangement of adjacent V2O7 units. Moreover, the V2O7 units were found to persist under selective oxidation reaction conditions.

  2. Low voltage operation of electro-absorption modulator promising for high-definition 3D imaging application using a three step asymmetric coupled quantum well structure

    In this paper, we propose a transmission type electro-absorption modulator (EAM) operating at 850 nm having low operating voltage and high absorption change with low insertion loss using a novel three step asymmetric coupled quantum well (3 ACQW) structure which can be used as an optical image shutter for high-definition (HD) three dimensional (3D) imaging. Theoretical calculations show that the exciton red shift of 3 ACQW structure is more than two times larger than that of rectangular quantum well (RQW) structure while maintaining high absorption change. The EAM having coupled cavities with 3 ACQW structure shows a wide spectral bandwidth and high amplitude modulation at a bias voltage of only -8V, which is 41% lower in operating voltage than that of RQW, making the proposed EAM highly attractive as an optical image shutter for HD 3D imaging applications

  3. Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy.

    Shelby, Megan L; Lestrange, Patrick J; Jackson, Nicholas E; Haldrup, Kristoffer; Mara, Michael W; Stickrath, Andrew B; Zhu, Diling; Lemke, Henrik T; Chollet, Matthieu; Hoffman, Brian M; Li, Xiaosong; Chen, Lin X

    2016-07-20

    Photoexcited Nickel(II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through multiple electronic states following an initial porphyrin-based excitation, some involving metal centered electronic configuration changes that could be harnessed catalytically before excited state relaxation. While a NiTMP excited state present at 100 ps was previously identified by X-ray transient absorption (XTA) spectroscopy at a synchrotron source as a relaxed (d,d) state, the lowest energy excited state (J. Am. Chem. Soc., 2007, 129, 9616 and Chem. Sci., 2010, 1, 642), structural dynamics before thermalization were not resolved due to the ∼100 ps duration of the available X-ray probe pulse. Using the femtosecond (fs) X-ray pulses of the Linac Coherent Light Source (LCLS), the Ni center electronic configuration from the initial excited state to the relaxed (d,d) state has been obtained via ultrafast Ni K-edge XANES (X-ray absorption near edge structure) on a time scale from hundreds of femtoseconds to 100 ps. This enabled the identification of a short-lived Ni(I) species aided by time-dependent density functional theory (TDDFT) methods. Computed electronic and nuclear structure for critical excited electronic states in the relaxation pathway characterize the dependence of the complex's geometry on the electron occupation of the 3d orbitals. Calculated XANES transitions for these excited states assign a short-lived transient signal to the spectroscopic signature of the Ni(I) species, resulting from intramolecular charge transfer on a time scale that has eluded previous synchrotron studies. These combined results enable us to examine the excited state structural dynamics of NiTMP prior to thermal relaxation and to capture intermediates of potential photocatalytic significance. PMID:27286410

  4. Artificial intelligence applied to the automatic analysis of absorption spectra. Objective measurement of the fine structure constant

    Bainbridge, Matthew B

    2016-01-01

    A new and fully-automated method is presented for the analysis of high-resolution absorption spectra (GVPFIT). The method has broad application but here we apply it specifically to the problem of measuring the fine structure constant at high redshift. For this we need objectivity and reproducibility. GVPFIT is also motivated by the importance of obtaining a large statistical sample of measurements of $\\Delta\\alpha/\\alpha$. Interactive analyses are both time consuming and complex and automation makes obtaining a large sample feasible. Three numerical methods are unified into one artificial intelligence process: a genetic algorithm that emulates the Darwinian processes of reproduction, mutation and selection, non-linear least-squares with parameter constraints (VPFIT), and Bayesian model averaging. In contrast to previous methodologies, which relied on a particular solution as being the most likely model, GVPFIT plus Bayesian model averaging derives results from a large set of models, and helps overcome systema...

  5. Note: Construction of x-ray scattering and x-ray absorption fine structure beamline at the Pohang Light Source

    A new hard x-ray beamline, 10B KIST-PAL beamline (BL10B), has been designed and constructed at the Pohang Light Source (PLS) in Korea. The beamline, operated by Pohang Accelerator Laboratory-Korean Institute of Science and Technology consortium, is dedicated to x-ray scattering (XRS) and x-ray absorption fine structure (XAFS) experiments. X rays with photon energies from 4.0 to 16.0 keV are delivered to the experimental station passing a collimating mirror, a fixed-exit double-crystal Si(111) monochromator, and a toroidal mirror. Basic experimental equipments for XAFS measurement, a high resolution diffractometry, an image plate detector system, and a hot stage have been prepared for the station. From our initial commissioning and performance testing of the beamline, it is observed that BL10B beamline can perform XRS and XAFS measurements successfully.

  6. Warm gas at high redshift clues to gravitational structure formation from optical spectroscopy of Lyman $\\alpha$ absorption systems

    Rauch, M

    1995-01-01

    We discuss the effects of gravitational collapse on the shape of absorption line profiles for low column density (log N(HI) < 14) Lyman Alpha forest clouds and argue by comparison with cosmological simulations that Lyman alpha forest observations show the signs of ongoing gravitational structure formation at high redshift. The departures of observed line profiles from thermal Voigt profiles (caused by bulk motion of infalling gas and compressional heating) are evident from the results of profile fitting as a correlation in velocity space among pairs of components with discrepant Doppler parameters. This correlation also allows us to qualitatively understand the meaning of the Doppler parameter - column density (b vs. N(HI)) diagram for intergalactic gas.

  7. Electrochemical discharge of nanocrystalline magnetite: structure analysis using X-ray diffraction and X-ray absorption spectroscopy.

    Menard, Melissa C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

    2013-11-14

    Magnetite (Fe3O4) is an abundant, low cost, environmentally benign material with potential application in batteries. Recently, low temperature coprecipitation methods have enabled preparation of a series of nanocrystalline magnetite samples with a range of crystallite sizes. Electrochemical cells based on Li/Fe3O4 show a linear increase in capacity with decreasing crystallite size at voltages ≥1.2 V where a 2× capacity improvement relative to commercial (26.2 nm) magnetite is observed. In this report, a combination of X-ray powder diffraction (XRD) and X-ray absorption spectroscopy (XAS) is used to measure magnetite structural changes occurring upon electrochemical reduction, with parent Fe3O4 crystallite size as a variable. Notably, XAS provides evidence of metallic iron formation at high levels of electrochemical reduction. PMID:24077019

  8. Electron transfer during selenium reduction by iron surfaces in aqueous solution: High resolution X-ray absorption study

    Kvashnina, K. O.; Butorin, S. M.; Cui, D.; Vegelius, J.; Puranen, A.; Gens, R.; Glatzel, P.

    2009-11-01

    We present a study of selenate (SeO42-) on an iron surface in ground water solution by X-ray absorption near-edge spectroscopy. Spectral sharpening is obtained by using the high energy resolution fluorescence detection technique that also efficiently suppresses the strong fluorescence signal from the Fe surface in the highly dilute samples (Se concentration < 3 ppm). We observe fully reduced Se on polished Fe surfaces while no changes are found for Se on oxidized Fe surface.

  9. Electronic Structure and Bonding in Complex Biomolecule

    Ouyang, Lizhi

    2005-03-01

    For over a century vitamin B12 and its enzyme cofactor derivates have persistently attracted research efforts for their vital biological role, unique Co-C bonding, rich red-ox chemistry, and recently their candidacies as drug delivery vehicles etc. However, our understanding of this complex metalorganic molecule's efficient enzyme activated catalytic power is still controversial. We have for the first time calculated the electronic structure, Mulliken effective charge and bonding of a whole Vitamin B12 molecule without any structural simplification by first- principles approaches based on density functional theory using structures determined by high resolution X-ray diffraction. A partial density of states analysis shows excellent agreement with X-ray absorption data and has been used successfully to interpret measured optical absorption spectra. Mulliken bonding analysis of B12 and its derivatives reveal noticeable correlations between the two axial ligands which could be exploited by the enzyme to control the catalytic process. Our calculated X-ray near edge structure of B12 and its derivates using Slater's transition state theory are also in good agreement with experiments. The same approach has been applied to other B12 derivatives, ferrocene peptides, and recently DNA molecules.

  10. Structure of collagen adsorbed on a model implant surface resolved by polarization modulation infrared reflection-absorption spectroscopy.

    Brand, Izabella; Habecker, Florian; Ahlers, Michael; Klüner, Thorsten

    2015-03-01

    The polarization modulation infrared reflection-absorption spectra of collagen adsorbed on a titania surface and quantum chemical calculations are used to describe components of the amide I mode to the protein structure at a sub-molecular level. In this study, imino acid rich and poor fragments, representing the entire collagen molecule, are taken into account. The amide I mode of the collagen triple helix is composed of three absorption bands which involve: (i) (∼1690cm(-1)) the CO stretching modes at unhydrated groups, (ii) (1655-1673cm(-1)) the CO stretching at carbonyl groups at imino acids and glycine forming intramolecular hydrogen bonds with H atoms at both NH2 and, unusual for proteins, CH2 groups at glycine at a neighbouring chain and (iii) (∼1640cm(-1)) the CO stretching at carbonyl groups forming hydrogen bonds between two, often charged, amino acids as well as hydrogen bonds to water along the entire helix. The IR spectrum of films prepared from diluted solutions (c<50μgml(-1)) corresponds to solution spectra indicating that native collagen molecules interact with water adsorbed on the titania surface. In films prepared from solutions (c⩾50μgml(-1)) collagen multilayers are formed. The amide I mode is blue-shifted by 18cm(-1), indicating that intramolecular hydrogen bonds at imino acid rich fragments are weakened. Simultaneous red-shift of the amide A mode implies that the strength of hydrogen bonds at the imino acid poor fragments increases. Theoretically predicted distortion of the collagen structure upon adsorption on the titania surface is experimentally confirmed. PMID:25498816

  11. Coordinates of the Absorption Capacity of Structural and Cohesion Funds at EU Level

    Anca Simina POPESCU

    2015-09-01

    Full Text Available The structural and cohesion funds are considered an attractive instrument for the funding of investments opportunities especially in times of crisis when the private investments are reduced. Nevertheless, they have not been factually highlighted in order to empirically document the role of European funds in supporting the short-term economic growth, at macroeconomic level. The target of absorbing as much European financial non-refundable aid requires constant efforts made by the member states and administration authorities, the involvement of regional and local public administrations in each stage of the process, as well as an appropriate capacity of institutional structures and management and control systems, they being basic premises of this objective achievement.

  12. High resolution simulations of energy absorption in dynamically loaded cellular structures

    Winter, R. E.; Cotton, M.; Harris, E. J.; Eakins, D. E.; McShane, G.

    2016-04-01

    Cellular materials have potential application as absorbers of energy generated by high velocity impact. CTH, a Sandia National Laboratories Code which allows very severe strains to be simulated, has been used to perform very high resolution simulations showing the dynamic crushing of a series of two-dimensional, stainless steel metal structures with varying architectures. The structures are positioned to provide a cushion between a solid stainless steel flyer plate with velocities ranging from 300 to 900 m/s, and an initially stationary stainless steel target. Each of the alternative architectures under consideration was formed by an array of identical cells each of which had a constant volume and a constant density. The resolution of the simulations was maximised by choosing a configuration in which one-dimensional conditions persisted for the full period over which the specimen densified, a condition which is most readily met by impacting high density specimens at high velocity. It was found that the total plastic flow and, therefore, the irreversible energy dissipated in the fully densified energy absorbing cell, increase (a) as the structure becomes more rodlike and less platelike and (b) as the impact velocity increases. Sequential CTH images of the deformation processes show that the flow of the cell material may be broadly divided into macroscopic flow perpendicular to the compression direction and jetting-type processes (microkinetic flow) which tend to predominate in rod and rodlike configurations and also tend to play an increasing role at increased strain rates. A very simple analysis of a configuration in which a solid flyer impacts a solid target provides a baseline against which to compare and explain features seen in the simulations. The work provides a basis for the development of energy absorbing structures for application in the 200-1000 m/s impact regime.

  13. Time-Resolved Pump-Probe X-ray Absorption Fine Structure Spectroscopy of Gaq3

    Dicke, Benjamin

    2014-01-01

    Gallium(tris-8-hydroxyquinoline) (Gaq3) belongs to a class of metal organic compounds, usedas electron transport layer and emissive layer in organic light emitting diodes. Many researchactivities have concentrated on the optical and electronic properties, especially of the homologuemolecule aluminum(tris-8-hydroxyquinoline) (Alq3). Knowledge of the first excited state S1structure of these molecules could provide deeper insight into the processes involved into the operationof electronic device...

  14. Water absorption, cooking properties and cell structure of gamma irradiated soybeans

    Gamma irradiation was applied to soybean(Glycine max.), Hwangkeum, at dose levels of 0, 5, 10 and 20 kGy to improve the physical properties of soybeans. The time to reach a fixed moisture content was reduced depending on the increment of soaking temperatures and applied irradiation dose levels. Irradiation at 5~20 kGy resulted in reduction in soaking time of the soybeans by about 3~6 hrs at soaking temperature of 20°. The degree of cooking of soybeans in boiling water was determined by measuring the maximum cutting force of cotyledon. The cutting force to reach complete cooking was about 145g/g. Irradiation at 5~20 kGy resulted in a reduction of cooking time of soybeans by 55~75% as compared to the nonirradiated soybean. In electron microscopic observation of seed coat inner, the parenchyma of nonirradiated soybean showed tight fibrillar structure, whereas that of irradiated soybeans showed loosened and deformed structure. The microstructure of compressed cells and cotyledon epidermis was also deformed by gamma irradiation. In subcellular structure of cotyledon, the roundness of protein body was deformed and changed to spike shape at 20 kGy. Also, the size of lipid body decreased as the irradiation dose levels increased

  15. In-situ structural investigation of non-stoichiometric HfO{sub 2-x} films using quick-scanning extended X-ray absorption fine structure

    Liu, Milias, E-mail: milias.liu@pc.rwth-aachen.de [Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, 52056 Aachen (Germany); JARA — Fundamentals of Future Information Technologies (Germany); Leichtweiß, Thomas; Janek, Jürgen [Institute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 58, 35392 Giessen (Germany); Martin, Manfred [Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, 52056 Aachen (Germany); JARA — Fundamentals of Future Information Technologies (Germany)

    2013-07-31

    In this work, we report our results on the synthesis and structural characterization of hafnium oxide thin films prepared by means of pulsed laser deposition. During the deposition, different gas atmospheres (O{sub 2,} Ar, Ar/H{sub 2}) were used. Electron probe micro analysis and X-ray photoelectron spectroscopy measurements show that films deposited in Ar or Ar/H{sub 2} are oxygen deficient, while films deposited in O{sub 2} are stoichiometric. X-ray diffraction data confirm that the as-prepared films are amorphous and form the monoclinic HfO{sub 2} phase during annealing. In-situ quick-scanning extended X-ray absorption fine structure measurements carried out at elevated temperatures up to 440 °C showed an increase in the Hf–Hf order. From the time-resolved data the crystallization kinetics are extracted and analyzed using the Avrami model. - Highlights: • Thin films of HfO{sub 2-x} were deposited by pulsed laser deposition on glass substrates. • Different gas atmospheres (O{sub 2}, Ar, Ar/H{sub 2}) were used to control the stoichiometry. • Films deposited under reducing conditions are highly non-stoichiometric. • As-prepared films are amorphous but crystallize upon heating up to 440 °C. • Time resolved in-situ X-ray absorption spectroscopy analysis of crystallization.

  16. Structure and optical absorption properties of NiTiO3 nanocrystallites

    Li, Ming-Wei; Yuan, Jin-Pei; Gao, Xiao-Mei; Liang, Er-Qian; Wang, Cheng-Yang

    2016-08-01

    Nickel titanate (NiTiO3) nanocrystallites are synthesized via a solid-state reaction from a precursor prepared by a homogeneous precipitation method. Ilmenite-structural NiTiO3 consists of alternating layers of NiO6 and TiO6 octahedra. It not only strongly absorbs ultraviolet light (wavelength water. It is proposed that the visible light absorbance peaks of NiTiO3 mainly originate from the Ni: d → d charge-transfer transitions within its valence band. NiTiO3 has wide energy gaps from the hybridized Ni 3 d and O 2 p orbitals to the Ti 3 d orbitals, which block both Ni2+ → Ti4+ and O2- → Ti4+ charge-transfer transitions between valence band and conduction band, and thus baffle its photocatalytic performance.

  17. Determining biological fine structure by differential absorption of soft x-rays

    The use of soft x-ray contact microscopy in examining histochemically treated human tissue embedded in plastic and exposed as unstained thin sections is demonstrated. When our preliminary data revealed that we could clearly image not only the histochemical reaction product, but the unstained biological fine structure of the surrounding tissues, we decided to test our hypothesis further and see if we could image unstained biological molecular aggregates as well. For this part of the investigation, we chose to examine hydrated proteoglycan aggregates. Proteoglycans are an essential component of the organic matrix of cartilage, and play a primary role in the retention and maintenance of extracellular water. To avoid any artifacts due to the introduction of exogeneous materials, and examine the proteoglycan aggregates in their hydrated, natural configuration, we made contact x-ray images of isolated proteoglycan aggregates in water

  18. Experimental studies on the electronic structure of pyrite FeS2 films prepared by thermally sulfurizing iron films

    Pyrite FeS2 films have been prepared by thermally sulfurizing iron films deposited by magnetron sputtering. The electronic structures were studies by X-ray absorption near edge structure and X-ray photoemission spectrum. The results show that an S 3p valence band with relatively higher intensity compared to the calculation exists in 2-10 eV range and a high density below the Fermi level of Fe 3d states were detected. A second gap of 2.8 eV in the unoccupied density of states was found above the conduction band which was 2.4 eV by experimentally calculation. The difference between t2g and eg which were formed in an octahedral crystal field was computed to be 2.1 eV. (authors)

  19. Analysis of Local Structures around Ni Atoms Doped in ZnO-Based Diluted Magnetic Semiconductors by Fluorescence EXAFS

    LI Bin-Bin; XIU Xiang-Qian; ZHANG Rong; TAO Zhi-Kuo; CHEN Lin; XIE Zi-Li; ZHENG You-Dou; HE Bo

    2006-01-01

    @@ Zn1-xNixO (x = 0.001, 0.01, 0.02, 0.05 and 0.20) powders are prepared by sol-gel method. An extended x-ray absorption fine structure technique (EXAFS) for the Ni K-edge is employed to probe the local structures around Ni atoms doped in ZnO powders by fluorescence mode. The near edge EXAFS of the samples does not change in the range of Ni concentration from x = 0.001 to 0.05, which is consistent with the results of x-ray diffraction of the samples. The simulation results for the first shell EXAFS signals indicated that Ni atoms are substituted in Zn sites.

  20. Crystal structure, hydrogen absorption properties and crystal structure of the deuterides of some Nb-Ni derived μ phase compounds

    Ternary compounds in the Nb-Ni-V system with the structure of the μ phase (structure type W6Fe7, R3-bar m) have been investigated as regards their hydrogenation properties as a function of V content. On the other hand, the crystal structures of the μ phase deuterides Nb57Ni43D44 (Nb7.2Ni5.8D5.03, R3-bar m, a=5.103(1)A, c=27.649(3)A, Z=3, RBragg=11.6%), Nb42Ni31V27D64 (Nb5.32Ni4.08V3.6D8.73, R3-bar m, a=5.136(1)A, c=27.815(3)A, Z=3, RBragg=7.5%) and Nb48Ni23Al29D36 (Nb6.27Ni2.93Al3.8D4.37, R3-bar m, a=5.113(1)A, c=27.926(3)A, Z=3, RBragg=7.4%) have been studied by powder neutron diffraction and are discussed in terms of the metal atom distribution in the metallic substructure, the latter being established by means of joint refinement of neutron and X-ray diffraction data