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Sample records for extended x-ray-absorption fine

  1. Extended X-ray absorption fine structure of bimetallic nanoparticles

    PubMed Central

    2011-01-01

    Summary Electronic and magnetic properties strongly depend on the structure of the material, especially on the crystal symmetry and chemical environment. In nanoparticles, the break of symmetry at the surface may yield different physical properties with respect to the corresponding bulk material. A useful tool to investigate the electronic structure, magnetic behaviour and local crystallographic structure is X-ray absorption spectroscopy. In this review, recent developments in the field of extended X-ray absorption fine structure measurements and in the analysis methods for structural investigations of bimetallic nanoparticles are highlighted. The standard analysis based on Fourier transforms is compared to the relatively new field of wavelet transforms that have the potential to outperform traditional analysis, especially in bimetallic alloys. As an example, the lattice expansion and inhomogeneous alloying found in FePt nanoparticles is presented, and this is discussed below in terms of the influence of employed density functional theory calculations on the magnetic properties. PMID:21977436

  2. Extended x-ray absorption fine structure studies of hemoglobin

    SciTech Connect

    Shulman, R.G.

    1987-02-01

    Results of extended x-ray absorption fine structure (EXAFS) studies of the iron atom in deoxygenated hemoglobin are reviewed. It is shown that the iron-porphinato nitrogen distance has been determined to be 2.06 +/- 0.01 A by two independent investigations. Difficulties experienced in using this distance to calculate the iron's distance above the plane by triangulation are shown to be due to ignoring differences between ferrous and ferric hemes. It is concluded that the iron is 0.2 +/- 0.1/0.2 A above the plane of the nitrogens as originally shown.

  3. Novel angular encoder for a quick-extended x-ray absorption fine structure monochromator

    SciTech Connect

    Stoetzel, J.; Luetzenkirchen-Hecht, D.; Frahm, R.; Fonda, E.; De Oliveira, N.; Briois, V.

    2008-08-15

    New concepts for time-resolved x-ray absorption spectroscopy using the quick-extended x-ray absorption fine structure (QEXAFS) method are presented. QEXAFS is a powerful tool to gain structural information about, e.g., fast chemical reactions or phase transitions on a subsecond scale. This can be achieved with a monochromator design that employs a channel-cut crystal on a cam driven tilt table for rapid angular oscillations of the Bragg angle. A new angular encoder system and a new data acquisition were described and characterized that were applied to a QEXAFS monochromator to get spectra with a directly measured accurate energy scale. New electronics were designed to allow a fast acquisition of the Bragg angle values and the absorption data during the measurements simultaneously.

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

    SciTech Connect

    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.

  5. Extended X-ray absorption fine structure (EXAFS) study of CaSO 4:Dy phosphors

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, D.; Bakshi, A. K.; Ciatto, G.; Aquilanti, G.; Pradhan, A. S.; Pascarelli, S.

    2006-03-01

    Extended X-ray absorption fine structure (EXAFS) measurements have been carried out on CaSO 4:Dy phosphors at the Dy L 3 edge with synchrotron radiation. The data have been analysed to find out the Dy-S and Dy-O bond lengths in the neighborhood of the Dy atoms. Measurements have been carried out over several samples thermally annealed for different cycles at 400 °C in air for 1 h and the change in bond lengths in samples with increasing number of annealing cycles have been studied by analyzing the EXAFS data.

  6. The coefficient of bond thermal expansion measured by extended x-ray absorption fine structure.

    PubMed

    Fornasini, P; Grisenti, R

    2014-10-28

    The bond thermal expansion is in principle different from the lattice expansion and can be measured by correlation sensitive probes such as extended x-ray absorption fine structure (EXAFS) and diffuse scattering. The temperature dependence of the coefficient α(bond)(T) of bond thermal expansion has been obtained from EXAFS for CdTe and for Cu. A coefficient α(tens)(T) of negative expansion due to tension effects has been calculated from the comparison of bond and lattice expansions. Negative lattice expansion is present in temperature intervals where α(bond) prevails over α(tens); this real-space approach is complementary but not equivalent to the Grüneisen theory. The relevance of taking into account the asymmetry of the nearest-neighbours distribution of distances in order to get reliable bond expansion values and the physical meaning of the third cumulant are thoroughly discussed.

  7. Local structure studies of some cobalt (II) complexes using extended X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Mishra, Ashutosh; Ninama, Samrath; Trivedi, Apurva

    2014-09-01

    Extended X-ray Absorption Fine Structure (EXAFS) analysis of Cobalt (II) complex as a ligand of 2 -methyl-3-[(bis-aniline(R) phenyl]-3H-l,5 benzodiazepine for finding local structure using conventional method .The Co(II) complexes were prepared by chemical root method. The EXAFS spectra were recorded at Cobalt K-edge i.e.; 7709 eV using Dispersive EXFAS beam line at 2.5GeV Indus-2 Synchrotron Radiation Source(SRS) at RRCAT, Indore, India. The recorded EXAFS data were analysed using the computer software Athena for determine the nearest neighbouring distances (bond lengths) of these complexes with conventional methods and it compared with Fourier transform(FT) analysis. The Fourier Transform convert EXAFS data signal into r-space or k-space. This is useful for visualizing the major contributions to the EXAFS spectrum.

  8. Geometric Structure Determination of N694C Lipoxygenase: a Comparative Near-Edge X-Ray Absorption Spectroscopy And Extended X-Ray Absorption Fine Structure Study

    SciTech Connect

    Sarangi, R.; Hocking, R.K.; Neidig, M.L.; Benfatto, M.; Holman, T.R.; Solomon, E.I.; Hodgson, K.O.; Hedman, B.

    2009-05-27

    The mononuclear nonheme iron active site of N694C soybean lipoxygenase (sLO1) has been investigated in the resting ferrous form using a combination of Fe-K-pre-edge, near-edge (using the minuit X-ray absorption near-edge full multiple-scattering approach), and extended X-ray absorption fine structure (EXAFS) methods. The results indicate that the active site is six-coordinate (6C) with a large perturbation in the first-shell bond distances in comparison to the more ordered octahedral site in wild-type sLO1. Upon mutation of the asparigine to cystiene, the short Fe-O interaction with asparigine is replaced by a weak Fe-(H{sub 2}O), which leads to a distorted 6C site with an effective 5C ligand field. In addition, it is shown that near-edge multiple scattering analysis can give important three-dimensional structural information, which usually cannot be accessed using EXAFS analysis. It is further shown that, relative to EXAFS, near-edge analysis is more sensitive to partial coordination numbers and can be potentially used as a tool for structure determination in a mixture of chemical species.

  9. Extended x-ray absorption fine structure studies of IBS Fe--Tb alloy films

    SciTech Connect

    Harris, V.G.; Aylesworth, K.D.; Kim, K.H.; Elam, W.T.; Koon, N.C. )

    1991-11-15

    We have employed extended x-ray absorption fine structure (EXAFS) analysis to study the compositional dependence of the atomic structure in Fe--Tb alloy films. Fourier transforms of EXAFS data, relative to both the Fe {ital K} and the Tb {ital L}{sub III} absorption edges, provide information about the local atomic environments relative to each atom. Results indicate the Fe EXAFS data to be dominated by Fe--Fe correlations, and consists of contributions from two Fe atomic shells at radial distances near 2.47 and 2.66 A and a Tb shell near 2.91 A. The coordination number of the Fe shells are measured to increase, while radial distances decrease, with increased Fe content. The Tb EXAFS data was found to have an atomic shells of Fe and Tb at 2.91 and 3.47 A, respectively. Analysis suggests that the Fe shell is very disordered and is comprised of approximately 9.5 atoms while the Tb shell has {approx}3 atoms.

  10. Photoluminescence and extended X-ray absorption fine structure studies on cadmium telluride material

    NASA Astrophysics Data System (ADS)

    Liu, Xiangxin

    The direct-band-gap semiconductor CdTe is an important material for fabricating high efficiency, polycrystalline thin-film solar cells in a heterojunction configuration. The outstanding physical properties of this material such as its good band-gap match to the solar spectrum, ease of fabrication of stoichiometric films, and easy grain boundary passivation make it an important candidate for large area, thin-film solar cells. However, there are several poorly understood processing steps that are commonly utilized in cell fabrication. One of these is a CdCl2 treatment near 400°C in the presence of oxygen, which can improve the cell efficiency a factor of two or more. Another factor is the role of copper in cell performance. In high performance CdS/CdTe thin-film solar cells, copper is usually included in the fabrication of low-resistance back contacts to obtain heavy p-type doping of the absorber CdTe at the contact. However, most of the copper is not electrically active. For example, secondary ion mass spectroscopy (SIMS) on typical CdTe cells has shown Cu concentrations of 1019 atoms/cm3 and even higher, although capacitance-voltage (C-V) measurements indicate typical ionized acceptor levels on the order of 1014/cm 3. Thus, there is great interest in the location and role of this inactive copper in CdTe photovoltaic (PV) devices. In this thesis, I will describe results obtained on magnetron-sputtered CdTe films that were diffused with copper following the procedure used for creating a cell back contact. Extended X-ray Absorption Fine Structure (EXAFS) measurements identified the chemical environment of the majority of the copper and show major differences depending on whether the CdTe film has been treated with chloride prior to the Cu diffusion. The EXAFS data indicate that the Cu chemistry is strongly affected by the chloride treatments---predominantly Cu2Te when Cu was diffused into the as-deposited CdTe film, but a Cu2O environment when Cu was diffused after

  11. Extended x-ray-absorption fine structure—Auger process for surface structure analysis: Theoretical considerations of a proposed experiment

    PubMed Central

    Landman, Uzi; Adams, David L.

    1976-01-01

    A method for surface structure analysis is proposed. The proposed process combines x-ray photoabsorption and Auger electron emission. The extended x-ray-absorption fine structure, occurring for photon energies above an atomic absorption edge, contains structural information of the microscopic environment due to the coupling of the photoelectron final state with the atomic initial state. Measurement of the variations in the intensity of particular Auger lines, as a function of the incident radiation energy, provides a surface sensitive measure of the photoabsorption cross section in the media. Theoretical considerations of the physical processes underlying the proposed experiment and its feasibility, and a discussion of background contributions are presented. PMID:16592339

  12. Quick extended x-ray absorption fine structure instrument with millisecond time scale, optimized for in situ applications.

    PubMed

    Khalid, S; Caliebe, W; Siddons, P; So, I; Clay, B; Lenhard, T; Hanson, J; Wang, Q; Frenkel, A I; Marinkovic, N; Hould, N; Ginder-Vogel, M; Landrot, G L; Sparks, D L; Ganjoo, A

    2010-01-01

    In order to learn about in situ structural changes in materials at subseconds time scale, we have further refined the techniques of quick extended x-ray absorption fine structure (QEXAFS) and quick x-ray absorption near edge structure (XANES) spectroscopies at beamline X18B at the National Synchrotron Light Source. The channel cut Si (111) monochromator oscillation is driven through a tangential arm at 5 Hz, using a cam, dc motor, pulley, and belt system. The rubber belt between the motor and the cam damps the mechanical noise. EXAFS scan taken in 100 ms is comparable to standard data. The angle and the angular range of the monochromator can be changed to collect a full EXAFS or XANES spectrum in the energy range 4.7-40.0 KeV. The data are recorded in ascending and descending order of energy, on the fly, without any loss of beam time. The QEXAFS mechanical system is outside the vacuum system, and therefore changing the mode of operation from conventional to QEXAFS takes only a few minutes. This instrument allows the acquisition of time resolved data in a variety of systems relevant to electrochemical, photochemical, catalytic, materials, and environmental sciences.

  13. Applications of extended X-ray absorption fine-structure spectroscopy to studies of bimetallic nanoparticle catalysts.

    PubMed

    Frenkel, Anatoly I

    2012-12-21

    Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to study short range order in heterometallic alloys for almost four decades. In this critical review, experimental, theoretical and data analytical approaches are revisited to examine their power, and limitations, in studies of bimetallic nanocatalysts. This article covers the basics of EXAFS experiments, data analysis, and modelling of nanoscale clusters. It demonstrates that, in the best case scenario, quantitative information about the nanocatalyst's size, shape, details of core-shell architecture, as well as static and dynamic disorder in metal-metal bond lengths can be obtained. The article also emphasizes the main challenge accompanying such insights: the need to account for the statistical nature of the EXAFS technique, and discusses corrective strategies.

  14. Iron distances in hemoglobin: comparison of x-ray crystallographic and extended x-ray absorption fine structure studies

    SciTech Connect

    Fermi, G.; Perutz, M.F.; Shulman, R.G.

    1987-09-01

    A comparison is presented of the structures obtained around the iron atom in deoxyhemoglobin (Hb). The data come from extended x-ray absorption fine structure (EXAFS) studies of the iron, which gave Fe-porphyrin nitrogen distances of 2.06 +- 0.01 A, and from the most recent high-resolution x-ray crystallographic study, which gave exactly the same distance-2.06 +- 0.02 A. The distance of Fe above the plane of the porphyrin nitrogens was 0.38 +- 0.04 A from the crystallographic study; this value is not far from the upper limit of the distances 0.20 +- /sub 0.20//sup 0.10/ A calculated from the EXAFS experiment by triangulation. These distances above the nitrogen plane are shorter than those estimated in the earliest x-ray structures

  15. Modeling the structure and composition of nanoparticles by extended X-Ray absorption fine-structure spectroscopy

    SciTech Connect

    Frenkel, Anatoly I.; Yevick, Aaron; Cooper, Chana; Vasic, Relja

    2011-07-19

    Many metal clusters in the 1-nm size range are catalytically active, and their enhanced reactivity is often attributed to their size, structure, morphology, and details of alloying. Synchrotron sources provide a wide range of opportunities for studying catalysis. Among them, extended X-ray absorption fine-structure (EXAFS) spectroscopy is the premier method for investigating structure and composition of nanocatalysts. In this review, we summarize common methods of EXAFS analysis for geometric and compositional characterization of nanoparticles. We discuss several aspects of the experiments and analyses that are critical for reliably modeling EXAFS data. The most important are sample homogeneity, the width of the size and compositional distribution functions, and accounting for multiple-scattering contributions to EXAFS. We focus on the contribution of structural disorder and structural/compositional heterogeneity to the accuracy of three-dimensional modeling.

  16. Extended X-ray absorption fine structural studies of copper and nickel ferrites

    NASA Astrophysics Data System (ADS)

    Malviya, P. K.; Sharma, P.; Mishra, Ashutosh; Bhalse, D.

    2014-09-01

    The Cu-Ni ferrites with general formula Cu1-xNix Fe2O4 (where x=0.0, 0.05, 0.10, 0. 15, 0.20) were prepared by solid state root method. X-ray, K- absorption fine structural measurements were carried out. EXAFS spectra have been recorded at the K-edge of Fe using the dispersive EXAFS (DEXAFS) beam line at 2.5GeV Indus-2 synchrotron radiation source RRCAT, Indore, India. The EXAFS data have been analysed using the computer software Athena. These have been used to determine the bond lengths in these ferrites with the help of four different methods, namely, Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods.

  17. Non-patchy strategy for inter-atomic distances from Extended X-ray Absorption Fine Structure

    PubMed Central

    Xu, Gu; Li, Guifang; LI, Xianya; Liang, Yi; Feng, Zhechuan

    2017-01-01

    Extended X-ray Absorption Fine Structure (EXAFS) has been one of the few structural probes available for crystalline, non-crystalline and even highly disordered specimens. However, the data analysis involves a patchy and tinkering process, including back-and-forth fitting and filtering, leading to ambiguous answers sometimes. Here we try to resolve this long standing problem, to extract the inter-atomic distances from the experimental data by a single step minimization, in order to replace the tedious and tinkering process. The new strategy is built firmly by the mathematical logic, and made straightforward and undeniable. The finding demonstrates that it is possible to break off from the traditional patchy model fitting, and to remove the logical confusion of a priori prediction of the structure to be matched with experimental data, making it a much more powerful technique than the existing methods. The new method is expected to benefit EXAFS users covering all disciplines. Also, it is anticipated that the current work to be the motivation and inspiration to the further efforts. PMID:28181529

  18. Non-patchy strategy for inter-atomic distances from Extended X-ray Absorption Fine Structure

    NASA Astrophysics Data System (ADS)

    Xu, Gu; Li, Guifang; Li, Xianya; Liang, Yi; Feng, Zhechuan

    2017-02-01

    Extended X-ray Absorption Fine Structure (EXAFS) has been one of the few structural probes available for crystalline, non-crystalline and even highly disordered specimens. However, the data analysis involves a patchy and tinkering process, including back-and-forth fitting and filtering, leading to ambiguous answers sometimes. Here we try to resolve this long standing problem, to extract the inter-atomic distances from the experimental data by a single step minimization, in order to replace the tedious and tinkering process. The new strategy is built firmly by the mathematical logic, and made straightforward and undeniable. The finding demonstrates that it is possible to break off from the traditional patchy model fitting, and to remove the logical confusion of a priori prediction of the structure to be matched with experimental data, making it a much more powerful technique than the existing methods. The new method is expected to benefit EXAFS users covering all disciplines. Also, it is anticipated that the current work to be the motivation and inspiration to the further efforts.

  19. Structural analysis of ultrafast extended x-ray absorption fine structure with subpicometer spatial resolution: Application to spin crossover complexes

    SciTech Connect

    Gawelda, W.; Bressler, C.; Pham, V.-T.; Veen, R. M. van der; Chergui, M.; Grolimund, D.; Abela, R.

    2009-03-28

    We present a novel analysis of time-resolved extended x-ray absorption fine structure (EXAFS) spectra based on the fitting of the experimental transients obtained from optical pump/x-ray probe experiments. We apply it to the analysis of picosecond EXAFS data on aqueous [Fe{sup II}(bpy){sub 3}]{sup 2+}, which undergoes a light induced conversion from its low-spin (LS) ground state to the short-lived ({tau}{approx_equal}650 ps) excited high-spin (HS) state. A series of EXAFS spectra were simulated for a collection of possible HS structures from which the ground state fit spectrum was subtracted to generate transient difference absorption (TA) spectra. These are then compared with the experimental TA spectrum using a least-squares statistical analysis to derive the structural change. This approach reduces the number of required parameters by cancellation in the differences. It also delivers a unique solution for both the fractional population and the extracted excited state structure. We thus obtain a value of the Fe-N bond elongation in the HS state with subpicometer precision (0.203{+-}0.008 A)

  20. Structural analysis of ultrafast extended x-ray absorption fine structure with subpicometer spatial resolution: application to spin crossover complexes.

    PubMed

    Gawelda, W; Pham, V-T; van der Veen, R M; Grolimund, D; Abela, R; Chergui, M; Bressler, C

    2009-03-28

    We present a novel analysis of time-resolved extended x-ray absorption fine structure (EXAFS) spectra based on the fitting of the experimental transients obtained from optical pump/x-ray probe experiments. We apply it to the analysis of picosecond EXAFS data on aqueous [Fe(II)(bpy)(3)](2+), which undergoes a light induced conversion from its low-spin (LS) ground state to the short-lived (tau approximately 650 ps) excited high-spin (HS) state. A series of EXAFS spectra were simulated for a collection of possible HS structures from which the ground state fit spectrum was subtracted to generate transient difference absorption (TA) spectra. These are then compared with the experimental TA spectrum using a least-squares statistical analysis to derive the structural change. This approach reduces the number of required parameters by cancellation in the differences. It also delivers a unique solution for both the fractional population and the extracted excited state structure. We thus obtain a value of the Fe-N bond elongation in the HS state with subpicometer precision (0.203+/-0.008 A).

  1. Extended x-ray absorption fine structure measurements of quasi-isentropically compressed vanadium targets on the OMEGA laser

    SciTech Connect

    Yaakobi, B.; Boehly, T. R.; Sangster, T. C.; Meyerhofer, D. D.; Remington, B. A.; Allen, P. G.; Pollaine, S. M.; Lorenzana, H. E.; Lorenz, K. T.; Hawreliak, J. A.

    2008-06-15

    The use of in situ extended x-ray absorption fine structure (EXAFS) for characterizing nanosecond laser-shocked vanadium, titanium, and iron has recently been demonstrated. These measurements are extended to laser-driven, quasi-isentropic compression experiments (ICE). The radiation source (backlighter) for EXAFS in all of these experiments is obtained by imploding a spherical target on the OMEGA laser [T. R. Boehly et al., Rev. Sci. Instrum. 66, 508 (1995)]. Isentropic compression (where the entropy is kept constant) enables to reach high compressions at relatively low temperatures. The absorption spectra are used to determine the temperature and compression in a vanadium sample quasi-isentropically compressed to pressures of up to {approx}0.75 Mbar. The ability to measure the temperature and compression directly is unique to EXAFS. The drive pressure is calibrated by substituting aluminum for the vanadium and interferometrically measuring the velocity of the back target surface by the velocity interferometer system for any reflector (VISAR). The experimental results obtained by EXAFS and VISAR agree with each other and with the simulations of a hydrodynamic code. The role of a shield to protect the sample from impact heating is studied. It is shown that the shield produces an initial weak shock that is followed by a quasi-isentropic compression at a relatively low temperature. The role of radiation heating from the imploding target as well as from the laser-absorption region is studied. The results show that in laser-driven ICE, as compared with laser-driven shocks, comparable compressions can be achieved at lower temperatures. The EXAFS results show important details not seen in the VISAR results.

  2. Extended x-ray absorption fine structure studies of the atomic structure of nanoparticles in different metallic matrices.

    PubMed

    Baker, S H; Roy, M; Gurman, S J; Binns, C

    2009-05-06

    It has been appreciated for some time that the novel properties of particles in the size range 1-10 nm are potentially exploitable in a range of applications. In order to ultimately produce commercial devices containing nanosized particles, it is necessary to develop controllable means of incorporating them into macroscopic samples. One way of doing this is to embed the nanoparticles in a matrix of a different material, by co-deposition for example, to form a nanocomposite film. The atomic structure of the embedded particles can be strongly influenced by the matrix. Since some of the key properties of materials, including magnetism, strongly depend on atomic structure, the ability to determine atomic structure in embedded nanoparticles is very important. This review focuses on nanoparticles, in particular magnetic nanoparticles, embedded in different metal matrices. Extended x-ray absorption fine structure (EXAFS) provides an excellent means of probing atomic structure in nanocomposite materials, and an overview of this technique is given. Its application in probing catalytic metal clusters is described briefly, before giving an account of the use of EXAFS in determining atomic structure in magnetic nanocomposite films. In particular, we focus on cluster-assembled films comprised of Fe and Co nanosized particles embedded in various metal matrices, and show how the crystal structure of the particles can be changed by appropriate choice of the matrix material. The work discussed here demonstrates that combining the results of structural and magnetic measurements, as well as theoretical calculations, can play a significant part in tailoring the properties of new magnetic cluster-assembled materials.

  3. High resolution spectrometer for extended x-ray absorption fine structure measurements in the 6 keV to 15 keV energy range

    NASA Astrophysics Data System (ADS)

    Seely, J. F.; Hudson, L. T.; Henins, Albert; Feldman, U.

    2016-11-01

    A Cauchois transmission-crystal spectrometer has been developed with high crystal resolving power in the 6 keV-15 keV energy range and sufficient sensitivity to record single-shot spectra from the Lawrence Livermore National Laboratory (LLNL) Titan laser and other comparable or more energetic lasers. The spectrometer capabilities were tested by recording the W L transitions from a laboratory source and the extended x-ray absorption fine structure (EXAFS) spectrum through a Cu foil.

  4. State of manganese in the photosynthetic apparatus. 1. Extended x-ray absorption fine structure studies on chloroplasts and di-.mu.-oxo-bridged dimanganese model compounds

    SciTech Connect

    Kirby, J. A.; Robertson, A. S.; Smith, J. P.; Thompson, A. C.; Cooper, S. R.; Klein, M. P.

    1981-09-01

    In this paper, extended X-ray absorption fine structure studies on the manganese contained in spinach chloroplasts and on certain di-p-oxo-bridged manganese dimers of the form (X2Mn)O2(MnX2) (X = 2,2'-bipyridine and 1 ,10-phenanthroline) are reported. From these studies, the manganese associated with photosynthetic oxygen evolution is suggested to occur as a bridged transition-metal dimer with most likely another manganese. Finally, extensive details on the analysis are included.

  5. Low-temperature adsorption of H2S on Ni(001) studied by near-edge- and surface-extended-x-ray-absorption fine structure

    NASA Astrophysics Data System (ADS)

    McGrath, R.; MacDowell, A. A.; Hashizume, T.; Sette, F.; Citrin, P. H.

    1989-11-01

    The adsorption of H2S on Ni(001) has been studied with surface-extended x-ray-absorption fine structure and near-edge x-ray-absorption fine structure (NEXAFS) using the AT&T Bell Laboratories X15B beamline at the National Synchrotron Light Source. At 95 K and full saturation coverage, ~0.45 monolayer (ML) of S atoms in fourfold-hollow sites are produced, characteristic of room-temperature adsorption, accompanied by ~0.05 ML of oriented molecular H2S. Both these atomic and molecular chemisorbed species are buried under ~0.9 ML of disordered physisorbed H2S. No evidence for HS is found. Above 190 K the two molecular H2S phases desorb, leaving only dissociated S. These findings differ from previously reported interpretations of data obtained with high-resolution electron-energy-loss spectroscopy. They also exemplify the utility of NEXAFS for identifying and quantifying atomic and molecular surface species even when their difference involves only H and the two species coexist.

  6. Extended x-ray absorption fine structure spectroscopy and first-principles study of SnWO4

    NASA Astrophysics Data System (ADS)

    Kuzmin, A.; Anspoks, A.; Kalinko, A.; Timoshenko, J.; Kalendarev, R.

    2014-04-01

    The local atomic structure in α- and β-SnWO4 was studied by synchrotron radiation W L3-edge x-ray absorption spectroscopy at 10 and 300 K. Strongly distorted WO6 octahedra were found in α-SnWO4, whereas nearly regular WO4 tetrahedra were observed in β-SnWO4, confirming previous results. The structural results obtained were supported by the first-principles calculations, suggesting that the second-order Jahn-Teller effect is responsible for octahedral distortion.

  7. In-situ extended X-ray absorption fine structure study of electrostriction in Gd doped ceria

    SciTech Connect

    Korobko, Roman; Wachtel, Ellen; Lubomirsky, Igor; Lerner, Alyssa; Li, Yuanyuan; Frenkel, Anatoly I.

    2015-01-26

    Studying electric field-induced structural changes in ceramics is challenging due to the very small magnitude of the atomic displacements. We used differential X-ray absorption spectroscopy, an elementally specific and spatially sensitive method, to detect such changes in Gd-doped ceria, recently shown to exhibit giant electrostriction. We found that the large electrostrictive stress generation can be associated with a few percent of unusually short Ce-O chemical bonds that change their length and degree of order under an external electric field. The remainder of the lattice is reduced to the role of passive spectator. This mechanism is fundamentally different from that in electromechanically active materials currently in use.

  8. Extended x-ray-absorption fine-structure study of the position of Zr within the unit cell of Sm sub 2 Co sub 17

    SciTech Connect

    Rabenberg, L. ); Barrera, E.V. ); Maury, C.E.; Allibert, C.H. , ENSEEG, B. P. 75, 38402 St. Martin-d'Heres, ); Heald, S.M. )

    1991-04-15

    Extended x-ray-absorption fine-structure spectroscopy (EXAFS) has been used to determine the position of Zr within the unit cell of Sm{sub 2}Co{sub 17}. Induction-melted Sm{sub 2}Co{sub 17}:Zr ternary alloys, aged at 1180 {degree}C, then quenched, consisted of intimately mixed H2:17 and R2:17 having Zr in solid solution as well some regions of R2:17 that were poor in Zr. EXAFS spectroscopy of these specimens indicates that the most probable position for Zr is a site having 2 Sm near-neighbor atoms and 11 Co atoms distributed over three different interatomic distances. This is consistent with a direct substitution of Zr for Co in the Co site in the mixed planes (12{ital j} in {ital P}6{sub 3}/{ital mmc} or 18{ital f} in {ital R}3{ital m}).

  9. Thermal and magnetic anomalies of α-iron: an exploration by extended x-ray absorption fine structure spectroscopy and synchrotron x-ray diffraction.

    PubMed

    Boccato, Silvia; Sanson, Andrea; Kantor, Innokenty; Mathon, Olivier; Dyadkin, Vadim; Chernyshov, Dmitry; Carnera, Alberto; Pascarelli, Sakura

    2016-09-07

    The local structure and dynamics of α-iron have been investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy and x-ray diffraction (XRD) in order to shed light on some thermal and magnetic anomalies observed in the last decades. The quantitative EXAFS analysis of the first two coordination shells reveals a peculiar local vibrational dynamics of α-iron: the second neighbor distance exhibits anharmonicity and vibrational anisotropy larger than the first neighbor distance. We search for possible distortions of the bcc structure to justify the unexplained magnetostriction anomalies of α-iron and provide a value for the maximum dislocation of the central Fe atom. No thermal anomalies have been detected from the current XRD data. On the contrary, an intriguing thermal anomaly at about 150 K, ascribed to a stiffening of the Fe-Fe bonds, was found by EXAFS.

  10. The structure of Mn-doped tris(8-hydroxyquinoline)gallium by extended x-ray absorption fine structure spectroscopy and first principles calculations

    NASA Astrophysics Data System (ADS)

    Fang, Shaojie; Pang, Zhiyong; Du, Yonghua; Zheng, Lirong; Zhang, Xijian; Wang, Fenggong; Yuan, Huimin; Han, Shenghao

    2012-12-01

    Metal-Mqx (M = Al, Ga, Zn, Be, and Ca, x = 2 or 3) complexes play a key role in organic spintronics and organic optoelectronics. However, the accurate structure determination of these complexes has been a challenge for a long time. Here, we report the structure of Mn-Gaq3 investigated by using first-principle density functional theory (DFT) calculations and extended X-ray absorption fine structure (EXAFS) spectroscopy. First, the structures of Mn-Gaq3 were predicted by first-principle DFT calculations. Then, all reasonable structures achieved from the calculations were used to fit the EXAFS spectra. By this method, the structure of Mn-Gaq3 is well obtained. We believe this method is also applicable to other metal-Mqx films.

  11. Thermal and magnetic anomalies of α-iron: an exploration by extended x-ray absorption fine structure spectroscopy and synchrotron x-ray diffraction

    NASA Astrophysics Data System (ADS)

    Boccato, Silvia; Sanson, Andrea; Kantor, Innokenty; Mathon, Olivier; Dyadkin, Vadim; Chernyshov, Dmitry; Carnera, Alberto; Pascarelli, Sakura

    2016-09-01

    The local structure and dynamics of α-iron have been investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy and x-ray diffraction (XRD) in order to shed light on some thermal and magnetic anomalies observed in the last decades. The quantitative EXAFS analysis of the first two coordination shells reveals a peculiar local vibrational dynamics of α-iron: the second neighbor distance exhibits anharmonicity and vibrational anisotropy larger than the first neighbor distance. We search for possible distortions of the bcc structure to justify the unexplained magnetostriction anomalies of α-iron and provide a value for the maximum dislocation of the central Fe atom. No thermal anomalies have been detected from the current XRD data. On the contrary, an intriguing thermal anomaly at about 150 K, ascribed to a stiffening of the Fe-Fe bonds, was found by EXAFS.

  12. The fate of silver ions in the photochemical synthesis of gold nanorods: an extended X-ray absorption fine structure analysis.

    PubMed

    Giannici, Francesco; Placido, Tiziana; Curri, Maria Lucia; Striccoli, Marinella; Agostiano, Angela; Comparelli, Roberto

    2009-12-14

    Water-soluble gold nanorods (Au NRs) were synthesized using a silver-ion mediated photochemical route under UV irradiation. Extended X-ray Absorption Fine Structure (EXAFS) measurements on the Ag K-edge were performed on samples obtained at different Ag/Au ratios and at increasing irradiation times in order to investigate the fate of silver ions during the growth of Au NRs. EXAFS measurements allowed to probe the chemical state and the local environment of silver in the final product. Experimental data suggest that Ag atoms are placed on top of the Au particles as metallic Ag(0), while no significant contribution to the EXAFS spectra comes from AgBr or other Ag(+) based species. The reported results strongly support the deposition of Ag(0) islands on the (110) surfaces of the Au particles, thus driving the anisotropic growth via the (111) surfaces.

  13. Study of atomic clusters in neutron irradiated reactor pressure vessel surveillance samples by extended X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Cammelli, S.; Degueldre, C.; Kuri, G.; Bertsch, J.; Lützenkirchen-Hecht, D.; Frahm, R.

    2009-03-01

    Copper and nickel impurities in nuclear reactor pressure vessel (RPV) steel can form nano-clusters, which have a strong impact on the ductile-brittle transition temperature of the material. Thus, for control purposes and simulation of long irradiation times, surveillance samples are submitted to enhanced neutron irradiation. In this work, surveillance samples from a Swiss nuclear power plant were investigated by extended X-ray absorption fine structure spectroscopy (EXAFS). The density of Cu and Ni atoms determined in the first and second shells around the absorber is affected by the irradiation and temperature. The comparison of the EXAFS data at Cu and Ni K-edges shows that these elements reside in arrangements similar to bcc Fe. However, the EXAFS analysis reveals local irradiation damage in the form of vacancy fractions, which can be determined with a precision of ∼5%. There are indications that the formation of Cu and Ni clusters differs significantly.

  14. Extended X-ray absorption fine structure data analysis of copper (II) hydroxamic acid mixed ligand complexes

    NASA Astrophysics Data System (ADS)

    Parsai, N.; Mishra, A.; Shrivastava, B. D.

    2014-09-01

    The X-ray absorption spectra of copper mixed ligand complexes, having hydroxamic acid as one of the ligands, have been recorded at the K-edge of copper at BL-8 Dispersive EXAFS beamline at the 2.5 GeV INDUS-2 Synchrotron, RRCAT, Indore, India. For the analysis of EXAFS data, crystallographic data of the complex or of its analog is required, which is not available. Hence, for the analysis of EXAFS data, theoretical EXAFS data of the studied complexes have been generated using the EXAFS equation employing computer software program Mathcad. Firstly, the experimental data has been processed using the computer program Athena to obtain the normalized absorption versus energy data. From the experimental EXAFS data, the phase shift parameter (an energy independent constant 5) has been computed using Lytle, Sayers and Stern's (LSS) method. The backscattering amplitude has been taken from the available theoretical tabulations and other parameters have been taken from crystallographic data of the copper metal. Fourier transforms of both the experimental and theoretical data have been computed, and the two Fourier transforms are found to agree with each other for all the complexes. The position of the first peak in the Fourier transform gives the value of the first shell bond length, which is shorter than the actual bond length as a result of energy dependence of the phase factor (5(k)) in the sine function of the EXAFS equation. Since, the Fourier transform method and LSS method both are uncorrected for phase and other parameters of the EXAFS equation, the present method gives phase uncorrected bond length of the first coordination shell.

  15. Extended X-ray absorption fine structure data analysis of copper (II) hydroxamic acid mixed ligand complexes

    NASA Astrophysics Data System (ADS)

    Parsai, N.; Mishra, A.; Shrivastava, B. D.

    2014-09-01

    The X-ray absorption spectra of copper mixed ligand complexes, having hydroxamic acid as one of the ligands, have been recorded at the K-edge of copper at BL-8 Dispersive EXAFS beamline at the 2.5 GeV INDUS-2 Synchrotron, RRCAT, Indore, India. For the analysis of EXAFS data, crystallographic data of the complex or of its analog is required, which is not available. Hence, for the analysis of EXAFS data, theoretical EXAFS data of the studied complexes have been generated using the EXAFS equation employing computer software program Mathcad. Firstly, the experimental data has been processed using the computer program Athena to obtain the normalized absorption versus energy data. From the experimental EXAFS data, the phase shift parameter (an energy independent constant 5) has been computed using Lytle, Sayers and Stern's (LSS) method. The backscattering amplitude has been taken from the available theoretical tabulations and other parameters have been taken from crystallographic data of the copper metal. Fourier transforms of both the experimental and theoretical data have been computed, and the two Fourier transforms are found to agree with each other for all the complexes. The position of the first peak in the Fourier transform gives the value of the first shell bond length, which is shorter than the actual bond length as a result of energy dependence of the phase factor (δ(k)) in the sine function of the EXAFS equation. Since, the Fourier transform method and LSS method both are uncorrected for phase and other parameters of the EXAFS equation, the present method gives phase uncorrected bond length of the first coordination shell.

  16. Nearest-neighbor oxygen distances in liquid water and ice observed by x-ray Raman based extended x-ray absorption fine structure.

    PubMed

    Bergmann, Uwe; Di Cicco, Andrea; Wernet, Philippe; Principi, Emiliano; Glatzel, Pieter; Nilsson, Anders

    2007-11-07

    We report the nearest-neighbor oxygen-oxygen radial distribution function (NN O-O RDF) of room temperature liquid water and polycrystalline ice Ih (-16.8 degrees C) obtained by x-ray Raman based extended x-ray absorption fine structure (EXAFS) spectroscopy. The spectra of the two systems were taken under identical experimental conditions using the same procedures to obtain the NN O-O RDFs. This protocol ensured a measurement of the relative distance distribution with very small systematic errors. The NN O-O RDF of water is found to be more asymmetric (tail extending to longer distances) with longer average distance (2.81 A for water and 2.76 A for ice) but a slightly shorter peak position (2.70 A for water and 2.71 A for ice). The refinement also showed a small but significant contribution from the linear O-H-O multiple scattering signal. The high sensitivity to short range distances of the EXAFS probe will set further restrictions to the range of possible models of liquid water.

  17. EXAFS (Extended X-ray Absorption Fine-Structure Spectroscopy) study of the position of Zr within the unit cell of Sm sub 2 Co sub 17

    SciTech Connect

    Rabenberg, L. . Center for Materials Science and Engineering); Barrera, E.V. . Dept. of Mechanical Engineering and Materials Science); Maury, C.E.; Allibert, C.H. . Lab. de Thermodynamique et PhysicoChimie Metallurgiques); Heald, S.M. (Brookhaven National Lab

    1990-01-01

    Extended X-ray Absorption Fine-Structure Spectroscopy (EXAFS) has been used to determine the position of Zr within the unit cell of Sm{sub 2}Co{sub 17}. Zr is routinely added to Sm{sub 2}Co{sub 17} permanent magnet alloys because of its effects on their metallurgical development, but the details of its behavior remain controversial. Induction melted Sm{sub 2}Co{sub 17}:Zr ternary alloys, aged at 1180{degrees}C, then quenched, consisted of intimately mixed H2:17 and R2:17 having Zr in solid solution as well some regions of R2:17 that were poor in Zr. EXAFS spectroscopy of these specimens indicates that the most probable position for Zr is a site having two Sm near neighbor atoms and 11 Co atoms distributed over three different interatomic distances. This is consistent with a direct substitution of Zr for Co in the Co site in the mixed planes (12j in P6{sub 3}/mmc, or 18f in R3m). These results are discussed in terms of the metallurgy of 2:17 magnet alloys. 20 refs., 2 figs.

  18. Local vibrational dynamics of hematite (α-Fe{sub 2}O{sub 3}) studied by extended x-ray absorption fine structure and molecular dynamics

    SciTech Connect

    Sanson, A.; Mathon, O.; Pascarelli, S.

    2014-06-14

    The local vibrational dynamics of hematite (α-Fe{sub 2}O{sub 3}) has been investigated by temperature-dependent extended x-ray absorption fine structure spectroscopy and molecular dynamics simulations. The local dynamics of both the short and long nearest-neighbor Fe–O distances has been singled out, i.e., their local thermal expansion and the parallel and perpendicular mean-square relative atomic displacements have been determined, obtaining a partial agreement with molecular dynamics. No evidence of the Morin transition has been observed. More importantly, the strong anisotropy of relative thermal vibrations found for the short Fe–O distance has been related to its negative thermal expansion. The differences between the local dynamics of short and long Fe–O distances are discussed in terms of projection and correlation of atomic motion. As a result, we can conclude that the short Fe–O bond is stiffer to stretching and softer to bending than the long Fe–O bond.

  19. Local vibrational dynamics of hematite (α-Fe₂O₃) studied by extended x-ray absorption fine structure and molecular dynamics.

    PubMed

    Sanson, A; Mathon, O; Pascarelli, S

    2014-06-14

    The local vibrational dynamics of hematite (α-Fe2O3) has been investigated by temperature-dependent extended x-ray absorption fine structure spectroscopy and molecular dynamics simulations. The local dynamics of both the short and long nearest-neighbor Fe-O distances has been singled out, i.e., their local thermal expansion and the parallel and perpendicular mean-square relative atomic displacements have been determined, obtaining a partial agreement with molecular dynamics. No evidence of the Morin transition has been observed. More importantly, the strong anisotropy of relative thermal vibrations found for the short Fe-O distance has been related to its negative thermal expansion. The differences between the local dynamics of short and long Fe-O distances are discussed in terms of projection and correlation of atomic motion. As a result, we can conclude that the short Fe-O bond is stiffer to stretching and softer to bending than the long Fe-O bond.

  20. Nearest-neighbor nitrogen and oxygen distances in the iron(II)-DNA complex studied by extended X-ray absorption fine structure.

    PubMed

    Bertoncini, Clelia R A; Meneghini, Rogerio; Tolentino, Helio

    2010-11-01

    In mammalian cells, DNA-bound Fe(II) reacts with H₂O₂ producing the highly reactive hydroxyl radical (OH) in situ. Since ·OH attacks nearby DNA residue generating oxidative DNA damage, many questions have arisen regarding iron-DNA complex formations and their implication in pre-malignant mutations and aging. In this work, a solid sample of Fe(II)-DNA complex containing one Fe(II) per 10 nucleotides was analyzed from extended X-ray absorption fine structure (EXAFS) spectra collected in a synchrotron radiation light source. Best fitting parameters of the EXAFS signal for the first two shells provide evidence of five oxygen atoms at 1.99 ± 0.02 Å and one nitrogen atom at 2.20 ± 0.02 Å in the inner coordination sphere of the Fe(II)-DNA complex. Considering that both purine base moieties bearing nitrogen atoms are prone to chelate iron, these results are consistent with the previously observed lower levels of DNA damage in cytosine nucleotides relative to adenine and guanine sites in cells under more physiological conditions of Fe(II) Fenton reaction.

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  2. Determination of bond lengths from extended X-ray absorption fine structure in cobalt(III)-oxo cubane-like clusters

    NASA Astrophysics Data System (ADS)

    Nitin Nair, N.; Shrivastava, B. D.; Das, Birinchi Kumar

    2016-10-01

    The extended X-ray absorption fine structure (EXAFS) at the K-edge of cobalt has been studied in two cobalt complexes having Co(III)-oxo cubane-like clusters of the type Co4O4(O2CR)4L4 where R is CH3 and L is pyridine (py) in one of the complex and ammonia (NH3) in the other complex. The spectra have been recorded at BL-9 scanning EXAFS beamline at the 2.5-GeV INDUS-2 Synchrotron, RRCAT, Indore, India. The positions of EXAFS maxima and minima have been reported. Using this data, the bond length has been determined by simple bond determination methods, viz., Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. The normalized EXAFS spectra have been Fourier transformed and the value of the bond length has also been determined from the position of the first peak in the Fourier transform. This distance is the phase-uncorrected bond length. LSS method also gives such bond length. The results obtained from Fourier transform and LSS methods have been found to be comparable to each other. For the pyridine complex, the value obtained from Levy's method has been found to be in agreement with the available crystallographic value.

  3. Strain in epitaxial MnSi films on Si(111) in the thick film limit studied by polarization-dependent extended x-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Figueroa, A. I.; Zhang, S. L.; Baker, A. A.; Chalasani, R.; Kohn, A.; Speller, S. C.; Gianolio, D.; Pfleiderer, C.; van der Laan, G.; Hesjedal, T.

    2016-11-01

    We report a study of the strain state of epitaxial MnSi films on Si(111) substrates in the thick film limit (100-500 Å) as a function of film thickness using polarization-dependent extended x-ray absorption fine structure (EXAFS). All films investigated are phase-pure and of high quality with a sharp interface between MnSi and Si. The investigated MnSi films are in a thickness regime where the magnetic transition temperature Tc assumes a thickness-independent enhanced value of ≥43 K as compared with that of bulk MnSi, where Tc≈29 K . A detailed refinement of the EXAFS data reveals that the Mn positions are unchanged, whereas the Si positions vary along the out-of-plane [111] direction, alternating in orientation from unit cell to unit cell. Thus, for thick MnSi films, the unit cell volume is essentially that of bulk MnSi—except in the vicinity of the interface with the Si substrate (thin film limit). In view of the enhanced magnetic transition temperature we conclude that the mere presence of the interface, and its specific characteristics, strongly affects the magnetic properties of the entire MnSi film, even far from the interface. Our analysis provides invaluable information about the local strain at the MnSi/Si(111) interface. The presented methodology of polarization dependent EXAFS can also be employed to investigate the local structure of other interesting interfaces.

  4. Extended x-ray absorption fine structure and micro-Raman spectra of Bridgman grown Cd1-xZnxTe ternary alloys

    NASA Astrophysics Data System (ADS)

    Talwar, Devki N.; Feng, Zhe Chuan; Lee, Jyh-Fu; Becla, P.

    2014-03-01

    We have performed low-temperature micro-Raman scattering and extended x-ray absorption fine-structure (EXAFS) measurements on the Bridgman-grown bulk zinc-blende Cd1-x Zn x Te (1.0 ≧̸ x ≧̸ 0.03) ternary alloys to comprehend their structural and lattice dynamical properties. The micro-Raman results are carefully appraised to authenticate the classical two-phonon mode behavior insinuated by far-infrared (FIR) reflectivity study. The composition-dependent EXAFS experiments have revealed a bimodal distribution of the nearest-neighbor bond lengths—its analysis by first-principles bond-orbital model enabled us to estimate the lattice relaxations around Zn/Cd atoms in CdTe/ZnTe to help evaluate the necessary force constant variations for constructing the impurity-perturbation matrices. The simulated results of impurity vibrational modes by average-t-matrix Green’s function (ATM-GF) theory has put our experimental findings of the gap mode ˜153 cm-1 near x ≈ 1 on a much firmer ground.

  5. Unrelaxation of the semiconductor surface at low-coverage Ag/InP(110) interfaces as determined by photoemission extended x-ray-absorption fine structure

    NASA Astrophysics Data System (ADS)

    Choudhary, K. M.; Mangat, P. S.; Kilday, D.; Margaritondo, G.

    1990-04-01

    The atomic geometries of Ag/InP(110) interfaces for metal coverages in the cluster regime have been determined by photoemission extended x-ray-absorption fine structure (PEXAFS). P 2p PEXAFS for InP(110)+0.5 Å Ag and InP(110)+1 Å Ag (at room temperature) were acquired. The data were analyzed by conventional Fourier-transform methods using the theoretical backscattering phase function of McKale et al. plus the absorber phase function of Teo and Lee. For both noble-metal coverages on the semiconductor surface, our measurements show that the relaxation (about 4% contraction) in the P-In bond length of the clean InP(110) surface is mostly removed. This is in contrast to our recent PEXAFS results, reported in the literature, for reactive-metal Al/InP(110) or Na/InP(110) interfaces, where low-coverage metal-induced reconstruction of the P-In bond length has been observed. The low-coverage noble-metal-induced unrelaxation of the P-In bond length might contribute to Fermi-level movements during Schottky-barrier formation.

  6. Lead is not off center in PbTe: the importance of r-space phase information in extended x-ray absorption fine structure spectroscopy.

    PubMed

    Keiber, T; Bridges, F; Sales, B C

    2013-08-30

    PbTe is a well-known thermoelectric material. Recent x-ray total scattering studies suggest that Pb moves off center along 100 in PbTe, by ∼0.2  Å at 300 K, producing a split Pb-Te pair distribution. We present an extended x-ray absorption fine structure spectroscopy (EXAFS) study of PbTe (and Tl doped PbTe) to determine if Pb or Te is off center. EXAFS provides sensitive r- or k-space phase information which can differentiate between a split peak for the Pb-Te distribution (indicative of off-center Pb) and a thermally broadened peak. We find no evidence for a split peak for Pb-Te or Te-Pb. At 300 K, the vibration amplitude for Pb-Te (or Te-Pb) is large; this thermally induced disorder is indicative of weak bonds, and the large disorder is consistent with the low thermal conductivity at 300 K. We also find evidence of an anharmonic potential for the nearest Pb-Te bonds, consistent with the overall anharmonicity found for the phonon modes. This effect is modeled by a "skew" factor (C3) which significantly improves the fit of the Pb-Te and Te-Pb peaks for the high temperature EXAFS data; C3 becomes significant above approximately 150-200 K. The consequences of these results will be discussed.

  7. Extended x-ray absorption fine structure in Ga1-xMnxN/SiC films with high Mn content

    NASA Astrophysics Data System (ADS)

    Sancho-Juan, O.; Martínez-Criado, O.; Cantarero, A.; Garro, N.; Salomé, M.; Susini, J.; Olguín, D.; Dhar, S.; Ploog, K.

    2011-05-01

    In this study, the local atomic structure of highly homogeneous Ga1-xMnxN alloy films (0.03extended x-ray absorption fine structure measurements. From the curve fitting, the structural parameters corresponding to the first two atomic shells surrounding both Ga and Mn atoms are reported. In the Ga1-xMnxN films, grown by molecular beam epitaxy, the Mn atoms are in tetrahedral configuration, independent of the Mn concentration; that is, they are in a substitutional site, MnGa, in the wurtzite structure. A small increase in the interatomic distances has been found with increasing Mn content. The Debye-Waller factor does not show a significant trend as Mn content increases, which suggests the presence of short-range disorder in the GaN lattice. Ab initio calculations of the structural parameter for two different Mn concentrations are consistent with the experimental results.

  8. A combined fit of total scattering and extended x-ray absorption fine structure data for local-structure determination in crystalline materials

    SciTech Connect

    Proffen, Thomas E; Krayzman, Victor; Levin, Igor; Tucker, Matt

    2009-01-01

    Reverse Monte Carlo (RMC) refinements of local structure using a simultaneous fit of X-ray/neutron total scattering and extended X-ray absorption fine structure (EXAFS) data were developed to incorporate an explicit treatment of both single- and multiple-scattering contributions to EXAFS. The refinement algorithm, implemented as an extension to the public domain computer software RMCProfile, enables accurate modeling of EXAFS over distances encompassing several coordination shells around the absorbing species. The approach was first tested on Ni, which exhibits extensive multiple scattering in EXAFS, and then applied to perovskite-like SrAl{sub 1/2}Nb{sub 1/2}O{sub 3}. This compound crystal1izes with a cubic double-perovskite structure but presents a challenge for local-structure determination using a total pair-distribution function (PDF) alone because of overlapping peaks of the constituent partial PDFs (e.g. Al-O and Nb-O or Sr-O and O-O). The results obtained here suggest that the combined use of the total scattering and EXAFS data provides sufficient constraints for RMC refinements to recover fine details of local structure in complex perovskites. Among other results, it was found that the probability density distribution for Sr in SrAl{sub 1/2}Nb{sub 1/2}O{sub 3} adopts T{sub d} point-group symmetry for the Sr sites, determined by the ordered arrangement of Al and Nb, as opposed to a spherical distribution commonly assumed in traditional Rietveld refinements.

  9. Optimizing the crystal environment through extended x-ray absorption fine structure to increase the luminescent lifetimes of Er3+ doped Y2O3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Dorman, James A.; Choi, Ju H.; Kuzmanich, Gregory; Bargar, John R.; Chang, Jane P.

    2012-04-01

    To predict and optimize luminescence efficiency of rare-earth ion doped (RE) nanophosphors, a relationship between the RE-concentration and the luminescent parameters is often obtained by Judd-Ofelt analysis, where the quality factor (χ =Ω4/Ω6) depends on the Er interactions with other RE elements in the second nearest neighboring shell. In this work, a detailed analysis of the local bonding environment by extended x-ray absorption fine structure (EXAFS) analyses is shown as effective as the Judd-Ofelt analysis to quantify the Er↔RE interaction in the second nearest neighboring shell (ρN=IREr↔RE2/IREr↔RE1). As the physical basis of ρN is consistent to that of χ, the EXAFS analysis becomes a viable alternative to replace Judd-Ofelt analysis to predict the optimum dopant concentration. This approach was corroborated based on analysis of Er3+:Y2O3 and core-shell Er3+:Y2O3|Y2O3 (5 nm shell) nanoparticles (NPs), with Er3+ concentrations up to 20 mol %. The ρN ratio from EXAFS analysis was shown to strongly correlate to the lifetimes extracted from the Judd-Ofelt analysis, both predicting the optimal dopant concentrations to be at 5 mol % and 2 mol % for the Er3+:Y2O3 and core-shell NPs, respectively. This confirms that EXAFS analysis can be used as a more time efficient method to achieve the same outcome typically obtained by Judd-Ofelt analysis, enabling the optimization of the luminescent lifetimes of RE doped nano-phosphors.

  10. Speciation and localization of Zn in the hyperaccumulator Sedum alfredii by extended X-ray absorption fine structure and micro-X-ray fluorescence.

    PubMed

    Lu, Lingli; Liao, Xingcheng; Labavitch, John; Yang, Xiaoe; Nelson, Erik; Du, Yonghua; Brown, Patrick H; Tian, Shengke

    2014-11-01

    Differences in metal homeostasis among related plant species can give important information of metal hyperaccumulation mechanisms. Speciation and distribution of Zn were investigated in a hyperaccumulating population of Sedum alfredii by using extended X-ray absorption fine structure and micro-synchrotron X-ray fluorescence (μ-XRF), respectively. The hyperaccumulator uses complexation with oxygen donor ligands for Zn storage in leaves and stems, and variations in the Zn speciation was noted in different tissues. The dominant chemical form of Zn in leaves was most probably a complex with malate, the most prevalent organic acid in S. alfredii leaves. In stems, Zn was mainly associated with malate and cell walls, while Zn-citrate and Zn-cell wall complexes dominated in the roots. Two-dimensional μ-XRF images revealed age-dependent differences in Zn localization in S. alfredii stems and leaves. In old leaves of S. alfredii, Zn was high in the midrib, margin regions and the petiole, whereas distribution of Zn was essentially uniform in young leaves. Zinc was preferentially sequestered by cells near vascular bundles in young stems, but was highly localized to vascular bundles and the outer cortex layer of old stems. The results suggest that tissue- and age-dependent variations of Zn speciation and distribution occurred in the hyperaccumulator S. alfredii, with most of the Zn complexed with malate in the leaves, but a shift to cell wall- and citric acid-Zn complexes during transportation and storage in stems and roots. This implies that biotransformation in Zn complexation occurred during transportation and storage processes in the plants of S. alfredii.

  11. Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite I: X-ray absorption extended fine structure spectroscopy analysis

    USGS Publications Warehouse

    Waychunas, G.A.; Fuller, C.C.; Davis, J.A.

    2002-01-01

    "Two-line" ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10-5 to 10-3 M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(0.2) A?? and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) A?? and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) A?? in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorption samples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH)6 octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH)6 polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further

  12. Structural Studies of Clean Semiconductor Surfaces and Metal-Semiconductor Interfaces by Photoemission Extended X-Ray Absorption Fine Structure Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Mangat, Pawitterjit Singh

    We determined the atomic geometries for clean InP(110)-(1 x 1) and Si(111)-(2 x 1) surfaces and Al/InP(110), Ag/InP(110), Bi/InP(110), Na/InP(110) and Al/Si(111) interfaces by photoemission extended x-ray absorption fine structure (PEXAFS) spectroscopy to understand the correlation between electrical Schottky barrier heights and interfacial structure. P 2p PEXAFS for the InP(110) surface and Si 2p PEXAFS for the Si(111) surface were acquired which yielded information on the short range order of substrate atoms on the surface or at the interface. For Al/Si(111) interfaces, we also obtained Al 2p PEXAFS. The data analyzed by Fourier analysis and curve-fitting procedures. The theoretical backscattering phase function of McKale et al. (J. Am. Chem. Soc. 110, 3763 (1988)) and absorber phase function of Teo and Lee (J. Am. Chem. Soc. 101, 2815 (1979)) were used for phase analysis to determine the interatomic bond lengths. For the clean InP(110) surface, we observed surface relaxation. For the Si(111)-(2 x 1) surface, we found 10% contraction in the second near neighborhood Si-Si distance which is not reported in any model. For low coverage reactive metal (Al, Na)/InP(110) interfaces, we observed metal induced surface structural changes which involve removal of relaxation and change in the basis of the surface unit mesh of the substrate. For Ag/InP(110) interfaces, the noble metal atoms were found to remove the relaxation of the first P-In bond length at the interface. These changes in the substrate might bring in interface states within the semiconductor band gap and, consequently, influencing Fermi-level pinning during the Schottky barrier formation. For the Bi/InP(110) interfaces, the relaxation of the clean InP(110) surface is not removed by the deposited Bi atoms. Hence, the Bi/InP(110) interface might not have Fermi-level pinning by interface states due to the interfacial structure of InP. For Al/Si(111) interfaces, the Al atoms do not induce drastic surface

  13. Extended x-ray-absorption and electron-energy-loss fine-structure studies of the local atomic structure of amorphous unhydrogenated and hydrogenated silicon carbide

    NASA Astrophysics Data System (ADS)

    Kaloyeros, Alain E.; Rizk, Richard B.; Woodhouse, John B.

    1988-12-01

    Extended x-ray-absorption (EXAFS) and electron-energy-loss fine-structure (EXELFS) measurements have been performed on amorphous unhydrogenated silicon carbide, a-SiC, and amorphous hydrogenated silicon carbide, a-SiC:H. Two hydrogenated samples with hydrogen concentrations corresponding, respectively, to H flows of 4 sccm (20% of argon flow) and 8 sccm (40% of argon flow) during the reactive sputtering process, were analyzed (sccm denotes standard cubic centimeters per minute at STP). It is found that short-range order (SRO), consisting of the same tetrahedrally coordinated units present in cubic crystalline c-SiC (zinc-blende structure), where a Si atom is surrounded by nearly four C atoms and vice versa, does exist in all the amorphous samples. This SRO, however, is detected only at a level of the first C and Si coordination shells in a-SiC and a-SiC:H. The structural disorder of the first Si and C coordination shells in all forms of amorphous SiC is somewhat greater than c-SiC, and it decreases appreciably as hydrogen is added. The a-SiC sample exhibits large Si and C coordination numbers, almost identical to c-SiC, a low atomic density, and virtually the same Si-C bond length as c-SiC. These results indicate that a relatively small concentration of large voids exist in a highly disordered a-SiC matrix. The a-SiC:H samples, on the other hand, exhibit a decrease in the C coordination number relative to a-SiC, which is independent of H concentration, low Si and C atomic densities, comparable to a-SiC, and virtually the same Si coordination number as a-SiC. These EXAFS-EXELFS results are consistent with a model where part of the H is substituting for Si in the local tetrahedra surrounding C atoms, while the rest is located inside internal voids in the a-SiC:H samples. The surface of the voids is composed of C atoms which have at least one bond to H, and of Si atoms. Finally, a straightforward computational procedure is applied to estimate the size of these voids

  14. X-ray absorption fine structure study of heavily P doped (111) and (001) diamond

    NASA Astrophysics Data System (ADS)

    Shikata, Shinichi; Yamaguchi, Koji; Fujiwara, Akihiko; Tamenori, Yusuke; Yahiro, Jumpei; Kunisu, Masahiro; Yamada, Takatoshi

    2017-02-01

    X-ray absorption fine structure (XANES) measurements were carried out for P doped (111) and (001) diamond films, and the results were compared with those from simulations. For the (111) spectrum, the main strong peak observed at 2147.0 eV and three broad peaks centered at 2150 eV, 2157 eV, and 2165 eV were observed. The assignment with the estimation by the simulation of the XANES peaks showed the interstitial sites additional to the substitutional site. The Extended X-ray Absorption Fine Structure (EXAFS) result of the P doped (111) diamond showed that the first and second neighboring peaks are observed at 1.21 A and 2.0 A, respectively. The assignment with the estimation by the simulation of the EXAFS peaks also showed the interstitial sites additional to the substitutional site. Overall, P in diamonds presumably has dopant sites in both the substitutional and interstitial sites.

  15. X-ray Absorption Spectroscopy

    SciTech Connect

    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.

  16. X-Ray Absorption Fine Structure Study for Fe60Ni40 Alloy

    SciTech Connect

    Yang, Dong-Seok; Oh, Kyuseung; Na, Wonkyung; Kim, Nayoung; Yoo, Yong-Goo; Min, Seung-Gi; Yu, Seong-Cho

    2007-02-02

    Fe60Ni40 alloys were fabricated by the mechanical alloying process with process periods of 1, 2, 4, 6, 12 and 24 hours, respectively. The formation of alloy and the structural evolution of the alloy were examined by X-ray diffraction and extended X-ray absorption fine structure methods. With increase of alloying time the BCC phase of iron was changed significantly during the mechanical alloying process. The alloying was activated in about 6 hours and completed in about 24 hours.

  17. Structural Analysis of the Mn(IV)/Fe(III) Cofactor of Chlamydia Trachomatis Ribonucleotide Reductase By Extended X-Ray Absorption Fine Structure Spectroscopy And Density Functional Theory Calculations

    SciTech Connect

    Younker, J.M.; Krest, C.M.; Jiang, W.; Krebs, C.; Bollinger, J.M.Jr.; Green, M.T.

    2009-05-28

    The class Ic ribonucleotide reductase from Chlamydia trachomatis (C{bar A}) uses a stable Mn(lV)/ Fe(lll) cofactor to initiate nucleotide reduction by a free-radical mechanism. Extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) calculations are used to postulate a structure for this cofactor. Fe and Mn K-edge EXAFS data yield an intermetallic distance of -2.92 {angstrom}. The Mn data also suggest the presence of a short 1.74 {angstrom} Mn-O bond. These metrics are compared to the results of DFT calculations on 12 cofactor models derived from the crystal structure of the inactive Fe2(lll/ III) form of the protein. Models are differentiated by the protonation states of their bridging and terminal OH{sub x} ligands as well as the location of the Mn(lV) ion (site 1 or 2). The models that agree best with experimental observation feature a{mu}-1, 3-carboxylate bridge (E120), terminal solvent (H{sub 2}O/OH) to site 1, one {mu}-O bridge, and one {mu}-OH bridge. The site-placement of the metal ions cannot be discerned from the available data.

  18. Invited article: The fast readout low noise camera as a versatile x-ray detector for time resolved dispersive extended x-ray absorption fine structure and diffraction studies of dynamic problems in materials science, chemistry, and catalysis

    NASA Astrophysics Data System (ADS)

    Labiche, Jean-Claude; Mathon, Olivier; Pascarelli, Sakura; Newton, Mark A.; Ferre, Gemma Guilera; Curfs, Caroline; Vaughan, Gavin; Homs, Alejandro; Carreiras, David Fernandez

    2007-09-01

    Originally conceived and developed at the European Synchrotron Radiation Facility (ESRF) as an "area" detector for rapid x-ray imaging studies, the fast readout low noise (FReLoN) detector of the ESRF [J.-C. Labiche, ESRF Newsletter 25, 41 (1996)] has been demonstrated to be a highly versatile and unique detector. Charge coupled device (CCD) cameras at present available on the public market offer either a high dynamic range or a high readout speed. A compromise between signal dynamic range and readout speed is always sought. The parameters of the commercial cameras can sometimes be tuned, in order to better fulfill the needs of specific experiments, but in general these cameras have a poor duty cycle (i.e., the signal integration time is much smaller than the readout time). In order to address scientific problems such as time resolved experiments at the ESRF, a FReLoN camera has been developed by the Instrument Support Group at ESRF. This camera is a low noise CCD camera that combines high dynamic range, high readout speed, accuracy, and improved duty cycle in a single image. In this paper, we show its application in a quasi-one-dimensional sense to dynamic problems in materials science, catalysis, and chemistry that require data acquisition on a time scale of milliseconds or a few tens of milliseconds. It is demonstrated that in this mode the FReLoN can be applied equally to the investigation of rapid changes in long range order (via diffraction) and local order (via energy dispersive extended x-ray absorption fine structure) and in situations of x-ray hardness and flux beyond the capacity of other detectors.

  19. Invited article: The fast readout low noise camera as a versatile x-ray detector for time resolved dispersive extended x-ray absorption fine structure and diffraction studies of dynamic problems in materials science, chemistry, and catalysis

    SciTech Connect

    Labiche, Jean-Claude; Mathon, Olivier; Pascarelli, Sakura; Newton, Mark A.; Ferre, Gemma Guilera; Curfs, Caroline; Vaughan, Gavin; Homs, Alejandro; Carreiras, David Fernandez

    2007-09-15

    Originally conceived and developed at the European Synchrotron Radiation Facility (ESRF) as an 'area' detector for rapid x-ray imaging studies, the fast readout low noise (FReLoN) detector of the ESRF [J.-C. Labiche, ESRF Newsletter 25, 41 (1996)] has been demonstrated to be a highly versatile and unique detector. Charge coupled device (CCD) cameras at present available on the public market offer either a high dynamic range or a high readout speed. A compromise between signal dynamic range and readout speed is always sought. The parameters of the commercial cameras can sometimes be tuned, in order to better fulfill the needs of specific experiments, but in general these cameras have a poor duty cycle (i.e., the signal integration time is much smaller than the readout time). In order to address scientific problems such as time resolved experiments at the ESRF, a FReLoN camera has been developed by the Instrument Support Group at ESRF. This camera is a low noise CCD camera that combines high dynamic range, high readout speed, accuracy, and improved duty cycle in a single image. In this paper, we show its application in a quasi-one-dimensional sense to dynamic problems in materials science, catalysis, and chemistry that require data acquisition on a time scale of milliseconds or a few tens of milliseconds. It is demonstrated that in this mode the FReLoN can be applied equally to the investigation of rapid changes in long range order (via diffraction) and local order (via energy dispersive extended x-ray absorption fine structure) and in situations of x-ray hardness and flux beyond the capacity of other detectors.

  20. Quantitative chemical imaging of element diffusion into heterogeneous media using laser ablation inductively coupled plasma mass spectrometry, synchrotron micro-X-ray fluorescence, and extended X-ray absorption fine structure spectroscopy.

    PubMed

    Wang, H A O; Grolimund, D; Van Loon, L R; Barmettler, K; Borca, C N; Aeschlimann, B; Günther, D

    2011-08-15

    Quantitative chemical imaging of trace elements in heterogeneous media is important for the fundamental understanding of a broad range of chemical and physical processes. The primary aim of this study was to develop an analytical methodology for quantitative high spatial resolution chemical imaging based on the complementary use of independent microanalytical techniques. The selected scientific case study is focused on high spatially resolved quantitative imaging of major elements, minor elements, and a trace element (Cs) in Opalinus clay, which has been proposed as the host rock for high-level radioactive waste repositories. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), providing quantitative chemical information, and synchrotron radiation based micro-X-ray fluorescence (SR-microXRF), providing high spatial resolution images, were applied to study Cs migration into Opalinus clay rock. The results indicate that combining the outputs achievable by the two independent techniques enhances the imaging capabilities significantly. The qualitative high resolution image of SR-microXRF is in good agreement with the quantitative image recorded with lower spatial resolution by LA-ICPMS. Combining both techniques, it was possible to determine that the Opalinus clay sample contains two distinct domains: (i) a clay mineral rich domain and (ii) a calcium carbonate dominated domain. The two domains are separated by sharp boundaries. The spatial Cs distribution is highly correlated to the distribution of the clay. Furthermore, extended X-ray absorption fine structure analysis indicates that the trace element Cs preferentially migrates into clay interlayers rather than into the calcite domain, which complements the results acquired by LA-ICPMS and SR-microXRF. By using complementary techniques, the quantification robustness was improved to quantitative micrometer spatial resolution. Such quantitative, microscale chemical images allow a more detailed

  1. Effect of different thickness crystalline SiC buffer layers on the ordering of MgB{sub 2} films probed by extended x-ray absorption fine structure

    SciTech Connect

    Putri, W. B. K.; Tran, D. H.; Kang, B.; Lee, O. Y.; Kang, W. N.; Miyanaga, T.; Yang, D. S.

    2014-03-07

    Extended X-ray absorption fine structure (EXAFS) spectroscopy is a powerful method to investigate the local structure of thin films. Here, we have studied EXAFS of MgB{sub 2} films grown on SiC buffer layers. Crystalline SiC buffer layers with different thickness of 70, 100, and 130 nm were deposited on the Al{sub 2}O{sub 3} (0001) substrates by using a pulsed laser deposition method, and then MgB{sub 2} films were grown on the SiC buffer layer by using a hybrid physical-chemical vapor deposition technique. Transition temperature of MgB{sub 2} film decreased with increasing thickness of SiC buffer layer. However, the T{sub c} dropping went no farther than 100 nm-thick-SiC. This uncommon behavior of transition temperature is likely to be created from electron-phonon interaction in MgB{sub 2} films, which is believed to be related to the ordering of MgB{sub 2} atomic bonds, especially in the ordering of Mg–Mg bonds. Analysis from Mg K-edge EXAFS measurements showed interesting ordering behavior of MgB{sub 2} films. It is noticeable that the ordering of Mg–B bonds is found to decrease monotonically with the increase in SiC thickness of the MgB{sub 2} films, while the opposite happens with the ordering in Mg–Mg bonds. Based on these results, crystalline SiC buffer layers in MgB{sub 2} films seemingly have evident effects on the alteration of the local structure of the MgB{sub 2} film.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Study on the Coordination Structure of Pt Sorbed on Bacterial Cells Using X-Ray Absorption Fine Structure Spectroscopy

    PubMed Central

    Tanaka, Kazuya; Watanabe, Naoko

    2015-01-01

    Biosorption has been intensively investigated as a promising technology for the recovery of precious metals from solution. However, the detailed mechanism responsible for the biosorption of Pt on a biomass is not fully understood because of a lack of spectroscopic studies. We applied X-ray absorption fine structure spectroscopy to elucidate the coordination structure of Pt sorbed on bacterial cells. We examined the sorption of Pt(II) and Pt(IV) species on bacterial cells of Bacillus subtilis and Shewanella putrefaciens in NaCl solutions. X-ray absorption near-edge structure and extended X-ray absorption fine structure (EXAFS) of Pt-sorbed bacteria suggested that Pt(IV) was reduced to Pt(II) on the cell’s surface, even in the absence of an organic material as an exogenous electron donor. EXAFS spectra demonstrated that Pt sorbed on bacterial cells has a fourfold coordination of chlorine ions, similar to PtCl42-, which indicated that sorption on the protonated amine groups of the bacterial cells. This work clearly demonstrated the coordination structure of Pt sorbed on bacterial cells. The findings of this study will contribute to the understanding of Pt biosorption on biomass, and facilitate the development of recovery methods for rare metals using biosorbent materials. PMID:25996945

  4. Study of the Local Structure of GALLIUM(X)INDIUM(1 -X)ARSENIDE(Y)ANTIMONY(1-Y), a Quaternary Iii-V Semiconductor Alloy, Using the Extended X-Ray Absorption Fine Structure (exafs) Technique.

    NASA Astrophysics Data System (ADS)

    Islam, Shaheen Momtaz

    The technological importance of quaternary semiconductor alloys has stimulated considerable interest in the basic physics of these materials. Understanding of the local structure of these alloys is of fundamental importance. In this work, the extended x-ray absorption fine structure (EXAFS) technique has been used to investigate the atomic-scale structure of the III-V quaternary alloy series Ga_{rm x}In _{rm 1-x}As _{rm y}Sb_ {rm 1-y}, where Ga and In atoms occupy one sublattice and As and Sb atoms are distributed over the other sublattice. Two series of these alloys were studied with varying x (from 0.05 to 0.95) and keeping y constant (y = 0.05 or y = 0.10). The samples were polycrystalline powders of various compositions. EXAFS data were obtained at the As K-edge at room temperature for all these alloys. Our measurements reveal the number and types of atoms and the nearest neighbor distances about the average As atom. Our results show a consistent deviation from random site occupation in all these alloys, with Ga-As (and therefore In-Sb) pairs being clearly preferred over In-As and Ga -Sb pairs. This result is consistent with a theoretical model based on the pair approximation. From EXAFS measurements we also observe that the variation of Ga-As and In-As near-neighbor distances with composition is linear and that the bond-lengths remain nearly constant, closer to those in the pure binary compounds and varying only by 0.03 to 0.05A. On the other hand, the x-ray diffraction results show that the average cation -anion distance in the alloys changes by as much as 0.165A in accordance with Vegard's law. This linear variation of lattice constant with composition between the end members suggests that the atomic volume is conserved regardless of the details of the local distortions of lattice.

  5. Structural characterization of Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3} as a function of temperature using neutron powder diffraction and extended X-ray absorption fine structure techniques

    SciTech Connect

    Mansour, A. N.; Wong-Ng, W.; Huang, Q.; Tang, W.; Thompson, A.; Sharp, J.

    2014-08-28

    The structure of Bi{sub 2}Te{sub 3} (Seebeck coefficient Standard Reference Material (SRM™ 3451)) and the related phase Sb{sub 2}Te{sub 3} have been characterized as a function of temperature using the neutron powder diffraction (NPD) and the extended X-ray absorption fine structure (EXAFS) techniques. The neutron structural studies were carried out from 20 K to 300 K for Bi{sub 2}Te{sub 3} and from 10 K to 298 K for Sb{sub 2}Te{sub 3}. The EXAFS technique for studying the local structure of the two compounds was conducted from 19 K to 298 K. Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3} are isostructural, with a space group of R3{sup ¯}m. The structure consists of repeated quintuple layers of atoms, Te2-M-Te1-M-Te2 (where M = Bi or Sb) stacking along the c-axis of the unit cell. EXAFS was used to examine the bond distances and static and thermal disorders for the first three shells of Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3} as a function of temperature. The temperature dependencies of thermal disorders were analyzed using the Debye and Einstein models for lattice vibrations. The Debye and Einstein temperatures for the first two shells of Bi{sub 2}Te{sub 3} are similar to those of Sb{sub 2}Te{sub 3} within the uncertainty in the data. However, the Debye and Einstein temperatures for the third shell of Bi-Bi are significantly lower than those of the third shell of Sb-Sb. The Einstein temperature for the third shell is consistent with a soft phonon mode in both Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3}. The lower Einstein temperature of Bi-Bi relative to Sb-Sb is consistent with the lower value of thermal conductivity of Bi{sub 2}Te{sub 3} relative to Sb{sub 2}Te{sub 3}.

  6. Extended X-ray absorption fine structure studies of Zn/sub 2/Fe/sub 2/ hybrid hemoglobins: absence of heme bond length changes in half-ligated species

    SciTech Connect

    Simolo, K.; Korszun, Z.R.; Stucky, G.; Moffat, K.; McLendon, G.

    1986-07-01

    Metal hybrid hemoglobins, in which Zn(II) replaces Fe(II), have been structurally characterized by extended X-ray absorption structure (EAFS) studies. Since Zn and Fe have very different K absorption edge energies, the structures of the ligated (Fe) and unligated (Zn) sites could be examined independently within a single molecule that mimics an intermediate ligation state. The observed EXAFS spectra and associated structural parameters are compared among the ligand free (..cap alpha..Zn)/sub 2/(..beta..Zn)/sub 2/, half-ligated (..cap alpha..FeCO)/sub 2/(..beta..Zn)/sub 2/ and (..cap alpha..Zn)/sub 2/(..beta..FeCO)/sub 2/, and fully ligated (..cap alpha..FeCO)/sub 2/(..beta..FeCO)/sub 2/ systems.

  7. The O2-Evolving Complex of Photosystem II: Recent Insights from Quantum Mechanics/Molecular Mechanics (QM/MM), Extended X-ray Absorption Fine Structure (EXAFS), and Femtosecond X-ray Crystallography Data.

    PubMed

    Askerka, Mikhail; Brudvig, Gary W; Batista, Victor S

    2017-01-17

    Efficient photoelectrochemical water oxidation may open a way to produce energy from renewable solar power. In biology, generation of fuel due to water oxidation happens efficiently on an immense scale during the light reactions of photosynthesis. To oxidize water, photosynthetic organisms have evolved a highly conserved protein complex, Photosystem II. Within that complex, water oxidation happens at the CaMn4O5 inorganic catalytic cluster, the so-called oxygen-evolving complex (OEC), which cycles through storage "S" states as it accumulates oxidizing equivalents and produces molecular oxygen. In recent years, there has been significant progress in understanding the OEC as it evolves through the catalytic cycle. Studies have combined conventional and femtosecond X-ray crystallography with extended X-ray absorption fine structure (EXAFS) and quantum mechanics/molecular mechanics (QM/MM) methods and have addressed changes in protonation states of μ-oxo bridges and the coordination of substrate water through the analysis of ammonia binding as a chemical analog of water. These advances are thought to be critical to understanding the catalytic cycle since protonation states regulate the relative stability of different redox states and the geometry of the OEC. Therefore, establishing the mechanism for substrate water binding and the nature of protonation/redox state transitions in the OEC is essential for understanding the catalytic cycle of O2 evolution. The structure of the dark-stable S1 state has been a target for X-ray crystallography for the past 15 years. However, traditional X-ray crystallography has been hampered by radiation-induced reduction of the OEC. Very recently, a revolutionary X-ray free electron laser (XFEL) technique was applied to PSII to reveal atomic positions at 1.95 Å without radiation damage, which brought us closer than ever to establishing the ultimate structure of the OEC in the S1 state. However, the atom positions in this crystal

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

    SciTech Connect

    Lezama-pacheco, Juan S; Conradson, Steven D; Clark, David L

    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.

  9. X-ray absorption fine structure and X-ray excited optical luminescence studies of II-VI semiconducting nanostructures

    NASA Astrophysics Data System (ADS)

    Murphy, Michael Wayne

    2010-06-01

    of 0, 1,3, and 10% and annealed at 400, 600 and 800°C in air. XAFS spectra show that low dopant concentrations and low processing temperatures limit the amount of secondary phase formation. The nanopowders did not show roomtemperature ferromagnetism and increased secondary phase formation increases the paramagnetic character of the hysteresis curves at 5°K. Keywords: X-ray absorption fine structures (XAFS), X-ray absorption near-edge structures (XANES), extended X-ray absorption fine structure (EXAFS), X-ray absorption spectroscopy(XAS), X-ray excited optical luminescence (XEOL), time-resolved, II-VI semiconductors, nanostructure, nanomaterial, nanoribbon, nanowire, nanopartic1e, heterostructure, ZnO, ZnS, ZnO-ZnS, CdS, CdSe, CdSSe, ZnO:Mn, ZnO:Co, ZnS:Mn, dilute magnetic semiconductor (DMS), dilute magnetic oxide (DMO), spintronics, magnetism, paramagnetism, ferromagnetism.

  10. Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

    SciTech Connect

    Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

    2007-11-27

    Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

  11. Sorption mechanisms of zinc to calcium silicate hydrate: X-ray absorption fine structure (XAFS) investigation.

    PubMed

    Ziegler, F; Scheidegger, A M; Johnson, C A; Dähn, R; Wieland, E

    2001-04-01

    In this study, X-ray absorption fine structure (XAFS) spectroscopy has been used to further elucidate the binding mechanisms of Zn(II) to calcium silicate hydrate (C-S-H), the quantitatively most important cement mineral. Such knowledge is essential for the assessment of the longterm behavior of cement-stabilized waste materials. XAFS spectra of the Zn(II) equilibrated with C-S-H(I) for up to 28 days are best modeled by tetrahedral coordination of Zn(II) by four O atoms in the first atomic shell. Beyond the first coordination shell, data analysis of more highly concentrated samples suggests the presence of two distinct Zn distances and possibly the presence of an Si shell. On the basis of the comparison with a set of reference compounds, this coordination environment can be reasonably related to the structure of hemimorphite, a naturally occurring zinc silicate, and/or the presence of gamma-Zn(OH)2. At the lowest Zn uptake, the above fitting approach failed and data could be described best with a Zn-Si and a Zn-Ca shell. Previous work has been able to show that Zn(II) diffuses into the C-S-H(I) particles and does not form discrete precipitates, so the findings appear to confirm the incorporation of Zn(II) in the interlayer of C-S-H(I).

  12. Applications of x ray absorption fine structure to the in situ study of the effect of cobalt in nickel hydrous oxide electrodes for fuel cells and rechargeable batteries

    NASA Technical Reports Server (NTRS)

    Kim, Sunghyun; Tryk, Donald A.; Scherson, Daniel A.; Antonio, Mark R.

    1993-01-01

    Electronic and structural aspects of composite nickel-cobalt hydrous oxides have been examined in alkaline solutions using in situ X-ray absorption fine structure (XAFS). The results obtained have indicated that cobalt in this material is present as cobaltic ions regardless of the oxidation state of nickel in the lattice. Furthermore, careful analysis of the Co K-edge Extended X-ray absorption fine structure data reveals that the co-electrodeposition procedure generates a single phase, mixed metal hydrous oxide, in which cobaltic ions occupy nickel sites in the NiO2 sheet-like layers and not two intermixed phases each consisting of a single metal hydrous oxide.

  13. The Effect of X-Ray Absorption Fine Structure in Soft X-ray Astronomical Telescopes

    NASA Astrophysics Data System (ADS)

    Owens, Alan; Denby, Michael; Wells, Alan; Keay, Adam; Graessle, Dale E.; Blake, Richard L.

    1997-02-01

    Recent in-orbit measurements by high resolution soft X-ray telescopes have revealed low-level fine structure in target spectra that cannot be attributed to a celestial source. Ultimately, this can be traced to the ability of the new high spectral resolution silicon detectors to resolve X-ray absorption fine structure (XAFS) produced in the various detection subsystems. Based on measurements taken at the Daresbury Synchrotron Radiation Source (SRS) and the National Synchrotron Light Source (NSLS), we have modeled the full-up response function of the Joint European X-ray Telescope (JET-X), taking into account edge structure generated in the detectors, filters, and mirrors. It is found that unfolding celestial source spectra using a response function in which the detailed edge shapes are calculated from standard absorption cross sections leads to the generation of spectral artifacts at every absorption edge. These in turn produce unacceptably high values of χ2 in model fits for total source fluxes above ~4 × 104 counts. For JET-X, this corresponds to a source strength of ~0.4 millicrab observed for 105 s. Statistically significant ``linelike'' features are introduced into the derived source spectra with amplitudes as great as 10% of the source flux. For JET-X, these features rise above the 3 σ level for integral source exposures above ~5 × 104 source counts. The largest deviations in the residuals arise near 0.5 keV and 2.2 keV and are attributed to XAFS produced in the oxide surface layers of the CCD and the gold reflective surface of the mirrors, respectively. These results are significant for data interpretation tasks with the ASCA, JET-X, XMM, and Advanced X-Ray Astrophysics Facility (AXAF) telescopes.

  14. Radiation effects in water ice: a near-edge x-ray absorption fine structure study.

    PubMed

    Laffon, C; Lacombe, S; Bournel, F; Parent, Ph

    2006-11-28

    The changes in the structure and composition of vapor-deposited ice films irradiated at 20 K with soft x-ray photons (3-900 eV) and their subsequent evolution with temperatures between 20 and 150 K have been investigated by near-edge x-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K edge. We observe the hydroxyl OH, the atomic oxygen O, and the hydroperoxyl HO(2) radicals, as well as the oxygen O(2) and hydrogen peroxide H(2)O(2) molecules in irradiated porous amorphous solid water (p-ASW) and crystalline (I(cryst)) ice films. The evolution of their concentrations with the temperature indicates that HO(2), O(2), and H(2)O(2) result from a simple step reaction fuelled by OH, where O(2) is a product of HO(2) and HO(2) a product of H(2)O(2). The local order of ice is also modified, whatever the initial structure is. The crystalline ice I(cryst) becomes amorphous. The high-density amorphous phase (I(a)h) of ice is observed after irradiation of the p-ASW film, whose initial structure is the normal low-density form of the amorphous ice (I(a)l). The phase I(a)h is thus peculiar to irradiated ice and does not exist in the as-deposited ice films. A new "very high density" amorphous phase-we call I(a)vh-is obtained after warming at 50 K the irradiated p-ASW ice. This phase is stable up to 90 K and partially transforms into crystalline ice at 150 K.

  15. Adding diffuse reflectance infrared Fourier transform spectroscopy capability to extended x-ray-absorption fine structure in a new cell to study solid catalysts in combination with a modulation approach

    NASA Astrophysics Data System (ADS)

    Chiarello, Gian Luca; Nachtegaal, Maarten; Marchionni, Valentina; Quaroni, Luca; Ferri, Davide

    2014-07-01

    We describe a novel cell used to combine in situ transmission X-ray absorption spectroscopy (XAS) with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) in a single experiment. The novelty of the cell design compared to current examples is that both radiations are passed through an X-ray and IR transparent window in direct contact with the sample. This innovative geometry also offers a wide surface for IR collection. In order to avoid interference from the crystalline IR transparent materials (e.g., CaF2, MgF2, diamond) a 500 μm carbon filled hole is laser drilled in the center of a CaF2 window. The cell is designed to represent a plug flow reactor, has reduced dead volume in order to allow for fast exchange of gases and is therefore suitable for experiments under fast transients, e.g., according to the concentration modulation approach. High quality time-resolved XAS and DRIFTS data of a 2 wt.% Pt/Al2O3 catalyst are obtained in concentration modulation experiments where CO (or H2) pulses are alternated to O2 pulses at 150 °C. We show that additional information can be obtained on the Pt redox dynamic under working conditions thanks to the improved sensitivity given by the modulation approach followed by Phase Sensitive Detection (PSD) analysis. It is anticipated that the design of the novel cell is likely suitable for a number of other in situ spectroscopic and diffraction methods.

  16. Near Edge X-Ray Absorption Fine Structure Spectroscopy with X-Ray Free-Electron Lasers

    SciTech Connect

    Bernstein, D.P.; Acremann, Y.; Scherz, A.; Burkhardt, M.; Stohr, J.; Beye, M.; Schlotter, W.F.; Beeck, T.; Sorgenfrei, F.; Pietzsch, A.; Wurth, W.; Fohlisch, A.; /Hamburg U.

    2009-12-11

    We demonstrate the feasibility of Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy on solids by means of femtosecond soft x-ray pulses from a free-electron laser (FEL). Our experiments, carried out at the Free-Electron Laser at Hamburg (FLASH), used a special sample geometry, spectrographic energy dispersion, single shot position-sensitive detection and a data normalization procedure that eliminates the severe fluctuations of the incident intensity in space and photon energy. As an example we recorded the {sup 3}D{sub 1} N{sub 4,5}-edge absorption resonance of La{sup 3+}-ions in LaMnO{sub 3}. Our study opens the door for x-ray absorption measurements on future x-ray FEL facilities.

  17. X-ray Absorption Fine Structure Studies of Mn Coordination in Doped Perovskite SrTiO3

    SciTech Connect

    Levin, I.; Krayzman, V; Woicik, J; Tkach, A; Vilarinho, P

    2010-01-01

    The coordination of Mn in doped SrTiO{sub 3} ceramics having nominal compositions SrTi{sub 0.98}Mn{sub 0.02}O{sub 3} and Sr{sub 0.98}Mn{sub 0.02}TiO{sub 3} was analyzed using x-ray absorption fine structure (XAFS) measurements. As expected, Mn{sup 4+} substitution for Ti{sup 4+} leads to Mn occupancy of the octahedral B-sites of ABO{sub 3} perovskite lattice with a Mn-O bond distance of 1.902 {angstrom} (compared to 1.953 {angstrom} for Ti-O) and no significant local distortions around the Mn atoms. In contrast, for the composition Sr{sub 0.98}Mn{sup 0.02}TiO{sub 3}, Mn segregates to both the A-sites (as Mn{sup 2+}) and the B-sites (predominantly as Mn{sup 4+}). Extended XAFS confirms strong ({approx} 0.77 {angstrom}) displacements of Mn{sup 2+} cations off the ideal A-site positions along <001> directions with a significant distortion of several coordination shells around the dopant atoms.

  18. Chromium oxide as a metal diffusion barrier layer: An x-ray absorption fine structure spectroscopy study

    NASA Astrophysics Data System (ADS)

    Ahamad Mohiddon, Md.; Lakshun Naidu, K.; Ghanashyam Krishna, M.; Dalba, G.; Ahmed, S. I.; Rocca, F.

    2014-01-01

    The interaction at the interface between chromium and amorphous Silicon (a-Si) films in the presence of a sandwich layer of chromium oxide is investigated using X-ray absorption fine structure (XAFS) spectroscopy. The oxidized interface was created, in situ, prior to the deposition of a 400 nm tick a-Si layer over a 50 nm tick Cr layer. The entire stack of substrate/metallic Cr/Cr2O3/a-Si was then annealed at temperatures from 300 up to 700 °C. Analysis of the near edge and extended regions of each XAFS spectrum shows that only a small fraction of Cr is able to diffuse through the oxide layer up to 500 °C, while the remaining fraction is buried under the oxide layer in the form of metallic Cr. At higher temperatures, diffusion through the oxide layer is enhanced and the diffused metallic Cr reacts with a-Si to form CrSi2. At 700 °C, the film contains Cr2O3 and CrSi2 without evidence of unreacted metallic Cr. The activation energy and diffusion coefficient of Cr are quantitatively determined in the two temperature regions, one where the oxide acts as diffusion barrier and another where it is transparent to Cr diffusion. It is thus demonstrated that chromium oxide can be used as a diffusion barrier to prevent metal diffusion into a-Si.

  19. A Geometric and Electrostatic Study of the [4Fe-4S] Cluster of Adenosine-5´-Phosphosulfate Reductase from Broken Symmetry Density Functional Calculations and Extended X-ray Absorption Fine Structure Spectroscopy

    PubMed Central

    Bhave, Devayani P.; Han, Wen-Ge; Pazicni, Samuel; Penner-Hahn, James E.; Carroll, Kate S.; Noodleman, Louis

    2011-01-01

    Adenosine-5’-phosphosulfate reductase (APSR) is an iron-sulfur protein that catalyses the reduction of adenosine-5’-phosphosulfate (APS) to sulfite. APSR coordinates to a [4Fe-4S] cluster via a conserved CC-X~80-CXXC motif and the cluster is essential for catalysis. Despite extensive functional, structural and spectroscopic studies, the exact role of the iron-sulfur cluster in APS reduction remains unknown. To gain an understanding into the role of the cluster, density functional theory (DFT) analysis and extended X-ray fine structure spectroscopy (EXAFS) have been performed to reveal insights into the coordination, geometry and electrostatics of the [4Fe-4S] cluster. XANES data confirms that the cluster is in the [4Fe-4S]2+ state in both native and substrate-bound APSR while EXAFS data recorded at ~0.1 Å resolution indicates that there is no significant change in the structure of the [4Fe-4S] cluster between the native and substrate-bound forms of the protein. On the other hand, DFT calculations provide an insight into the subtle differences between the geometry of the cluster in the native and APS-bound forms of APSR. A comparison between models with and without the tandem cysteine pair coordination of the cluster suggests a role for the unique coordination in facilitating a compact geometric structure and ‘fine-tuning’ the electronic structure to prevent reduction of the cluster. Further, calculations using models in which residue Lys144 is mutated to Ala confirm the finding that Lys144 serves as a crucial link in the interactions involving the [4Fe-4S] cluster and APS. PMID:21678934

  20. Characterization of the Cu(Π) and Zn(Π) binding to the Amyloid-β short peptides by both the Extended X-ray Absorption Fine Structure and the Synchrotron Radiation Circular Dichroism spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiyin; Sun, Shuaishuai; Xu, Jianhua; Zhang, Jing; Huang, Yan; Zhang, Bingbing; Tao, Ye

    2013-04-01

    Alzheimer's disease (AD) is a progressive and devastating neurodegenerative pathology, clinically characterized by dementia, cognitive impairment, personality disorders and memory loss. It is generally accepted that, misfolding of Aβ peptides is the key element in pathogenesis and the secondary structure of Aβ can be changed to major β-strand with reasons unknown yet. Many studies have shown that the misfolding may be linked with some biometals, mainly copper and zinc ions. To characterize interactions of Aβ and metal ions, we utilized both the extended X-ray fine structure spectroscopy (EXAFS) and the synchrotron radiation circular dichroism spectroscopy (SRCD). Aβ (13-22), Aβ (13-21), Aβ (E22G) and Aβ(HH-AA) were selected to study the mechanism of copper and zinc binding to Aβ. We found that Cu interaction with H13 and H14 residues led to the disappearance of the PPΠ, while the Cu binding E22 residue caused a remarkable conformation change to β-sheet enrichment. The Zn ion, in contrast, made little effect on the conformation and it coordinated to only one histidine (H residue) or not.

  1. Local structure of Se in cancrinite: X-ray absorption fine structure theoretical analysis

    NASA Astrophysics Data System (ADS)

    Soldatov, A. V.; Yalovega, G. E.

    2000-04-01

    A theoretical "ab initio" analysis of the polarized X-ray absorption spectrum of selenium in a cancrinite matrix based on a full multiple-scattering theory has been performed. Comparison of the theoretical spectra with the experimental results shows that Se atoms form dimerized chains in the channels of the cancrinite matrix with an interchain distance of about 4.8 Å. In addition the distribution of unoccupied partial s-, p- and d- electronic states of Se has been obtained. Density of states analysis provides some insight into the chemical bonding of Se in cancrinite. The results suggest that the interaction of Se atoms with the matrix is the cause of the unusually large Se-Se distance in dimers.

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

    NASA Astrophysics Data System (ADS)

    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

  3. Vibronic fine structure in high-resolution x-ray absorption spectra from ion-bombarded boron nitride nanotubes

    SciTech Connect

    Petravic, Mladen; Peter, Robert; Varasanec, Marijana; Li Luhua; Chen Ying; Cowie, Bruce C. C.

    2013-05-15

    The authors have applied high-resolution near-edge x-ray absorption fine structure measurements around the nitrogen K-edge to study the effects of ion-bombardment on near-surface properties of boron nitride nanotubes. A notable difference has been observed between surface sensitive partial electron yield (PEY) and bulk sensitive total electron yield (TEY) fine-structure measurements. The authors assign the PEY fine structure to the coupling of excited molecular vibrational modes to electronic transitions in NO molecules trapped just below the surface. Oxidation resistance of the boron nitride nanotubes is significantly reduced by low energy ion bombardment, as broken B-N bonds are replaced by N-O bonds involving oxygen present in the surface region. In contrast to the PEY spectra, the bulk sensitive TEY measurements on as-grown samples do not exhibit any fine structure while the ion-bombarded samples show a clear vibronic signature of molecular nitrogen.

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

    SciTech Connect

    Montero-Cabrera, M. E. Fuentes-Cobas, L. E.; Macías-Ríos, E.; Fuentes-Montero, M. E.

    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})

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

    SciTech Connect

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

    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.

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

    NASA Astrophysics Data System (ADS)

    Montero-Cabrera, M. E.; Fuentes-Cobas, L. E.; Macías-Ríos, E.; Fuentes-Montero, M. E.

    2015-07-01

    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).

  7. Near-edge x-ray absorption fine structure measurements using a laboratory-scale XUV source

    NASA Astrophysics Data System (ADS)

    Peth, Christian; Barkusky, Frank; Mann, Klaus

    2008-05-01

    We present a compact setup for near-edge x-ray absorption spectroscopy at the carbon K-edge based on a laser-driven plasma source. To generate the required broad-band emission in the spectral range of the 'water window' (λ = 2.2-4.4 nm) a krypton gas puff target was used. The table-top setup consisting basically of the laser-plasma source and a flat-field spectrometer can be used for near-edge x-ray absorption fine structure experiments in transmission as well as reflection under grazing incidence conditions (ReflEXAFS). The latter method offers the advantage that thin film preparation is not necessary and that the surface sensitivity is strongly enhanced. The results obtained for thin polymer films show good agreement with synchrotron data. Furthermore, we use the ReflEXAFS method to investigate changes in the chemical composition of PMMA induced by extreme ultraviolet (EUV) radiation. The spectra indicate a loss of the carbonyl functional group upon irradiation as well as crosslinking effects at high EUV radiation doses.

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

    NASA Astrophysics Data System (ADS)

    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.

  9. X-ray absorption fine-structure spectroscopy studies of Fe sites in natural human neuromelanin and synthetic analogues.

    PubMed Central

    Kropf, A J; Bunker, B A; Eisner, M; Moss, S C; Zecca, L; Stroppolo, A; Crippa, P R

    1998-01-01

    X-ray absorption fine-structure spectroscopy is used to study the local environment of the iron site in natural (human) neuromelanin extracted from substantia nigra tissue and in various synthetic neuromelanins. All the materials show Fe centered in a nearest neighbor sixfold (distorted) oxygen octahedron; the Fe-O distances, while slightly different in the natural and synthetic neuromelanin, are both approximately 2.0 A. Appreciable differences arise, however, in the second (and higher) coordination shells. In this case the synthetic melanin has the four planar oxygens bound to carbon rings with Fe-C distances of approximately 2.82 and 4.13 A; the human sample does not show the 2.82 A link but instead indicates a double shell at approximately 3.45 and 3.78 A. PMID:9826634

  10. X-ray absorption fine structure (XAFS) analyses of Ni species trapped in graphene sheet of carbon nanofibers

    SciTech Connect

    Ushiro, Mayuko; Uno, Kanae; Fujikawa, Takashi; Sato, Yoshinori; Tohji, Kazuyuki; Watari, Fumio; Chun, W.-J.; Koike, Yuichiro; Asakura, Kiyotaka

    2006-04-01

    Metal impurities in the carbon nanotubes and carbon nanofibers play an important role in understanding their physical and chemical properties. We apply the Ni K-edge x-ray absorption fine structure analyses to the local electronic and geometric structures around embedded Ni impurities used as catalysts in a carbon nanofiber in combination with multiple scattering analyses. We find almost Ni catalysts as metal particles are removed by the purification treatment. Even after the purification, residual 100 ppm Ni species are still absorbed; most of them are in monomer structure with Ni-C bond length 1.83 A, and each of them is substituted for a carbon atom in a graphene sheet.

  11. Local Structure Around Te in Heavily Doped GaAs:Te using X-Ray Absorption Fine Structure

    SciTech Connect

    Pietnoczka, A.; Bacewicz, R.; Slupinski, T.; Antonowicz, J.; Wei, Su-Huai

    2012-04-01

    The annealing of heavily doped GaAs:Te can significantly change the free electron concentration in a reversible manner. These changes of electrical properties are accompanied by the structural changes of GaAs:Te solid solution. We used X-ray Absorption Fine Structure at K-edge of tellurium to determine local changes around Te atoms for different states of the GaAs:Te crystals caused by the annealing corresponding to different electron concentrations. The best EXAFS fit for the samples with high electron concentration was obtained for the substitutional Te{sub As} model with elongated Te-Ga bonds (as compared to the As-Ga distance). For the samples in the low concentration state the best fit was for the pairs of Te atoms forming a rhombohedral symmetry double-DX centre, with the proportional admixture of the substitutional tellurium.

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

    SciTech Connect

    Lee, Ik-Jae; Yu, Chung-Jong; Yun, Young-Duck; Lee, Chae-Soon; Seo, In Deuk; Kim, Hyo-Yun; Lee, Woul-Woo; Chae, Keun Hwa

    2010-02-15

    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.

  13. In situ X-ray absorption fine structure studies of a manganese dioxide electrode in a rechargeable MnO{sub 2}/Zn alkaline battery environment

    SciTech Connect

    Mo, Y.; Hu, Y.; Bae, I.T.; Miller, B.; Scherson, D.A.; Antonio, M.R.

    1996-12-31

    Electronic and structural aspects of a MnO{sub 2} electrode in a rechargeable MnO{sub 2}/Zn battery environment have been investigated by in situ Mn K-edge X-ray absorption fine structure (XAFS). The relative amplitudes of the three major Fourier transform shells of the EXAFS (extended XAFS) function of the rechargeable MnO{sub 2} electrode in the undischarged state were found to be similar to those found for ramsdellite, a MnO{sub 2} polymorph with substantial corner-sharing linkages among the basic MnO{sub 6} octahedral units. The analyses of the background-subtracted pre-edge peaks and absorption edge regions for the nominally 1-e{sup {minus}} discharged electrode were consistent with Mn{sup 3+} as being the predominant constituent species, rather than a mixture of Mn{sup 4+} and Mn{sup 2+} sites. Furthermore, careful inspection of both the XANES (X-ray absorption near edge structure) and EXAFS indicated that the full recharge of MnO, which had been previously discharged either by a 1- or 2-equivalent corner-sharing linkages compared to the original undischarged MnO{sub 2}.

  14. Structural characterization of CO-inhibited Mo-nitrogenase by combined application of nuclear resonance vibrational spectroscopy, extended X-ray absorption fine structure, and density functional theory: new insights into the effects of CO binding and the role of the interstitial atom.

    PubMed

    Scott, Aubrey D; Pelmenschikov, Vladimir; Guo, Yisong; Yan, Lifen; Wang, Hongxin; George, Simon J; Dapper, Christie H; Newton, William E; Yoda, Yoshitaka; Tanaka, Yoshihito; Cramer, Stephen P

    2014-11-12

    The properties of CO-inhibited Azotobacter vinelandii (Av) Mo-nitrogenase (N2ase) have been examined by the combined application of nuclear resonance vibrational spectroscopy (NRVS), extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT). Dramatic changes in the NRVS are seen under high-CO conditions, especially in a 188 cm(-1) mode associated with symmetric breathing of the central cage of the FeMo-cofactor. Similar changes are reproduced with the α-H195Q N2ase variant. In the frequency region above 450 cm(-1), additional features are seen that are assigned to Fe-CO bending and stretching modes (confirmed by (13)CO isotope shifts). The EXAFS for wild-type N2ase shows evidence for a significant cluster distortion under high-CO conditions, most dramatically in the splitting of the interaction between Mo and the shell of Fe atoms originally at 5.08 Å in the resting enzyme. A DFT model with both a terminal -CO and a partially reduced -CHO ligand bound to adjacent Fe sites is consistent with both earlier FT-IR experiments, and the present EXAFS and NRVS observations for the wild-type enzyme. Another DFT model with two terminal CO ligands on the adjacent Fe atoms yields Fe-CO bands consistent with the α-H195Q variant NRVS. The calculations also shed light on the vibrational "shake" modes of the interstitial atom inside the central cage, and their interaction with the Fe-CO modes. Implications for the CO and N2 reactivity of N2ase are discussed.

  15. X-ray absorption fine structure measurement with a 9 V electric battery x-ray emitter

    SciTech Connect

    Mitsuya, Shota; Ishii, Hideshi; Kawai, Jun; Tanaka, Keiichi

    2006-09-25

    X-ray absorption spectral analysis is a well known technique for analyzing the chemical environment of an element in a specimen. It has been believed that high intensity and monochromatized x rays such as the synchrotron radiation are required for an x-ray absorption experiment. In the present study, however, we demonstrate that the x-ray absorption spectral measurement of transition metal foils with an energy resolution of 10 eV is possible with a combination of a 9 V dry electric battery pyroelectric x-ray generator and a superconducting microcalorimeter.

  16. The forms of trace metals in an Illinois basin coal by x-ray absorption fine structure spectroscopy

    USGS Publications Warehouse

    Chou, I.-Ming; Bruinius, J.A.; Lytle, J.M.; Ruch, R.R.; Huggins, Frank E.; Huffman, G.P.; Ho, K.K.

    1997-01-01

    Utilities burning Illinois coals currently do not consider trace elements in their flue gas emissions. After the US EPA completes an investigation on trace elements, however, this may change and flue gas emission standards may be established. The mode of occurrence of a trace element may determine its cleanability and Hue gas emission potential. X-ray Absorption Fine Structure (XAFS) is a spectroscopic technique that can differentiate the mode of occurrence of an element, even at the low concentrations that trace elements are found in coal. This is principally accomplished by comparing the XAFS spectra of a coal to a database of reference sample spectra. This study evaluated the technique as a potential tool to examine six trace elements in an Illinois #6 coal. For the elements As and Zn, the present database provides a definitive interpretation on their mode of occurrence. For the elements Ti, V, Cr, and Mn the database of XAFS spectra of trace elements in coal was still too limited to allow a definitive interpretation. The data obtained on these elements, however, was sufficient to rule out several of the mineralogical possibilities that have been suggested previously. The results indicate that XAFS is a promising technique for the study of trace elements in coal.

  17. Mechanism of Pb Adsorption to Fatty Acid Langmuir Monolayers Studied by X-ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Boyanov, M.I.; Kmetko, J.; Shibata, T.; Datta, A.; Dutta, P.; Bunker, B.A.

    2010-09-30

    The local atomic environment of lead (Pb) adsorbed to a CH{sub 3}(CH{sub 2}){sub 19}COOH Langmuir monolayer was investigated in situ using grazing-incidence X-ray absorption fine structure (GI-XAFS) spectroscopy at the Pb L{sub III} edge. Measurements were performed at pH 6.5 of the 10{sup -5} M PbCl{sub 2} solution subphase, a condition under which grazing incidence diffraction (GID) revealed a large-area commensurate superstructure underneath the close-packed organic monolayer. The XAFS results indicate covalent binding of the Pb cations to the carboxyl headgroups, and the observed Pb-Pb coordination suggests that the metal is adsorbed as a hydrolysis polymer, rather than as individual Pb{sup 2+} ions. The data are consistent with a bidentate chelating mechanism and a one Pb atom to one carboxyl headgroup binding stoichiometry. We discuss how this adsorption model can explain the peculiarities observed with Pb in previous metal-Langmuir monolayer studies. A systematic study of lead perchlorate and lead acetate aqueous solutions is presented and used in the analysis. XAFS multiple scattering effects from alignment of the Pb-C-C atoms in the lead acetate solutions are reported.

  18. Mercury Speciation by X-ray Absorption Fine Structure Spectroscopy and Sequential Chemical Extractions: A Comparison of Speciation Methods

    USGS Publications Warehouse

    Kim, C.S.; Bloom, N.S.; Rytuba, J.J.; Brown, Gordon E.

    2003-01-01

    Determining the chemical speciation of mercury in contaminated mining and industrial environments is essential for predicting its solubility, transport behavior, and potential bioavailability as well as for designing effective remediation strategies. In this study, two techniques for determining Hg speciation-X-ray absorption fine structure (XAFS) spectroscopy and sequential chemical extractions (SCE)-are independently applied to a set of samples with Hg concentrations ranging from 132 to 7539 mg/kg to determine if the two techniques provide comparable Hg speciation results. Generally, the proportions of insoluble HgS (cinnabar, metacinnabar) and HgSe identified by XAFS correlate well with the proportion of Hg removed in the aqua regia extraction demonstrated to remove HgS and HgSe. Statistically significant (> 10%) differences are observed however in samples containing more soluble Hg-containing phases (HgCl2, HgO, Hg3S2O 4). Such differences may be related to matrix, particle size, or crystallinity effects, which could affect the apparent solubility of Hg phases present. In more highly concentrated samples, microscopy techniques can help characterize the Hg-bearing species in complex multiphase natural samples.

  19. Extended X-ray absorption studies of copper (II) dibenzoyal methane diquinoline complexes

    NASA Astrophysics Data System (ADS)

    Mishra, A.; Sharma, P.; Malviya, P. K.

    2013-06-01

    X-ray K-absorption spectroscopic studies have been carried out on copper (II) mixed-ligand complexes. Copper is a transition metal, which in the zero oxidation state has an electron configuration of [Ar] 4s24p63d9. Copper is found in three different oxidation states: Cu(I), Cu(II), and Cu(III). In the copper (II) oxidation state, the metal has 9 d electrons. Jahn-Teller distortion causes a splitting of eg and t2g orbitals. Most Cu(II) complexes are square planar for this reason. In a series of those compounds, we have prepared copper (II) complexes containing two nitrato ligands and a 2,2'-dipyridylamine(dpa) derivative ligand. The 2,2' - dipyridylamine and its derivatives have been widely used for metal complexes because of their good chelating property, structural flexibility. we have estimated the average metalligand bond distances from the fine structure data. We have determined the bond lengths for the copper (II) complexes with the help of Levy's, LSS, Fourier transform, Lytle's Methods.

  20. X-ray absorption fine structure spectroscopic studies of Octakis(DMSO)lanthanoid(III) complexes in solution and in the solid iodides.

    PubMed

    Persson, Ingmar; Risberg, Emiliana Damian; D'Angelo, Paola; De Panfilis, Simone; Sandström, Magnus; Abbasi, Alireza

    2007-09-17

    Octakis(DMSO)lanthanoid(III) iodides (DMSO = dimethylsulfoxide), [Ln(OS(CH3)2)8]I3, of most lanthanoid(III) ions in the series from La to Lu have been studied in the solid state and in DMSO solution by extended X-ray absorption fine structure (EXAFS) spectroscopy. L3-edge and also some K-edge spectra were recorded, which provided mean Ln-O bond distances for the octakis(DMSO)lanthanoid(III) complexes. The agreement with the average of the Ln-O bond distances obtained in a separate study by X-ray crystallography was quite satisfactory. The crystalline octakis(DMSO)lanthanoid(III) iodide salts have a fairly broad distribution of Ln-O bond distances, ca. 0.1 A, with a few disordered DMSO ligands. Their EXAFS spectra are in excellent agreement with those obtained for the solvated lanthanoid(III) ions in DMSO solution, both of which show slightly asymmetric distributions of the Ln-O bond distances. Hence, all lanthanoid(III) ions are present as octakis(DMSO)lanthanoid(III) complexes in DMSO solution, with the mean Ln-O distances centered at 2.50 (La), 2.45 (Pr), 2.43 (Nd), 2.41 (Sm), 2.40 (Eu), 2.39 (Gd), 2.37 (Tb), 2.36 (Dy), 2.34 (Ho), 2.33 (Er), 2.31 (Tm), and 2.29 A (Lu). This decrease in the Ln-O bond distances is larger than expected from the previously established ionic radii for octa-coordination. This indicates increasing polarization of the LnIII-O(DMSO) bonds with increasing atomic number. However, the S(1s) electron transition energies in the sulfur K-edge X-ray absorption near-edge structure (XANES) spectra, probing the unoccupied molecular orbitals of lowest energy of the DMSO ligands for the [Ln(OS(CH3)2)8](3+) complexes, change only insignificantly from Ln = La to Lu. This indicates that there is no appreciable change in the sigma-contribution to the S-O bond, probably due to a corresponding increase in the contribution from the sulfur lone pair to the bonding.

  1. X-Ray Absorption Fine Structure Spectroscopic Studies of Octakis(DMSO)Lanthanoid(III) Complexes in Solution And in the Solid Iodides

    SciTech Connect

    Persson, I.; Risberg, E.Damian; D'Angelo, P.; Panfilis, S.De; Sandstrom, M.; Abbasi, A.

    2009-06-04

    Octakis(DMSO)lanthanoid(III) iodides (DMSO = dimethylsulfoxide), [Ln(OS(CH{sub 3}){sub 2}){sub 8}]I{sub 3}, of most lanthanoid(III) ions in the series from La to Lu have been studied in the solid state and in DMSO solution by extended X-ray absorption fine structure (EXAFS) spectroscopy. L{sub 3}-edge and also some K-edge spectra were recorded, which provided mean Ln-O bond distances for the octakis(DMSO)lanthanoid(III) complexes. The agreement with the average of the Ln-O bond distances obtained in a separate study by X-ray crystallography was quite satisfactory. The crystalline octakis(DMSO)lanthanoid(III) iodide salts have a fairly broad distribution of Ln-O bond distances, ca. 0.1 {angstrom}, with a few disordered DMSO ligands. Their EXAFS spectra are in excellent agreement with those obtained for the solvated lanthanoid(III) ions in DMSO solution, both of which show slightly asymmetric distributions of the Ln-O bond distances. Hence, all lanthanoid(III) ions are present as octakis(DMSO)lanthanoid(III) complexes in DMSO solution, with the mean Ln-O distances centered at 2.50 (La), 2.45 (Pr), 2.43 (Nd), 2.41 (Sm), 2.40 (Eu), 2.39 (Gd), 2.37 (Tb), 2.36 (Dy), 2.34 (Ho), 2.33 (Er), 2.31 (Tm), and 2.29 {angstrom} (Lu). This decrease in the Ln-O bond distances is larger than expected from the previously established ionic radii for octa-coordination. This indicates increasing polarization of the Ln{sup III}-O(DMSO) bonds with increasing atomic number. However, the S(1s) electron transition energies in the sulfur K-edge X-ray absorption near-edge structure (XANES) spectra, probing the unoccupied molecular orbitals of lowest energy of the DMSO ligands for the [Ln(OS(CH{sub 3}){sub 2}){sub 8}]{sup 3+} complexes, change only insignificantly from Ln = La to Lu. This indicates that there is no appreciable change in the ?-contribution to the S-O bond, probably due to a corresponding increase in the contribution from the sulfur lone pair to the bonding.

  2. Cyclic voltammetry and near edge X-ray absorption fine structure spectroscopy at the Ag L3-edge on electrochemical halogenation of Ag layers on Au(111)

    NASA Astrophysics Data System (ADS)

    Endo, Osamu; Nakamura, Masashi

    2011-05-01

    One to three layers of Ag grown on a Au(111) electrode were studied by cyclic voltammetry in chloride and bromide solutions and by ex-situ near-edge X-ray absorption fine structure spectroscopy at the Ag L3-edge (Ag L3-NEXAFS). The one and two layers obtained by underpotential deposition exhibited reduced intensity at the absorption edge in the Ag L3-NEXAFS spectra, which suggests the gain of d-electrons in these layers. The cyclic voltammograms and the Ag L3-NEXAFS spectra indicate that the second and third layers of Ag halogenated at positive potentials, whereas the first layer remained in metallic form.

  3. Calculation of near-edge x-ray-absorption fine structure at finite temperatures: spectral signatures of hydrogen bond breaking in liquid water.

    PubMed

    Hetényi, Balázs; De Angelis, Filippo; Giannozzi, Paolo; Car, Roberto

    2004-05-08

    We calculate the near-edge x-ray-absorption fine structure of H(2)O in the gas, hexagonal ice, and liquid phases using heuristic density-functional based methods. We present a detailed comparison of our results with experiment. The differences between the ice and water spectra can be rationalized in terms of the breaking of hydrogen bonds around the absorbing molecule. In particular the increase in the pre-edge absorption feature from ice to water is shown to be due to the breaking of a donor hydrogen bond. We also find that in water approximately 19% of hydrogen bonds are broken.

  4. Separable-spherical-wave approximation: Application to x-ray-absorption fine-structure multiple scattering in ReO3

    NASA Astrophysics Data System (ADS)

    Houser, B.; Ingalls, R.; Rehr, J. J.

    1992-04-01

    Rehr and Albers have shown that the exact x-ray-absorption fine-structure (XAFS) propagator may be expanded in a separable matrix form, and that the lowest-order term in the expansion yields XAFS formulas that contain spherical-wave corrections, yet retain the simplicity of the plane-wave approximation. This separable-spherical-wave approximation was used to model the multiple-scattering contributions to the XAFS spectrum of rhenium trioxide. We report a modest improvement over the plane-wave approximation.

  5. Versatile plug flow catalytic cell for in situ transmission/fluorescence x-ray absorption fine structure measurements

    NASA Astrophysics Data System (ADS)

    Centomo, P.; Meneghini, C.; Zecca, M.

    2013-05-01

    A novel flow-through catalytic cell has been developed for in situ x-ray absorption spectroscopy (XAS) experiments on heterogeneous catalysts under working conditions and in the presence of a liquid and a gas phase. The apparatus allows to carry out XAS measurements in both the transmission and fluorescence modes, at moderate temperature (from RT to 50-80 °C) and low-medium gas pressure (up to 7-8 bars). The materials employed are compatible with several chemicals such as those involved in the direct synthesis of hydrogen peroxide (O2, H2, H2O2, methanol). The versatile design of the cell allows to fit it to different experimental setups in synchrotron radiation beamlines. It was used successfully for the first time to test nanostructured Pd catalysts during the direct synthesis of hydrogen peroxide (H2O2) in methanol solution from dihydrogen and dioxygen.

  6. The molecular pathway to ZIF-7 microrods revealed by in situ time-resolved small- and wide-angle X-ray scattering, quick-scanning extended X-ray absorption spectroscopy, and DFT calculations.

    PubMed

    Goesten, Maarten; Stavitski, Eli; Pidko, Evgeny A; Gücüyener, Canan; Boshuizen, Bart; Ehrlich, Steven N; Hensen, Emiel J M; Kapteijn, Freek; Gascon, Jorge

    2013-06-10

    We present an in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and quick-scanning extended X-ray absorption fine-structure (QEXAFS) spectroscopy study on the crystallization of the metal-organic framework ZIF-7. In combination with DFT calculations, the self-assembly and growth of ZIF-7 microrods together with the chemical function of the crystal growth modulator (diethylamine) are revealed at all relevant length scales, from the atomic to the full crystal size.

  7. Versatile plug flow catalytic cell for in situ transmission/fluorescence x-ray absorption fine structure measurements

    SciTech Connect

    Centomo, P.; Zecca, M.; Meneghini, C.

    2013-05-15

    A novel flow-through catalytic cell has been developed for in situ x-ray absorption spectroscopy (XAS) experiments on heterogeneous catalysts under working conditions and in the presence of a liquid and a gas phase. The apparatus allows to carry out XAS measurements in both the transmission and fluorescence modes, at moderate temperature (from RT to 50-80 Degree-Sign C) and low-medium gas pressure (up to 7-8 bars). The materials employed are compatible with several chemicals such as those involved in the direct synthesis of hydrogen peroxide (O{sub 2}, H{sub 2}, H{sub 2}O{sub 2}, methanol). The versatile design of the cell allows to fit it to different experimental setups in synchrotron radiation beamlines. It was used successfully for the first time to test nanostructured Pd catalysts during the direct synthesis of hydrogen peroxide (H{sub 2}O{sub 2}) in methanol solution from dihydrogen and dioxygen.

  8. How Accurately Can Extended X-ray Absorption Spectra Be Predicted from First Principles? Implications for Modeling the Oxygen-Evolving Complex in Photosystem II.

    PubMed

    Beckwith, Martha A; Ames, William; Vila, Fernando D; Krewald, Vera; Pantazis, Dimitrios A; Mantel, Claire; Pécaut, Jacques; Gennari, Marcello; Duboc, Carole; Collomb, Marie-Noëlle; Yano, Junko; Rehr, John J; Neese, Frank; DeBeer, Serena

    2015-10-14

    First principle calculations of extended X-ray absorption fine structure (EXAFS) data have seen widespread use in bioinorganic chemistry, perhaps most notably for modeling the Mn4Ca site in the oxygen evolving complex (OEC) of photosystem II (PSII). The logic implied by the calculations rests on the assumption that it is possible to a priori predict an accurate EXAFS spectrum provided that the underlying geometric structure is correct. The present study investigates the extent to which this is possible using state of the art EXAFS theory. The FEFF program is used to evaluate the ability of a multiple scattering-based approach to directly calculate the EXAFS spectrum of crystallographically defined model complexes. The results of these parameter free predictions are compared with the more traditional approach of fitting FEFF calculated spectra to experimental data. A series of seven crystallographically characterized Mn monomers and dimers is used as a test set. The largest deviations between the FEFF calculated EXAFS spectra and the experimental EXAFS spectra arise from the amplitudes. The amplitude errors result from a combination of errors in calculated S0(2) and Debye-Waller values as well as uncertainties in background subtraction. Additional errors may be attributed to structural parameters, particularly in cases where reliable high-resolution crystal structures are not available. Based on these investigations, the strengths and weaknesses of using first-principle EXAFS calculations as a predictive tool are discussed. We demonstrate that a range of DFT optimized structures of the OEC may all be considered consistent with experimental EXAFS data and that caution must be exercised when using EXAFS data to obtain topological arrangements of complex clusters.

  9. Electronic structure of individual hybrid colloid particles studied by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the X-ray microscope.

    PubMed

    Henzler, Katja; Guttmann, Peter; Lu, Yan; Polzer, Frank; Schneider, Gerd; Ballauff, Matthias

    2013-02-13

    The electronic structure of individual hybrid particles was studied by nanoscale near-edge X-ray absorption spectromicroscopy. The colloidal particles consist of a solid polystyrene core and a cross-linked poly-N-(isopropylacrylamide) shell with embedded crystalline titanium dioxide (TiO(2)) nanoparticles (d = 6 ± 3 nm). The TiO(2) particles are generated in the carrier network by a sol-gel process at room temperature. The hybrid particles were imaged with photon energy steps of 0.1 eV in their hydrated environment with a cryo transmission X-ray microscope (TXM) at the Ti L(2,3)-edge. By analyzing the image stacks, the obtained near-edge X-ray absorption fine structure (NEXAFS) spectra of our individual hybrid particles show clearly that our synthesis generates TiO(2) in the anastase phase. Additionally, our spectromicroscopy method permits the determination of the density distribution of TiO(2) in single carrier particles. Therefore, NEXAFS spectroscopy combined with TXM presents a unique method to get in-depth insight into the electronic structure of hybrid materials.

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

    SciTech Connect

    Dunn, J; Steel, A B

    2012-05-06

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

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

    PubMed

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

    2010-09-14

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

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

    SciTech Connect

    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.

  13. Time dependent density functional theory study of the near-edge x-ray absorption fine structure of benzene in gas phase and on metal surfaces.

    PubMed

    Asmuruf, Frans A; Besley, Nicholas A

    2008-08-14

    The near-edge x-ray absorption fine structure of benzene in the gas phase and adsorbed on the Au(111) and Pt(111) surfaces is studied with time dependent density functional theory. Excitation energies computed with hybrid exchange-correlation functionals are too low compared to experiment. However, after applying a constant shift the spectra are in good agreement with experiment. For benzene on the Au(111) surface, two bands arising from excitation to the e(2u)(pi(*)) and b(2g)(pi(*)) orbitals of benzene are observed for photon incidence parallel to the surface. On Pt(111) surface, a broader band arises from excitation to benzene orbitals that are mixed with the surface and have both sigma(*)(Pt-C) and pi(*) characters.

  14. Time-resolved near-edge x-ray absorption fine structure spectroscopy on photo-induced phase transitions using a tabletop soft-x-ray spectrometer

    NASA Astrophysics Data System (ADS)

    Grossmann, P.; Rajkovic, I.; Moré, R.; Norpoth, J.; Techert, S.; Jooss, C.; Mann, Klaus

    2012-05-01

    We present a table-top soft-x-ray spectrometer for the wavelength range λ = 1-5 nm based on a stable laser-driven x-ray source, making use of a gas-puff target. With this setup, optical light-pump/soft-x-ray probe near-edge x-ray absorption fine structure (NEXAFS) experiments with a temporal resolution of about 230 ps are feasible. Pump-probe NEXAFS measurements were carried out in the "water-window" region (2.28 nm-4.36 nm) on the manganite Pr0.7Ca0.3MnO3, investigating diminutive changes of the oxygen K edge that derive from an optically induced phase transition. The results show the practicability of the table-top soft-x-ray spectrometer on demanding investigations so far exclusively conducted at synchrotron radiation sources.

  15. X-ray absorption fine structure analysis of molybdenum added to BaTiO3-based ceramics used for multilayer ceramic capacitors

    NASA Astrophysics Data System (ADS)

    Ogata, Yoichiro; Shimura, Tetsuo; Ryu, Minoru; Iwazaki, Yoshiki

    2017-04-01

    The effect of slight molybdenum doping of perovskite-type BaTiO3-based ceramics on the reliability of a multilayer ceramic capacitor (MLCC) and on the valence state of molybdenum in the BaTiO3-based ceramics has been investigated by highly accelerated lifetime tests and X-ray absorption fine structure analysis. The molybdenum added to the BaTiO3-based ceramics is located at Ti sites and improves the highly accelerated lifetime and lowers the initial dielectric resistivity in MLCCs. Through sintering in a reducing atmosphere, which is an important process in the fabrication of BaTiO3-based MLCCs, the oxidation state of the molybdenum added could be adjusted from +6 to a value close to +4.

  16. Portable ultrahigh-vacuum sample storage system for polarization-dependent total-reflection fluorescence x-ray absorption fine structure spectroscopy

    SciTech Connect

    Watanabe, Yoshihide Nishimura, Yusaku F.; Suzuki, Ryo; Beniya, Atsushi; Isomura, Noritake; Uehara, Hiromitsu; Asakura, Kiyotaka; Takakusagi, Satoru; Nimura, Tomoyuki

    2016-03-15

    A portable ultrahigh-vacuum sample storage system was designed and built to investigate the detailed geometric structures of mass-selected metal clusters on oxide substrates by polarization-dependent total-reflection fluorescence x-ray absorption fine structure spectroscopy (PTRF-XAFS). This ultrahigh-vacuum (UHV) sample storage system provides the handover of samples between two different sample manipulating systems. The sample storage system is adaptable for public transportation, facilitating experiments using air-sensitive samples in synchrotron radiation or other quantum beam facilities. The samples were transferred by the developed portable UHV transfer system via a public transportation at a distance over 400 km. The performance of the transfer system was demonstrated by a successful PTRF-XAFS study of Pt{sub 4} clusters deposited on a TiO{sub 2}(110) surface.

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

    SciTech Connect

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

    1992-12-31

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

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

    SciTech Connect

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

    1992-01-01

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

  19. Dopant activation mechanism of Bi wire-δ-doping into Si crystal, investigated with wavelength dispersive fluorescence x-ray absorption fine structure and density functional theory.

    PubMed

    Murata, Koichi; Kirkham, Christopher; Shimomura, Masaru; Nitta, Kiyofumi; Uruga, Tomoya; Terada, Yasuko; Nittoh, Koh-Ichi; Bowler, David R; Miki, Kazushi

    2017-04-20

    We successfully characterized the local structures of Bi atoms in a wire-δ-doped layer (1/8 ML) in a Si crystal, using wavelength dispersive fluorescence x-ray absorption fine structure at the beamline BL37XU, in SPring-8, with the help of density functional theory calculations. It was found that the burial of Bi nanolines on the Si(0 0 1) surface, via growth of Si capping layer at 400 °C by molecular beam epitaxy, reduced the Bi-Si bond length from [Formula: see text] to [Formula: see text] Å. We infer that following epitaxial growth the Bi-Bi dimers of the nanoline are broken, and the Bi atoms are located at substitutional sites within the Si crystal, leading to the shorter Bi-Si bond lengths.

  20. Dopant activation mechanism of Bi wire-δ-doping into Si crystal, investigated with wavelength dispersive fluorescence x-ray absorption fine structure and density functional theory

    NASA Astrophysics Data System (ADS)

    Murata, Koichi; Kirkham, Christopher; Shimomura, Masaru; Nitta, Kiyofumi; Uruga, Tomoya; Terada, Yasuko; Nittoh, Koh-ichi; Bowler, David R.; Miki, Kazushi

    2017-04-01

    We successfully characterized the local structures of Bi atoms in a wire-δ-doped layer (1/8 ML) in a Si crystal, using wavelength dispersive fluorescence x-ray absorption fine structure at the beamline BL37XU, in SPring-8, with the help of density functional theory calculations. It was found that the burial of Bi nanolines on the Si(0 0 1) surface, via growth of Si capping layer at 400 °C by molecular beam epitaxy, reduced the Bi–Si bond length from 2.79+/- 0.01~{\\mathring{\\text{A}}} to 2.63+/- 0.02 Å. We infer that following epitaxial growth the Bi–Bi dimers of the nanoline are broken, and the Bi atoms are located at substitutional sites within the Si crystal, leading to the shorter Bi–Si bond lengths.

  1. Effect of site occupancy disorder on martensitic properties of Mn2NiIn type alloys: X-ray absorption fine structure study

    NASA Astrophysics Data System (ADS)

    Lobo, D. N.; Priolkar, K. R.; Koide, A.; Emura, S.

    2017-02-01

    We have carried out ab-initio calculations of the local structure of Mn and Ni in the Mn2Ni1.5In0.5 alloy with different site occupancies in order to understand the similarities in martensitic and magnetic properties of Mn2Ni1+xIn1-x and Ni2Mn1+xIn1-x alloys. Our results show that in Mn2Ni1+xIn1-x alloys, there is a strong possibility of Mn atoms occupying all the three X, Y, and Z sites of the X2YZ Heusler structure, while Ni atoms preferentially occupy the X sites. Such a site occupancy disorder of Mn atoms is in addition to a local structural disorder due to size differences between Mn and In atoms, which is also present in Ni2Mn1+xIn1-x alloys. Further, a comparison of the calculations with experimental x-ray absorption fine structure at the Mn and Ni K edges in Mn2-yNi1.6+yIn0.4 (-0.08 ≤ y ≤ 0.08) indicates a strong connection between martensitic transformation and occupancy of Z sites by Mn atoms.

  2. Fluorescence x-ray absorption fine structure studies of Fe-Ni-S and Fe-Ni-Si melts to 1600 K

    SciTech Connect

    Manghnani, M.H.; Hong, X.; Balogh, J.; Amulele, G.; Sekar, M.; Newville, M.

    2008-04-29

    We report Ni K-edge fluorescence x-ray absorption fine structure spectra (XAFS) for Fe{sub 0.75}Ni{sub 0.05}S{sub 0.20} and Fe{sub 0.75}Ni{sub 0.05}Si{sub 0.20} ternary alloys from room temperature up to 1600 K. A high-temperature furnace designed for these studies incorporates two x-ray transparent windows and enables both a vertical orientation of the molten sample and a wide opening angle, so that XAFS can be measured in the fluorescence mode with a detector at 90{sup o} with respect to the incident x-ray beam. An analysis of the Ni XAFS data for these two alloys indicates different local structural environments for Ni in Fe{sub 0.75}Ni{sub 0.05}S{sub 0.20} and Fe{sub 0.75}Ni{sub 0.05}Si{sub 0.20} melts, with more Ni-Si coordination than Ni-S coordination persisting from room temperature through melting. These results suggest that light elements such as S and Si may impact the structural and chemical properties of Fe-Ni alloys with a composition similar to the earth's core.

  3. X-ray absorption fine structure (XAFS) studies of copper (II) mixed ligand complexes having tetramethylethylenediamine as one of the ligands

    NASA Astrophysics Data System (ADS)

    Sharma, Sharad; Joshi, S. K.; Shrivastava, B. D.; Hinge, V. K.; Prasad, J.; Srivastava, K.

    2014-09-01

    X-ray absorption fine structure (XAFS) has been studied at the K-edge of copper in copper(II) mixed ligand complexes, having tetramethylethylenediamine (tmen) as one of the ligands, viz., Cu(tmen)(gly)ClO4, Cu(tmen)(bipy)(ClO4)2 and Cu(tmen)(phen)(ClO4)2. The spectra have been recorded at the dispersive XAFS beamline (BL-8) at the 2.5 GeV INDUS-2 synchrotron, RRCAT, Indore, India. The data obtained has been processed and analyzed using the computer program Athena. It has been observed that K-edge has been found to split in two edges, K and K', in each of the complex. The chemical shift has been utilized to determine the oxidation state of copper in the complexes and also the effective nuclear charge (ENC). The EXAFS data has been analyzed to obtain the bond lengths in the complexes using Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. The first peak in the Fourier transform of the spectra gives the value of first shell phase uncorrected bond length. The results obtained from the Fourier transformation and LSS methods are in good agreement.

  4. Near-edge X-ray Absorption Fine Structure (NEXAFS) Spectroscopy study on Chlorinated Graphene through Plasma-based Surface Functionalization

    NASA Astrophysics Data System (ADS)

    Zhang, Xu; Schiros, Theanne; Nordlund, Dennis; Shin, Yong Cheol; Kong, Jing; Dresselhaus, Mildred; Palacios, Tomas; MIT/Columbia University/SLAC Collaboration

    2015-03-01

    Plasma-based chlorination is a promising technique to realize controllable doping in graphene, while maintaining its high mobility. Meanwhile, synchrotron-based X-ray spectroscopy provides us a sensitive probe to investigate the surface states of functionalizing dopants in graphene. Here, we systematically studied the electronic states of chlorinated graphene on different substrates, including surface binding energy, dopant concentration and work function shift by use of Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, XPS and photoemission threshold measurements. The concentration of absorbed chlorine is high enough to generate a distinct NEXAFS resonance at 286.2 eV (1s -> π* transition for C-Cl bonds). It is remarkable that the sp2 carbon core-hole exciton (291.85eV) retained its sharpness even after treatment, indicating the long-range periodicity in graphene is largely preserved. This distinguishes our approach as a noninvasive and effective doping method. The interaction between Cl and graphene also exhibits strong substrate effects: for Cu, graphene's Fermi level is shifted downwards by 0.35eV, while for graphene on SiO2, the much (4-5 times) higher chlorine concentration causes EF to shift by 0.9eV.

  5. Insights from arsenate adsorption on rutile (110): grazing-incidence X-ray absorption fine structure spectroscopy and DFT+U study.

    PubMed

    Yan, Li; Hu, Shan; Duan, Jinming; Jing, Chuanyong

    2014-07-03

    Insights into the bonding of As(V) at the metal oxide/aqueous interface can further our understanding of its fate and transport in the environment. The motivation of this work is to explore the interfacial configuration of As(V) on single crystal rutile (110) using grazing-incidence X-ray absorption fine structure spectroscopy (GI-XAFS) and planewave density functional calculations with on-site repulsion (DFT+U). In contrast to the commonly considered corner-sharing bidentate binuclear structure, tetrahedral As(V) binds as an edge/corner-sharing tridentate binuclear complex on rutile (110), as evidenced by observation of three As-Ti distances at 2.83, 3.36, and 4.05 Å. In agreement with the GI-XAFS analysis, our DFT+U calculations for this configuration resulted in the lowest adsorption energy among five possible alternatives. In addition, the electron density difference further demonstrated the transfer of charge between surface Ti atoms and O atoms in AsO4. This charge transfer consequently induced the formation of a chemical bond, which is also confirmed by the partial density of states analysis. Our results may shed new light on coupling the GI-XAFS and DFT approaches to explore molecular-scale adsorption mechanisms on single crystal surfaces.

  6. PRELIMINARY IN-SITU X-RAY ABSORPTION FINE STRUCTURE EXAMINATION OF PT/C AND PTCO/C CATHODE CATALYSTS IN AN OPERATIONAL POLYMER ELECTROLYTE FUEL CELL

    SciTech Connect

    Phelan, B.T.; Myers, D.J.; Smith, M.C.

    2009-01-01

    State-of-the-art polymer electrolyte fuel cells require a conditioning period to reach optimized cell performance. There is insuffi cient understanding about the behavior of catalysts during this period, especially with regard to the changing environment of the cathode electrocatalyst, which is typically Pt nanoparticles supported on high surface area Vulcan XC-72 carbon (Pt/C). The purpose of this research was to record preliminary observations of the changing environment during the conditioning phase using X-Ray Absorption Fine Structure (XAFS) spectroscopy. XAFS was recorded for a Pt/C cathode at the Pt L3-edge and a PtCo/C cathode at both the Pt L3-edge and Co K-edge. Using precision machined graphite cell-blocks, both transmission and fl uorescence data were recorded at Sector 12-BM-B of Argonne National Laboratory’s Advanced Photon Source. The fl uorescence and transmission edge steps allow for a working description of the changing electrocatalyst environment, especially water concentration, at the anode and cathode as functions of operating parameters. These features are discussed in the context of how future analysis may correlate with potential, current and changing apparent thickness of the membrane electrode assembly through loss of catalyst materials (anode, cathode, carbon support). Such direct knowledge of the effect of the conditioning protocol on the electrocatalyst may lead to better catalyst design. In turn, this may lead to minimizing, or even eliminating, the conditioning period.

  7. Near-Edge X-ray Absorption Fine Structure Studies of Electrospun Poly(dimethylsiloxane)/Poly (methyl methacrylate)/Multiwall Carbon Nanotube Composites

    PubMed Central

    Winter, A. Douglas; Larios, Eduardo; Alamgir, Faisal M.; Jaye, Cherno; Fischer, Daniel; Campo, Eva M.

    2014-01-01

    This work describes the near conduction band edge structure of electrospun mats of MWCNT-PDMS-PMMA by near edge X-Ray absorption fine structure (NEXAFS) spectroscopy. Effects of adding nanofillers of different sizes were addressed. Despite observed morphological variations and inhomogeneous carbon nanotube distribution, spun mats appeared homogeneous under NEXAFS analysis. Spectra revealed differences in emissions from glancing and normal spectra; which may evidence phase separation within the bulk of the micron-size fibers. Further, dichroic ratios show polymer chains did not align, even in the presence of nanofillers. Addition of nanofillers affected emissions in the C-H, C=O and C-C regimes, suggesting their involvement in interfacial matrix-carbon nanotube bonding. Spectral differences at glancing angles between pristine and composite mats suggest that geometric conformational configurations are taking place between polymeric chains and carbon nanotubes. These differences appear to be carbon nanotube-dimension dependent, and are promoted upon room temperature mixing and shear flow during electrospinning. CH-π bonding between polymer chains and graphitic walls, as well as H-bonds between impurities in the as-grown CNTs and polymer pendant groups are proposed bonding mechanisms promoting matrix conformation. PMID:24308286

  8. Solving the Structure of Reaction Intermediates by Time-Resolved Synchrotron X-ray Absorption Spectroscopy

    SciTech Connect

    Wang, Q.; Hanson, J; Frenkel, A

    2008-01-01

    We present a robust data analysis method of time-resolved x-ray absorption spectroscopy experiments suitable for chemical speciation and structure determination of reaction intermediates. Chemical speciation is done by principal component analysis (PCA) of the time-resolved x-ray absorption near-edge structure data. Structural analysis of intermediate phases is done by theoretical modeling of their extended x-ray absorption fine-structure data isolated by PCA. The method is demonstrated using reduction and reoxidation of Cu-doped ceria catalysts where we detected reaction intermediates and measured fine details of the reaction kinetics. This approach can be directly adapted to many time-resolved x-ray spectroscopy experiments where new rapid throughput data collection and analysis methods are needed.

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

    SciTech Connect

    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.

  10. Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C{sub 6}-ring-containing molecules

    SciTech Connect

    Kolczewski, C.; Puettner, R.; Martins, M.; Schlachter, A.S.; Snell, G.; Sant'Anna, M.M.; Hermann, K.; Kaindl, G.

    2006-01-21

    We report high-resolution C 1s near-edge x-ray-absorption fine-structure (NEXAFS) spectra of the C{sub 6}-ring-containing molecules benzene (C{sub 6}H{sub 6}), 1,3- and 1,4-cyclohexadiene (C{sub 6}H{sub 8}), cyclohexene (C{sub 6}H{sub 10}), cyclohexane (C{sub 6}H{sub 12}), styrene (C{sub 8}H{sub 8}), and ethylbenzene (C{sub 8}H{sub 10}) which allow us to examine the gradual development of delocalization of the corresponding {pi} electron systems. Due to the high experimental resolution, vibrational progressions can be partly resolved in the spectra. The experimental spectra are compared with theoretical NEXAFS spectra obtained from density-functional theory calculations where electronic final-state relaxation is accounted for. The comparison yields very good agreement between theoretical spectra and experimental results. In all cases, the spectra can be described by excitations to {pi}*- and {sigma}*-type final-state orbitals with valence character, while final-state orbitals of Rydberg character make only minor contributions. The lowest C 1s{yields}1{pi}* excitation energy is found to agree in the (experimental and theoretical) spectra of all molecules except for 1,3-cyclohexadiene (C{sub 6}H{sub 8}) where an energy smaller by about 0.6 eV is obtained. The theoretical analysis can explain this result by different binding properties of this molecule compared to the others.

  11. Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy for mapping nano-scale distribution of organic carbon forms in soil: Application to black carbon particles

    NASA Astrophysics Data System (ADS)

    Lehmann, Johannes; Liang, Biqing; Solomon, Dawit; Lerotic, Mirna; LuizãO, Flavio; Kinyangi, James; SchäFer, Thorsten; Wirick, Sue; Jacobsen, Chris

    2005-03-01

    Small-scale heterogeneity of organic carbon (C) forms in soils is poorly quantified since appropriate analytical techniques were not available up to now. Specifically, tools for the identification of functional groups on the surface of micrometer-sized black C particles were not available up to now. Scanning Transmission X-ray Microscopy (STXM) using synchrotron radiation was used in conjunction with Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy to investigate nano-scale distribution (50-nm resolution) of C forms in black C particles and compared to synchrotron-based FTIR spectroscopy. A new embedding technique was developed that did not build on a C-based embedding medium and did not pose the risk of heat damage to the sample. Elemental sulfur (S) was melted to 220°C until it polymerized and quenched with liquid N2 to obtain a very viscous plastic S in which the black C could be embedded until it hardened to a noncrystalline state and was ultrasectioned. Principal component and cluster analysis followed by singular value decomposition was able to resolve distinct areas in a black carbon particle. The core of the studied biomass-derived black C particles was highly aromatic even after thousands of years of exposure in soil and resembled the spectral characteristics of fresh charcoal. Surrounding this core and on the surface of the black C particle, however, much larger proportions of carboxylic and phenolic C forms were identified that were spatially and structurally distinct from the core of the particle. Cluster analysis provided evidence for both oxidation of the black C particle itself as well as adsorption of non-black C. NEXAFS spectroscopy has great potential to allow new insight into black C properties with important implications for biogeochemical cycles such as mineralization of black C in soils and sediments, and adsorption of C, nutrients, and pollutants as well as transport in the geosphere, hydrosphere, and atmosphere.

  12. Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection–Absorption Spectroscopy, Near-Edge X-ray Absorption Fine Structure, and Density Functional Theory Studies

    PubMed Central

    2014-01-01

    Atomistic level understanding of interaction of α,β-unsaturated carbonyls with late transition metals is a key prerequisite for rational design of new catalytic materials with the desired selectivity toward C=C or C=O bond hydrogenation. The interaction of this class of compounds with transition metals was investigated on α,β-unsaturated ketone isophorone on Pd(111) as a prototypical system. In this study, infrared reflection–absorption spectroscopy (IRAS), near-edge X-ray absorption fine structure (NEXAFS) experiments, and density functional theory calculations including van der Waals interactions (DFT+vdW) were combined to obtain detailed information on the binding of isophorone to palladium at different coverages and on the effect of preadsorbed hydrogen on the binding and adsorption geometry. According to these experimental observations and the results of theoretical calculations, isophorone adsorbs on Pd(111) in a flat-lying geometry at low coverages. With increasing coverage, both C=C and C=O bonds of isophorone tilt with respect to the surface plane. The tilting is considerably more pronounced for the C=C bond on the pristine Pd(111) surface, indicating a prominent perturbation and structural distortion of the conjugated π system upon interaction with Pd. Preadsorbed hydrogen leads to higher tilting angles of both π bonds, which points to much weaker interaction of isophorone with hydrogen-precovered Pd and suggests the conservation of the in-plane geometry of the conjugated π system. The results of the DFT+vdW calculations provide further insights into the perturbation of the molecular structure of isophorone on Pd(111). PMID:26089998

  13. Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection-Absorption Spectroscopy, Near-Edge X-ray Absorption Fine Structure, and Density Functional Theory Studies.

    PubMed

    Dostert, Karl-Heinz; O'Brien, Casey P; Riedel, Wiebke; Savara, Aditya; Liu, Wei; Oehzelt, Martin; Tkatchenko, Alexandre; Schauermann, Swetlana

    2014-12-04

    Atomistic level understanding of interaction of α,β-unsaturated carbonyls with late transition metals is a key prerequisite for rational design of new catalytic materials with the desired selectivity toward C=C or C=O bond hydrogenation. The interaction of this class of compounds with transition metals was investigated on α,β-unsaturated ketone isophorone on Pd(111) as a prototypical system. In this study, infrared reflection-absorption spectroscopy (IRAS), near-edge X-ray absorption fine structure (NEXAFS) experiments, and density functional theory calculations including van der Waals interactions (DFT+vdW) were combined to obtain detailed information on the binding of isophorone to palladium at different coverages and on the effect of preadsorbed hydrogen on the binding and adsorption geometry. According to these experimental observations and the results of theoretical calculations, isophorone adsorbs on Pd(111) in a flat-lying geometry at low coverages. With increasing coverage, both C=C and C=O bonds of isophorone tilt with respect to the surface plane. The tilting is considerably more pronounced for the C=C bond on the pristine Pd(111) surface, indicating a prominent perturbation and structural distortion of the conjugated π system upon interaction with Pd. Preadsorbed hydrogen leads to higher tilting angles of both π bonds, which points to much weaker interaction of isophorone with hydrogen-precovered Pd and suggests the conservation of the in-plane geometry of the conjugated π system. The results of the DFT+vdW calculations provide further insights into the perturbation of the molecular structure of isophorone on Pd(111).

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

    SciTech Connect

    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.

  15. Near-Edge X-ray Absorption Fine Structure Imaging of Spherical and Flat Counterfaces of Ultrananocrystalline Diamond Tribological Contacts: A Correlation of Surface Chemistry and Friction

    SciTech Connect

    A Konicek; C Jaye; M Hamilton; W Sawyer; D Fischer; R Carpick

    2011-12-31

    A recently installed synchrotron radiation near-edge X-ray absorption fine structure (NEXAFS) full field imaging electron spectrometer was used to spatially resolve the chemical changes of both counterfaces from an ultra-nanocrystalline diamond (UNCD) tribological contact. A silicon flat and Si{sub 3}N{sub 4} sphere were both coated with UNCD, and employed to form two wear tracks on the flat in a linear reciprocating tribometer. The first wear track was produced using a new, unconditioned sphere whose surface was thus conditioned during this first experiment. This led to faster run-in and lower friction when producing a second wear track using the conditioned sphere. The large depth of field of the magnetically guided NEXAFS imaging detector enabled rapid, large area spectromicroscopic imaging of both the spherical and flat surfaces. Laterally resolved NEXAFS data from the tribological contact area revealed that both substrates had an as-grown surface layer that contained a higher fraction of sp{sup 2}-bonded carbon and oxygen which was mechanically removed. Unlike the flat, the film on the sphere showed evidence of having graphitic character, both before and after sliding. These results show that the graphitic character of the sphere is not solely responsible for low friction and short run-in. Rather, conditioning the sphere, likely by removing asperities and passivating dangling bonds, leads to lower friction with less chemical modification of the substrate in subsequent tests. The new NEXAFS imaging spectroscopy detector enabled a more complete understanding of the tribological phenomena by imaging, for the first time, the surface chemistry of the spherical counterface which had been in continual contact during wear track formation.

  16. Vanadium K-edge X-ray absorption spectroscopy of bromoperoxidase from Ascophyllum nodosum

    SciTech Connect

    Arber, J.M.; de Boer, E.; Garner, C.D.; Hasnain, S.S.; Wever, R. )

    1989-09-19

    Bromoperoxidase from Ascophyllum nodusum was the first vanadium-containing enzyme to be isolated. X-ray absorption spectra have now been collected in order to investigate the coordination of vanadium in the native, native plus bromide, native plus hydrogen peroxide, and dithionite-reduced forms of the enzyme. The edge and X-ray absorption near-edge structures show that, in the four samples studied, it is only on reduction of the native enzyme that the metal site is substantially altered. In addition, these data are consistent with the presence of vanadium(IV) in the reduced enzyme and vanadium(V) in the other samples. Extended X-ray absorption fine structure data confirm that there are structural changes at the metal site on reduction of the native enzyme, notably a lengthening of the average inner-shell distance, and the presence of terminal oxygen together with histidine and oxygen-donating residues.

  17. Structural characterization of poorly-crystalline scorodite, iron(III)-arsenate co-precipitates and uranium mill neutralized raffinate solids using X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, N.; Jiang, D. T.; Cutler, J.; Kotzer, T.; Jia, Y. F.; Demopoulos, G. P.; Rowson, J. W.

    2009-06-01

    X-ray absorption fine structure (XAFS) is used to characterize the mineralogy of the iron(III)-arsenate(V) precipitates produced during the raffinate (aqueous effluent) neutralization process at the McClean Lake uranium mill in northern Saskatchewan, Canada. To facilitate the structural characterization of the precipitated solids derived from the neutralized raffinate, a set of reference compounds were synthesized and analyzed. The reference compounds include crystalline scorodite, poorly-crystalline scorodite, iron(III)-arsenate co-precipitates obtained under different pH conditions, and arsenate-adsorbed on goethite. The poorly-crystalline scorodite (prepared at pH 4 with Fe/As = 1) has similar As local structure as that of crystalline scorodite. Both As and Fe K-edge XAFS of poorly-crystalline scorodite yield consistent results on As-Fe (or Fe-As) shell. From As K-edge analysis the As-Fe shell has an inter-atomic distance of 3.33 ± 0.02 Å and coordination number of 3.2; while from Fe K-edge analysis the Fe-As distance and coordination number are 3.31 ± 0.02 Å and 3.8, respectively. These are in contrast with the typical arsenate adsorption on bidentate binuclear sites on goethite surfaces, where the As-Fe distance is 3.26 ± 0.03 Å and coordination number is close to 2. A similar local structure identified in the poorly-crystalline scorodite is also found in co-precipitation solids (Fe(III)/As(V) = 3) when precipitated at the same pH (pH = 4): As-Fe distance 3.30 ± 0.03 Å and coordination number 3.9; while at pH = 8 the co-precipitate has As-Fe distance of 3.27 ± 0.03 Å and coordination number about 2, resembling more closely the adsorption case. The As local structure in the two neutralized raffinate solid series (precipitated at pH values up to 7) closely resembles that in the poorly-crystalline scorodite. All of the raffinate solids have the same As-Fe inter-atomic distance as that in the poorly-crystalline scorodite, and a systematic decrease in the

  18. Refinement of DNA structures through near-edge X-ray absorption fine structure analysis: applications on guanine and cytosine nucleobases, nucleosides, and nucleotides.

    PubMed

    Hua, Weijie; Gao, Bin; Li, Shuhua; Agren, Hans; Luo, Yi

    2010-10-21

    In this work we highlight the potential of NEXAFS—near-edge X-ray absorption fine structure—analysis to perform refinements of hydrogen-bond structure in DNA. For this purpose we have carried out first-principle calculations of the N1s NEXAFS spectra of the guanine and cytosine nucleobases and their tautomers, nucleosides, and nucleotides in the gas phase, as well as for five crystal structures of guanine, cytosine, or guanosine. The spectra all clearly show imine (π1*) and amine (π2*) nitrogen absorption bands with a characteristic energy difference (Δ). Among all of the intramolecule covalent connections, the tautomerism of hydrogens makes the largest influence, around ±0.4−0.5 eV change of Δ, to the spectra due to a switch of single−double bonds. Deoxyribose and ribose sugars can cause at most 0.2 eV narrowing of Δ, while the phosphate groups have nearly negligible effects on the spectra. Two kinds of intermolecule interactions are analyzed, the hydrogen bonds and the stacking effect, by comparing “compressed” and “expanded” models or by comparing models including or excluding the nearest stacking molecules. The shortening of hydrogen-bond length by 0.2−0.3 Å can result in the reduction of Δ by 0.2−0.8 eV. This is because the hydrogen bonds make the electrons more delocalized, and the amine and imine nitrogens become less distinguishable. Moreover, the hydrogen bond has a different ability to influence the spectra of different crystals, with guanine crystals as the largest (change by 0.8 eV) and the guanosine crystal as the smallest (change by 0.2 eV). The stacking has negligible effects on the spectra in all studied systems. A comparison of guanosine to guanine crystals shows that the sugars in the crystal could create “blocks” in the π-and hydrogen bonds network of bases and thus makes the imine and amine nitrogens more distinguishable with a larger Δ. Our theoretical calculations offer a good match with experimental findings

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

    SciTech Connect

    Willey, Trevor M.

    2004-04-01

    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 mechanically attached

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

    PubMed

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

    2011-05-12

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

  1. Antimony(III) complexing with O-bearing organic ligands in aqueous solution: An X-ray absorption fine structure spectroscopy and solubility study

    NASA Astrophysics Data System (ADS)

    Tella, Marie; Pokrovski, Gleb S.

    2009-01-01

    The stability and structure of aqueous complexes formed by trivalent antimony (Sb III) with carboxylic acids (acetic, adipic, malonic, lactic, oxalic, tartaric, and citric acid), phenols (catechol), and amino acids (glycine) having O- and N-functional groups (carboxyl, alcoholic hydroxyl, phenolic hydroxyl and amine) typical of natural organic matter, were determined at 20 and 60 °C from solubility and X-ray absorption fine structure (XAFS) spectroscopy measurements. In organic-free aqueous solutions and in the presence of acetic, adipic, malonic acids and glycine, both spectroscopic and solubility data are consistent with the dominant formation of Sb III hydroxide species, Sb(OH)3-nn+,Sb(OH)30andSb(OH)4-, at strongly acid, acid-to-neutral and basic pH, respectively, demonstrating negligible complexing with mono-functional organic ligands (acetic) or those having non adjacent carboxylic groups (adipic, malonic). In contrast, in the presence of poly-functional carboxylic and hydroxy-carboxylic acids and catechol, Sb III forms stable 1:1 and 1:2 complexes with the studied organic ligands over a wide pH range typical of natural waters (3 < pH < 9). XAFS spectroscopy measurements show that in these species the central Sb III atom has a distorted pseudo-trigonal pyramidal geometry composed of the lone pair of 5s 2 electrons of Sb and four oxygen atoms from two adjacent functional groups of the ligand (O dbnd C-OH and/or C sbnd OH), forming a five-membered bidendate chelate cycle. Stability constants for these species, generated from Sb 2O 3 (rhomb.) solubility experiments, were used to model Sb complexing with natural humic acids possessing the same functional groups as those investigated in this study. Our predictions show that in an aqueous solution of pH between 2 and 10, containing 1 μg/L of Sb and 5 mg/L of dissolved organic carbon (DOC), up to 35% of total dissolved Sb binds to aqueous organic matter via carboxylic and hydroxy-carboxylic groups. This amount of

  2. In Situ X-ray Absorption Fine Structure Studies on the Effect of pH on Pt Electronic Density during Aqueous Phase Reforming of Glycerol

    SciTech Connect

    Karim, Ayman M.; Howard, Christopher J.; Roberts, Benjamin Q.; Kovarik, Libor; Zhang, Liang; King, David L.; Wang, Yong

    2012-10-30

    In situ x-ray absorption spectroscopy (XAS) results on correlating the Pt local coordination and electronic structure with the Pt/C catalyst activity and selectivity during aqueous reforming of glycerol at different pH are reported. The results show that both low and high pH favor C-O cleavage over that of C-C. However, the selectivity towards C-O bond cleavage was higher under the acidic conditions. XANES measurements under reaction conditions showed that low pH increased the Pt electron density while the effect of basic conditions was minimal. ΔXANES was used to estimate the coverage of adsorbates under reaction conditions and the results suggest a change in the adsorbates coverage by the acidic conditions, resulting in higher electron density on Pt

  3. Picosecond and femtosecond X-ray absorption spectroscopy of molecular systems.

    PubMed

    Chergui, Majed

    2010-03-01

    The need to visualize molecular structure in the course of a chemical reaction, a phase transformation or a biological function has been a dream of scientists for decades. The development of time-resolved X-ray and electron-based methods is making this true. X-ray absorption spectroscopy is ideal for the study of structural dynamics in liquids, because it can be implemented in amorphous media. Furthermore, it is chemically selective. Using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) in laser pump/X-ray probe experiments allows the retrieval of the local geometric structure of the system under study, but also the underlying photoinduced electronic structure changes that drive the structural dynamics. Recent developments in picosecond and femtosecond X-ray absorption spectroscopy applied to molecular systems in solution are reviewed: examples on ultrafast photoinduced processes such as intramolecular electron transfer, low-to-high spin change, and bond formation are presented.

  4. An x-ray absorption spectroscopy study of Mo oxidation in Pb at elevated temperatures

    SciTech Connect

    Liu, Shanshan; Olive, Daniel; Terry, Jeff; Segre, Carlo U.

    2009-06-30

    The corrosion of fuel cladding and structural materials by lead and lead-bismuth eutectic in the liquid state at elevated temperatures is an issue that must be considered when designing advanced nuclear systems and high-power spallation neutron targets. In this work, lead corrosion studies of molybdenum were performed to investigate the interaction layer as a function of temperature by X-ray absorption spectroscopy. In situ X-ray absorption measurements on a Mo substrate with a 3-6 {micro}m layer of Pb deposited by thermal evaporation were performed at temperatures up to 900 C and at a 15{sup o} angle to the incident X-rays. The changes in the local atomic structure of the corrosion layer are visible in the difference extended X-ray absorption fine structure and the linear combination fitting of the X-ray absorption near-edge structure to as-deposited molybdenum sample and molybdenum oxide (MoO{sub 2} and MoO{sub 3}) standards. The data are consistent with the appearance of MoO{sub 3} in an intermediate temperature range (650-800 C) and the more stable MoO{sub 2} phase dominating at high and low temperatures.

  5. X-ray absorption studies of battery materials

    SciTech Connect

    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.

  6. Structural determination of a short-lived excited iron(II) complex by picosecond x-ray absorption spectroscopy.

    PubMed

    Gawelda, Wojciech; Pham, Van-Thai; Benfatto, Maurizio; Zaushitsyn, Yuri; Kaiser, Maik; Grolimund, Daniel; Johnson, Steven L; Abela, Rafael; Hauser, Andreas; Bressler, Christian; Chergui, Majed

    2007-02-02

    Structural changes of the iron(II)-tris-bipyridine ([Fe(II)(bpy)(3)](2+)) complex induced by ultrashort pulse excitation and population of its short-lived (< or =0.6 ns) quintet high spin state have been detected by picosecond x-ray absorption spectroscopy. The structural relaxation from the high spin to the low spin state was followed over the entire lifetime of the excited state. A combined analysis of the x-ray-absorption near-edge structure and extended x-ray-absorption fine structure spectroscopy features delivers an Fe-N bond elongation of 0.2 A in the quintet state compared to the singlet ground state.

  7. Tin Oxide Crystals Exposed by Low-Energy {110} Facets for Enhanced Electrochemical Heavy Metal Ions Sensing: X-ray Absorption Fine Structure Experimental Combined with Density-Functional Theory Evidence.

    PubMed

    Jin, Zhen; Yang, Meng; Chen, Shao-Hua; Liu, Jin-Huai; Li, Qun-Xiang; Huang, Xing-Jiu

    2017-02-21

    Herein, we revealed that the electrochemical behaviors on the detection of heavy metal ions (HMIs) would largely rely on the exposed facets of SnO2 nanoparticles. Compared to the high-energy {221} facet, the low-energy {110} facet of SnO2 possessed better electrochemical performance. The adsorption/desorption tests, density-functional theory (DFT) calculations, and X-ray absorption fine structure (XAFS) studies showed that the lower barrier energy of surface diffusion on {110} facet was critical for the superior electrochemical property, which was favorable for the ions diffusion on the electrode, and further leading the enhanced electrochemical performance. Through the combination of experiments and theoretical calculations, a reliable interpretation of the mechanism for electroanalysis of HMIs with nanomaterials exposed by different crystal facets has been provided. Furthermore, it provides a deep insight into understanding the key factor to improve the electrochemical performance for HMIs detection, so as to design high-performance electrochemical sensors.

  8. Confocal micrometer-scale X-ray fluorescence and X-ray absorption fine structure studies of uranium speciation in a tertiary sediment from a waste disposal natural analogue site.

    PubMed

    Denecke, Melissa A; Janssens, Koen; Proost, Kristof; Rothe, Jörg; Noseck, Ulrich

    2005-04-01

    Investigations by micrometer-scale X-ray fluorescence and X-ray absorption fine structure (micro-XRF and micro-XAFS) recorded in a confocal geometry on a bore core section of a uranium-rich tertiary sediment are performed in order to assess mechanisms leading to immobilization of the uranium during diagenesis. Results show uranium to be present as a tetravalent phosphate and that U(IV) is associated with As(V). Arsenic present is either As(V) or As(O); we found no evidence for As(III). The As(O) is observed to be intimately associated with the surface of Fe(II) nodules and likely arsenopyrite. A hypothesis for the mechanism of uranium immobilization is proposed, where arsenopyrite acted as reductant of groundwater-dissolved U(VI), leading to precipitation of less soluble U(IV) and thereby forming As(V).

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

    NASA Astrophysics Data System (ADS)

    Cutler, J. N.; Chen, N.; Jiang, D. T.; Demopoulos, G. P.; Jia, Y.; Rowson, J. W.

    2003-05-01

    In order to understand the evolving world of environmental issues, the ability to characterize and predict the stability and bioavailability of heavy métal 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.

  10. X-ray absorption spectroscopic studies of mononuclear non-heme iron enzymes

    SciTech Connect

    Westre, Tami E.

    1996-01-01

    Fe-K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the electronic and geometric structure of the iron active site in non-heme iron enzymes. A new theoretical extended X-ray absorption fine structure (EXAFS) analysis approach, called GNXAS, has been tested on data for iron model complexes to evaluate the utility and reliability of this new technique, especially with respect to the effects of multiple-scattering. In addition, a detailed analysis of the 1s→3d pre-edge feature has been developed as a tool for investigating the oxidation state, spin state, and geometry of iron sites. Edge and EXAFS analyses have then been applied to the study of non-heme iron enzyme active sites.

  11. Dimerization of single selenium chains confined in nanochannels of cancrinite: An x-ray absorption study

    NASA Astrophysics Data System (ADS)

    Kolobov, A. V.; Oyanagi, H.; Poborchii, V. V.; Tanaka, K.

    1999-04-01

    Local structure of selenium confined in nanochannels of cancrinite (Can-Se) single crystal and powder samples have been studied by polarized x-ray absorption. The spectra for a single crystal are strongly anisotropic implying linear arrangement of Se species. Polarization dependence of extended x-ray absorption fine structure (EXAFS) data provides direct evidence that dimers with the bond length of 2.40+/-0.01 Å are formed. Polarized x-ray absorption near-edge structure (XANES) spectra demonstrate that they are aligned along the channel of cancrinite. Deconvolution of XANES spectra into Lorentzians (localized states) and the remaining steplike function (continuous states) shows that two localized state peaks are present. While the one polarized parallel to the cancrinite axis is strongly polarized, the other one is essentially isotropic. Comparison of XANES peak positions for Can-Se with that for bulk selenium provides evidence for negative charge on dimers. Despite strong temperature dependence of Raman-scattering spectra found earlier, EXAFS data do not exhibit any noticeable temperature dependence. Possible mechanisms for dimer stabilization are discussed.

  12. X-RAY ABSORPTION SPECTROSCOPY OF YB3+-DOPED OPTICAL FIBERS

    SciTech Connect

    Citron, Robert; Kropf, A.J.

    2008-01-01

    Optical fibers doped with Ytterbium-3+ have become increasingly common in fiber lasers and amplifiers. Yb-doped fibers provide the capability to produce high power and short pulses at specific wavelengths, resulting in highly effective gain media. However, little is known about the local structure, distribution, and chemical coordination of Yb3+ in the fibers. This information is necessary to improve the manufacturing process and optical qualities of the fibers. Five fibers doped with Yb3+ were studied using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES), in addition to Yb3+ mapping. The Yb3+ distribution in each fiber core was mapped with 2D and 1D intensity scans, which measured X-ray fluorescence over the scan areas. Two of the five fibers examined showed highly irregular Yb3+ distributions in the core center. In four of the five fibers Yb3+ was detected outside of the given fiber core dimensions, suggesting possible Yb3+ diffusion from the core, manufacturing error, or both. X-ray absorption spectroscopy (XAS) analysis has so far proven inconclusive, but did show that the fibers had differing EXAFS spectra. The Yb3+ distribution mapping proved highly useful, but additional modeling and examination of fiber preforms must be conducted to improve XAS analysis, which has been shown to have great potential for the study of similar optical fi bers.

  13. X-ray absorption spectroscopic investigation of the electronic structure differences in solution and crystalline oxyhemoglobin

    PubMed Central

    Wilson, Samuel A.; Green, Evan; Mathews, Irimpan I.; Benfatto, Maurizio; Hodgson, Keith O.; Hedman, Britt; Sarangi, Ritimukta

    2013-01-01

    Hemoglobin (Hb) is the heme-containing O2 transport protein essential for life in all vertebrates. The resting high-spin (S = 2) ferrous form, deoxy-Hb, combines with triplet O2, forming diamagnetic (S = 0) oxy-Hb. Understanding this electronic structure is the key first step in understanding transition metal–O2 interaction. However, despite intense spectroscopic and theoretical studies, the electronic structure description of oxy-Hb remains elusive, with at least three different descriptions proposed by Pauling, Weiss, and McClure-Goddard, based on theory, spectroscopy, and crystallography. Here, a combination of X-ray absorption spectroscopy and extended X-ray absorption fine structure, supported by density functional theory calculations, help resolve this debate. X-ray absorption spectroscopy data on solution and crystalline oxy-Hb indicate both geometric and electronic structure differences suggesting that two of the previous descriptions are correct for the Fe–O2 center in oxy-Hb. These results support the multiconfigurational nature of the ground state developed by theoretical results. Additionally, it is shown here that small differences in hydrogen bonding and solvation effects can tune the ground state, tipping it into one of the two probable configurations. These data underscore the importance of solution spectroscopy and show that the electronic structure in the crystalline form may not always reflect the true ground-state description in solution. PMID:24062465

  14. Investigating the speciation of copper in secondary fly ash by X-ray absorption spectroscopy.

    PubMed

    Tian, Shulei; Yu, Meijuan; Wang, Wei; Wang, Qi; Wu, Ziyu

    2009-12-15

    Although some researchers have reported that chlorides may play an important part in the evaporation of copper during heat treatment of municipal solid waste incinerators (MSWI) fly ash (1, 2) , details on the copper speciation in volatile matters (secondary fly ash, SFA) are still lacking. In this work, we used in situ X-ray absorption spectroscopy (XAS) experiments involving three types of SFA, which was collected from a high-temperature tubular electric furnace by thermal treatment of municipal solid waste incinerator (MSWI) fly ash at 1000, 1150, and 1250 degrees C. The results obtained by a linear combination fit (LCF) of X-ray absorption near edge structure (XANES) spectra revealed that in MSWI fly ash copper mainly exists as CuO and CuSO(4).5H(2)O while chloride almost dominated all the content of the SFA conformation, which was more than 80%. Extended X-ray absorption fine structure (EXAFS) data analysis indicated the presence of both Cu-O and Cu-Cl bonds in the first coordination shell of Cu ions in all SFA, while only Cu-O bonds occur in the MSWI fly ash. Consequently, in the MSWI fly ash during heat treatment copper evaporated as chloride, and the latter plays an important role in the formation of copper chloride.

  15. Surface arsenic speciation of a drinking-water treatment residual using X-ray absorption spectroscopy.

    PubMed

    Makris, Konstantinos C; Sarkar, Dibyendu; Parsons, Jason G; Datta, Rupali; Gardea-Torresdey, Jorge L

    2007-07-15

    Drinking-water treatment residuals (WTRs) present a low-cost geosorbent for As-contaminated waters and soils. Previous work has demonstrated the high affinity of WTRs for As, but data pertaining to the stability of sorbed As is missing. Sorption/desorption and X-ray absorption spectroscopy (XAS), both XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) studies, were combined to determine the stability of As sorbed by an Fe-based WTR. Arsenic(V) and As(III) sorption kinetics were biphasic in nature, sorbing >90% of the initial added As (15,000 mg kg(-1)) after 48 h of reaction. Subsequent desorption experiments with a high P load (7500 mg kg(-1)) showed negligible As desorption for both As species, approximately <3.5% of sorbed As; the small amount of desorbed As was attributed to the abundance of sorption sites. XANES data showed that sorption kinetics for either As(III) or As(V) initially added to solution had no effect on the sorbed As oxidation state. EXAFS spectroscopy suggested that As added either as As(III) or as As(V) formed inner-sphere mononuclear, bidentate complexes, suggesting the stability of the sorbed As, which was further corroborated by the minimum As desorption from the Fe-WTR.

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

    NASA Astrophysics Data System (ADS)

    Zhao, W.; Chu, W. S.; Yang, F. F.; Yu, M. J.; Chen, D. L.; Guo, X. Y.; Zhou, D. W.; Shi, N.; Marcelli, A.; Niu, L. W.; Teng, M. K.; Gong, W. M.; Benfatto, M.; Wu, Z. Y.

    2007-09-01

    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.

  17. ODS steel raw material local structure analysis using X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Cintins, A.; Anspoks, A.; Purans, J.; Kuzmin, A.; Timoshenko, J.; Vladimirov, P.; Gräning, T.; Hoffmann, J.

    2015-03-01

    Oxide dispersion strengthened (ODS) steels are promising materials for fusion power reactors, concentrated solar power plants, jet engines, chemical reactors as well as for hydrogen production from thermolysis of water. In this study we used X-ray absorption spectroscopy at the Fe and Cr K-edges as a tool to get insight into the local structure of ferritic and austenitic ODS steels around Fe and Cr atoms and its transformation during mechanical alloying process. Using the analysis of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) we found that for austenitic samples a transformation of ferritic steel to austenitic steel is detectable after 10 hours of milling and proceeds till 40 hours of milling; only small amount of a-phase remains after 80 hours of milling. We found that the Cr K-edge EXAFS can be used to observe distortions inside the material and to get an impression on the formation of chromium clusters. In-situ EXAFS experiments offer a reliable method to investigate the ferritic to austenitic transformation.

  18. Analysis of the near-edge X-ray-absorption fine-structure of anthracene: A combined theoretical and experimental study

    SciTech Connect

    Klues, Michael; Witte, Gregor; Hermann, Klaus

    2014-01-07

    The near-edge fine structure of the carbon K-edge absorption spectrum of anthracene was measured and theoretically analyzed by density functional theory calculations implemented in the StoBe code. It is demonstrated that the consideration of electronic relaxation of excited states around localized core holes yields a significant improvement of the calculated excitation energies and reproduces the experimentally observed fine structure well. The detailed analysis of excitation spectra calculated for each symmetry inequivalent excitation center allows in particular to examine the influence of chemical shifts and core hole effects on the excitation energies. Moreover, the visualization of final states explains the large variations in the oscillator strength of various transitions as well as the nature of Rydberg-states that exhibit a notable density of states below the ionization potentials.

  19. Adsorption and stability of malonic acid on rutile TiO2 (110), studied by near edge X-ray absorption fine structure and photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Syres, Karen L.; Thomas, Andrew G.; Graham, Darren M.; Spencer, Ben F.; Flavell, Wendy R.; Jackman, Mark J.; Dhanak, Vinod R.

    2014-08-01

    The adsorption of malonic acid on rutile TiO2 (110) has been studied using photoelectron spectroscopy and C K-edge, near edge X-ray fine structure spectroscopy (NEXAFS). Analysis of the O 1s and Ti 2p spectra suggest that the molecule adsorbs dissociatively in a doubly-bidentate adsorption geometry as malonate. The data are unable to distinguish between a chelating bonding mode with the backbone of the molecule lying along the [001] azimuth or a bridging geometry along the direction. Work carried out on a wiggler beamline suggests that the molecule is unstable under irradiation by high-flux synchrotron radiation from this type of insertion device.

  20. Surface metallization on Si(001) at elevated temperatures studied by angle-resolved photoemission spectroscopy and near-edge x-ray absorption fine structure: Effect of thermal adatoms

    NASA Astrophysics Data System (ADS)

    Jeon, C.; Hwang, C. C.; Kang, T.-H.; Kim, K.-J.; Kim, B.; Kim, Y.; Noh, D. Y.; Park, C.-Y.

    2009-10-01

    We report the metallization of the Si(001)2×1 surface at elevated temperatures using angle-resolved photoemission spectroscopy (ARPES) and near-edge x-ray absorption fine structure (NEXAFS). A metallic state (Sm) over the EF , which corresponds to the empty (π∗) state of the 2×1 asymmetric dimer model, increases in the ARPES spectra, while the π∗ state decreases in the NEXAFS spectra with increasing temperature. Since Sm is observed even at 400 K, the structural phase transition at ˜900K [Phys. Rev. Lett. 91, 126103 (2003); Phys. Rev. Lett. 77, 3869 (1996)] is not related to the metallization. Thermal excitation seems to be too small to detect in ARPES in initial stage of the metallization and cannot account for the different behavior of Sm and the filled surface state of the up-dimer upon oxidation. We suggest, based on the existence of Sm even at 400 K and the oxidation behavior, that the metallization is attributed to thermal adatoms.

  1. Nondestructive Speciation Depth Profiling of Complex TiOx Nanolayer Structures by Grazing Incidence X-ray Fluorescence Analysis and Near Edge X-ray Absorption Fine Structure Spectroscopy.

    PubMed

    Pollakowski, Beatrix; Beckhoff, Burkhard

    2015-08-04

    An important challenge of modern material science is the depth-sensitive and nondestructive analysis of the chemical binding state of complex structures consisting of multiple thin layers. In general, the correlation of the material functionality and underlying chemical and physical properties is the key question in view of directed device development, performance, and quality control. It has been shown that the combined method grazing incidence X-ray fluorescence analysis (GIXRF) and near edge X-ray absorption fine structure spectroscopy (NEXAFS) can significantly contribute to the nondestructive chemical analysis of buried thin films and interface structures regarding chemical speciation. Recently, we have enhanced the method to allow for a depth-resolved analysis of multilayered nanoscaled thin film structures. By means of appropriate model systems, the methodology has been developed and successfully validated. The model systems basically consist of a carbon cap layer, two titanium layers differing in their oxidation states and separated by a thin carbon layer, and a silicon substrate covered with molybdenum and a carbon layer. A differential approach has been developed to derive the chemical species of each of the titanium layers.

  2. Interrogation of Surface, Skin, and Core Orientation in Thermotropic Liquid-Crystalline Copolyester Moldings by Near-Edge X-ray Absorption Fine Structure and Wide-Angle X-ray Scattering

    SciTech Connect

    Rendon,S.; Bubeck, R.; Thomas, L.; Burghardt, W.; Hexemer, A.; Fischer, D.

    2007-01-01

    Injection molding thermotropic liquid-crystalline polymers (TLCPs) usually results in the fabrication of molded articles that possess complex states of orientation that vary greatly as a function of thickness. 'Skin-core' morphologies are often observed in TLCP moldings. Given that both 'core' and 'skin' orientation states may often differ both in magnitude and direction, deconvolution of these complex orientation states requires a method to separately characterize molecular orientation in the surface region. A combination of two-dimensional wide-angle X-ray scattering (WAXS) in transmission and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is used to probe the molecular orientation in injection molded plaques fabricated from a 4,4'-dihydroxy-{alpha}-methylstilbene (DH{alpha}MS)-based thermotropic liquid crystalline copolyester. Partial electron yield (PEY) mode NEXAFS is a noninvasive ex situ characterization tool with exquisite surface sensitivity that samples to a depth of 2 nm. The effects of plaque geometry and injection molding processing conditions on surface orientation in the regions on- and off- axis to the centerline of injection molded plaques are presented and discussed. Quantitative comparisons are made between orientation parameters obtained by NEXAFS and those from 2D WAXS in transmission, which are dominated by the microstructure in the skin and core regions. Some qualitative comparisons are also made with 2D WAXS results from the literature.

  3. A high-resolution near-edge x-ray absorption fine structure investigation of the molecular orientation in the pentacene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) pentacene/system.

    PubMed

    Casu, M B; Cosseddu, P; Batchelor, D; Bonfiglio, A; Umbach, E

    2008-01-07

    We present x-ray photoemission spectroscopy and highly resolved near-edge x-ray absorption fine structure spectroscopy measurements taken on pentacene thin films of different thicknesses deposited on a spin coated poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) substrate. Thin films of pentacene were prepared by using organic molecular beam deposition in situ using strictly controlled evaporation conditions. Our investigations show that pentacene thin films on PEDOT:PSS are characterized by upright standing molecules. Due to the strong dichroic behavior, the calculated values of the molecular orientation give a clear indication not only of the real molecular arrangement in the films but also of a high orientational order. This high degree of molecular orientation order is a characteristic already of the first layer. The films show the tendency to grow on the PEDOT:PSS substrate following an island-fashion mode, with a relatively narrow intermixing zone at the interface between the pentacene and the polymer blend. The peculiarity of the growth of pentacene on PEDOT:PSS is due to the fact that the substrate does not offer any template for the nucleated films and thus exerts a lateral order toward the crystal structure arrangement. Under these conditions, the upright orientation of the molecules in the films minimizes the energy required for the system stability.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. In situ soft X-ray absorption spectroscopy of flames

    NASA Astrophysics Data System (ADS)

    Frank, Jonathan H.; Shavorskiy, Andrey; Bluhm, Hendrik; Coriton, Bruno; Huang, Erxiong; Osborn, David L.

    2014-10-01

    The feasibility of in situ soft X-ray absorption spectroscopy for imaging carbonaceous species in hydrocarbon flames is demonstrated using synchrotron radiation. Soft X-rays are absorbed by core level electrons in all carbon atoms regardless of their molecular structure. Core electron spectroscopy affords distinct advantages over valence spectroscopy, which forms the basis of traditional laser diagnostic techniques for combustion. In core level spectroscopy, the transition linewidths are predominantly determined by the instrument response function and the decay time of the core-hole, which is on the order of a femtosecond. As a result, soft X-ray absorption measurements can be performed in flames with negligible Doppler and collisional broadening. Core level spectroscopy has the further advantage of measuring all carbonaceous species regardless of molecular structure in the far-edge region, whereas near-edge features are molecule specific. Interferences from non-carbon flame species are unstructured and can be subtracted. In the present study, absorption measurements in the carbon K-edge region are demonstrated in low-pressure ( P total = 20-30 Torr) methane jet flames. Two-dimensional imaging of the major carbonaceous species, CH4, CO2, and CO, is accomplished by tuning the synchrotron radiation to the respective carbon K-edge, near-edge X-ray absorption fine structure (NEXAFS) transitions and scanning the burner.

  6. Electronic and lattice structures in SmFeAsO1-xFx probed by x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, C. J.; Oyanagi, H.; Sun, Z. H.; Kamihara, Y.; Hosono, H.

    2010-03-01

    Local lattice and electronic structures in the Fe-As layer of SmFeAsO1-xFx superconductors were studied by x-ray absorption spectroscopy, the FeK -edge and the AsK -edge extended x-ray absorption fine-structure, and x-ray absorption near-edge-structure experiments, respectively. Temperature-dependent local lattice distortions were observed in the Fe-As bond mean-square relative displacement of the superconducting samples. A strong coupling of the carrier-induced local lattice distortion (polaron) to the superconducting transition temperature in the oxypnictide superconductors is indicated. The near-edge spectra showed systematic temperature-dependent energy shifts, which indicate an intralayer electron redistribution from Fed states to Asp states due to orbital-selective band filling at low temperatures.

  7. Polarized Range-Extended X-Ray Absorption Spectroscopy of Oriented Photosystem II Membranes in the S[subscript 1] State

    SciTech Connect

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

    2007-11-13

    Detailed information about the orientation of particular Mn-Mn and Mn-Ca vectors in the oxygen evolving complex (OEC) of the Photosystem II in the S1 state provide a critical starting point for the analysis of the structural changes in the OEC along the catalytic S{sub i}-state cycle. The method of polarized range-extended EXAFS is an important technical development, that allows: (i) resolution of the 2.7 {angstrom} and 2.8 {angstrom} Mn-Mn interactions; (ii) resolution of 3.2 {angstrom} Mn-Mn and 3.4 {angstrom} Mn-Ca; (iii) determination of 2.7 {angstrom}, 2.8 {angstrom}, 3.2 {angstrom} Mn-Mn and 3.4 {angstrom} Mn-Ca vectors orientation relative to the membrane normal.

  8. Effect of Iron(II) on Arsenic Sequestration by δ-MnO2: Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy.

    PubMed

    Wu, Yun; Li, Wei; Sparks, Donald L

    2015-11-17

    Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO2) in the presence of Fe(II) prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO4(3-)) and calcium (Ca(2+)). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.

  9. Evolution of fcc Cu clusters and their structure changes in the soft magnetic Fe85.2Si1B9P4Cu0.8 (NANOMET) and FINEMET alloys observed by X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Matsuura, M.; Nishijima, M.; Takenaka, K.; Takeuchi, A.; Ofuchi, H.; Makino, A.

    2015-05-01

    It is known that Cu plays an essential role in reducing the grain size of precipitated bcc Fe(Si) nanocrystallites in a nanocrystalline soft-magnetic Fe85.2Si1B9P4Cu0.8 (NANOMET®) alloys like as an Fe73.5Si13.5B9Nb3Cu1 (FINEMET®). However, significant differences are there between two alloys; NANOMET has much higher iron content (˜85%) than FINEMET (73.5%) and the former contains P instead of Nb for the latter. In the present work, the local structure around Cu in FINEMET was measured by X-ray absorption fine structure (XAFS) at 20 K and compared with those of NANOMET during nanocrystallization. Definite differences between NANOMET and FINEMET are found in the way of the evolution of Cu clusters during nanocrystallization. In FINEMET, an fcc structure of Cu is recognized in an as-quenched ribbon indicating existence of a small number of Cu clusters or a very small size of Cu clusters which is stable up to 450 °C, while the fcc Cu clusters are developed rapidly above 450 °C. An fcc structure of the Cu clusters in FINEMET is retained all the way to the end of the nanocrystallization. On the contrary, for NANOMET the local structure around Cu changes in a sequence as "amorphous → fcc → bcc → fcc" by annealing. The reasons of such different behaviors of the local structure around Cu during nanocrystallization are discussed in terms of different contributions of Cu clusters in bcc Fe precipitation between FINEMET and NANOMET. A significantly fast crystallization process with an extraordinary large heat release can be another reason for the transition of the local structure around Cu from fcc to bcc for NANOMET.

  10. Retention of Nickel in Soils: Sorption-Desorption and Extended X-ray Absorption Fine Structure Experiments

    EPA Science Inventory

    Adsorption and desorption of heavy metals in soils are primary factors that influence their bioavailability and mobility in the soil profile. To examine the characteristics of nickel (Ni) adsorption-desorption in soils, kinetic batch experiments were carried out followed by Ni re...

  11. Local order in hydrogenated amorphous germanium thin films studied by extended x-ray absorption fine-structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Dalba, G.; Fornasini, P.; Grisenti, R.; Rocca, F.; Chambouleyron, I.; Graeff, C. F. O.

    1997-07-01

    The effect of hydrogenation on the local order in amorphous germanium has been studied by EXAFS. Measurements have been carried out on sputtered a-Ge:H films with hydrogen concentrations of 0, 7, 10, and 15 at.%, as a function of temperature in the range 11 - 300 K. The first-shell EXAFS data were analysed by the ratio method based on cumulant expansion. The asymmetric distributions reconstructed from cumulants are in very good agreement with a parametrized distribution obtained by other researchers using calculated phase-shifts. For the unhydrogenated a-Ge (deposited at 0953-8984/9/27/017/img7), increases of the interatomic distance, 0953-8984/9/27/017/img8 at 11 K, static disorder, 0953-8984/9/27/017/img9, and thermal disorder, 0953-8984/9/27/017/img10, have been found with respect to those for c-Ge. Both the static and the thermal disorder are smaller than for an evaporated sample (deposited at 0953-8984/9/27/017/img11) previously studied. The insertion of hydrogen in a-Ge produces a sharp reduction of the interatomic distance, static disorder, and asymmetry of the distribution already at the lowest H concentration (7%); then these parameters decrease almost linearly when the hydrogen content increases. No appreciable influence of hydrogenation on the thermal disorder has been detected.

  12. X-ray absorption and diffraction study of II VI dilute oxide semiconductor alloy epilayers

    NASA Astrophysics Data System (ADS)

    Boscherini, F.; Malvestuto, M.; Ciatto, G.; D'Acapito, F.; Bisognin, G.; DeSalvador, D.; Berti, M.; Felici, M.; Polimeni, A.; Nabetani, Y.

    2007-11-01

    Dilute oxide semiconductor alloys obtained by adding oxygen to a II-VI binary compound are of potential applicative interest for blue-light emitters in which the oxygen content could be used to tune the band gap. Moreover, their properties can be usefully compared to the more thoroughly studied dilute nitrides in order to gain insight into the common mechanisms which give rise to their highly non-linear physical properties. Recently, it has been possible to deposit ZnSeO and ZnSeOS epilayers on GaAs(001), which exhibit a red-shift of the band gap and giant optical bowing. In order to provide a structural basis for an understanding of their physical properties, we have performed a study of a set of ZnSeO and ZnSeOS epilayers on GaAs by high resolution x-ray diffraction and x-ray absorption fine structure. We have found that the strain goes from compressive to tensile with increasing O and S concentration and that, while all epilayers are never found to be pseudomorphic, the ternary ones exhibit a low relaxed fraction if compared to the ZnSe/GaAs sample. O K-edge x-ray absorption near edge spectra and corresponding simulations within the full multiple-scattering regime show that O is substitutionally incorporated in the host lattice. Zn and Se K-edge extended x-ray absorption fine structure detect the formation of Zn-O and Zn-S bonds; the analysis of these spectra within multiple-scattering theory has allowed us to measure the local structural parameters. The value of Zn-Se bond length is found to be in agreement with estimates based on models of local distortions in strained and relaxed epilayers; an increase of the mean-square relative displacement is detected at high O and S concentration and is related to both intrinsic and extrinsic factors.

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

    SciTech Connect

    Yadav, Ashok Kumar; Jha, S. N.; Bhattacharyya, D.; Haque, Sk Maidul; Shukla, Dinesh; Choudhary, Ram Janay

    2015-11-15

    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 L{sub 2,3} 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.

  14. X-ray Absorption Spectroscopy Characterization of Electrochemical Processes in Renewable Energy Storage and Conversion Devices

    SciTech Connect

    Farmand, Maryam

    2013-05-19

    The development of better energy conversion and storage devices, such as fuel cells and batteries, is crucial for reduction of our global carbon footprint and improving the quality of the air we breathe. However, both of these technologies face important challenges. The development of lower cost and better electrode materials, which are more durable and allow more control over the electrochemical reactions occurring at the electrode/electrolyte interface, is perhaps most important for meeting these challenges. Hence, full characterization of the electrochemical processes that occur at the electrodes is vital for intelligent design of more energy efficient electrodes. X-ray absorption spectroscopy (XAS) is a short-range order, element specific technique that can be utilized to probe the processes occurring at operating electrode surfaces, as well for studying the amorphous materials and nano-particles making up the electrodes. It has been increasingly used in recent years to study fuel cell catalysts through application of the and #916; and mgr; XANES technique, in combination with the more traditional X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) techniques. The and #916; and mgr; XANES data analysis technique, previously developed and applied to heterogeneous catalysts and fuel cell electrocatalysts by the GWU group, was extended in this work to provide for the first time space resolved adsorbate coverages on both electrodes of a direct methanol fuel cell. Even more importantly, the and #916; and mgr; technique was applied for the first time to battery relevant materials, where bulk properties such as the oxidation state and local geometry of a cathode are followed.

  15. A wavelet analysis for the X-ray absorption spectra of molecules.

    PubMed

    Penfold, T J; Tavernelli, I; Milne, C J; Reinhard, M; El Nahhas, A; Abela, R; Rothlisberger, U; Chergui, M

    2013-01-07

    We present a Wavelet transform analysis for the X-ray absorption spectra of molecules. In contrast to the traditionally used Fourier transform approach, this analysis yields a 2D correlation plot in both R- and k-space. As a consequence, it is possible to distinguish between different scattering pathways at the same distance from the absorbing atom and between the contributions of single and multiple scattering events, making an unambiguous assignment of the fine structure oscillations for complex systems possible. We apply this to two previously studied transition metal complexes, namely iron hexacyanide in both its ferric and ferrous form, and a rhenium diimine complex, [ReX(CO)(3)(bpy)], where X = Br, Cl, or ethyl pyridine (Etpy). Our results demonstrate the potential advantages of using this approach and they highlight the importance of multiple scattering, and specifically the focusing phenomenon to the extended X-ray absorption fine structure (EXAFS) spectra of these complexes. We also shed light on the low sensitivity of the EXAFS spectrum to the Re-X scattering pathway.

  16. A wavelet analysis for the X-ray absorption spectra of molecules

    SciTech Connect

    Penfold, T. J.; Tavernelli, I.; Rothlisberger, U.; Milne, C. J.; Abela, R.; Reinhard, M.; Nahhas, A. El; Chergui, M.

    2013-01-07

    We present a Wavelet transform analysis for the X-ray absorption spectra of molecules. In contrast to the traditionally used Fourier transform approach, this analysis yields a 2D correlation plot in both R- and k-space. As a consequence, it is possible to distinguish between different scattering pathways at the same distance from the absorbing atom and between the contributions of single and multiple scattering events, making an unambiguous assignment of the fine structure oscillations for complex systems possible. We apply this to two previously studied transition metal complexes, namely iron hexacyanide in both its ferric and ferrous form, and a rhenium diimine complex, [ReX(CO){sub 3}(bpy)], where X = Br, Cl, or ethyl pyridine (Etpy). Our results demonstrate the potential advantages of using this approach and they highlight the importance of multiple scattering, and specifically the focusing phenomenon to the extended X-ray absorption fine structure (EXAFS) spectra of these complexes. We also shed light on the low sensitivity of the EXAFS spectrum to the Re-X scattering pathway.

  17. Probing local structure of pyrochlore lead zinc niobate with synchrotron x-ray absorption spectroscopy technique

    NASA Astrophysics Data System (ADS)

    Kanchiang, Kanokwan; Pramchu, Sittichain; Yimnirun, Rattikorn; Pakawanit, Phakkhananan; Ananta, Supon; Laosiritaworn, Yongyut

    2013-08-01

    Local structure of lead zinc niobate (PZN) ceramic, synthesized via B-site oxide precursor route in atmospheric pressure, was investigated using synchrotron x-ray absorption spectroscopy (XAS) technique. The x-ray absorption near-edge structure (XANES) simulation was first carried out. The XANES simulation results indicate that the PZN ceramic is in pyrochlore phase having Zn2+ substituted on Nb5+ site. Afterwards, the extended x-ray absorption fine structure (EXAFS) analysis was performed to extract the bond length information between Zn2+ and its neighboring atoms. From the EXAFS fitting, the bond length between Zn2+ and Pb2+ in the pyrochlore phase was found to be longer than the previously reported bond length in the perovskite phase. Further, with the radial distribution information of Zn2+'s neighboring atoms, the formation energies along the precursor-to-pyrochlore and precursor-to-perovskite reaction paths were calculated using the density functional theory (DFT). The calculated results show that the formation energy of the perovskite phase is noticeably higher than that of the pyrochlore phase, which is influenced by the presence of energetic Pb2+ lone pair, as the perovskite phase has shorter Zn2+ to Pb2+ bonding. This therefore suggests the steric hindrance of Pb2+ lone pair and the mutual interactions between Pb2+ lone pair and Zn2+ are main causes of the instability of lead zinc niobate in the perovskite structure and confirm the efficacy of XAS and DFT analysis in revealing local structural details of complex pyrochlore materials.

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

    NASA Astrophysics Data System (ADS)

    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.

  19. X-ray absorption spectroscopic studies of the active sites of nickel- and copper-containing metalloproteins

    SciTech Connect

    Tan, G.O.

    1993-06-01

    X-ray absorption spectroscopy (XAS) is a useful tool for obtaining structural and chemical information about the active sites of metalloproteins and metalloenzymes. Information may be obtained from both the edge region and the extended X-ray absorption fine structure (EXAFS) or post-edge region of the K-edge X-ray absorption spectrum of a metal center in a compound. The edge contains information about the valence electronic structure of the atom that absorbs the X-rays. It is possible in some systems to infer the redox state of the metal atom in question, as well as the geometry and nature of ligands connected to it, from the features in the edge in a straightforward manner. The EXAFS modulations, being produced by the backscattering of the ejected photoelectron from the atoms surrounding the metal atom, provide, when analyzed, information about the number and type of neighbouring atoms, and the distances at which they occur. In this thesis, analysis of both the edge and EXAFS regions has been used to gain information about the active sites of various metalloproteins. The metalloproteins studied were plastocyanin (Pc), laccase and nickel carbon monoxide dehydrogenase (Ni CODH). Studies of Cu(I)-imidazole compounds, related to the protein hemocyanin, are also reported here.

  20. X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

    SciTech Connect

    Andrews, J.C. |

    1995-08-01

    In this study, oriented Photosystem II (PS II) particles from spinach chloroplasts are studied with electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) to determine more details of the structure of the oxygen evolving complex (OEC). The nature of halide binding to Mn is also studied with Cl K-edge and Mn EXAFS (extended x-ray absorption fine structure) of Mn-Cl model compounds, and with Mn EXAFS of oriented PS II in which Br has replaced Cl. Attention is focused on the following: photosynthesis and the oxygen evolving complex; determination of mosaic spread in oriented photosystem II particles from signal II EPR measurement; oriented EXAFS--studies of PS II in the S{sub 2} state; structural changes in PS II as a result of treatment with ammonia: EPR and XAS studies; studies of halide binding to Mn: Cl K-edge and Mn EXAFS of Mn-Cl model compounds and Mn EXAFS of oriented Br-treated photosystem II.

  1. X-ray absorption spectral studies of copper (II) mixed ligand complexes

    NASA Astrophysics Data System (ADS)

    Soni, B.; Dar, Davood Ah; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

    2014-09-01

    X-ray absorption spectra at the K-edge of copper have been studied in two copper mixed ligand complexes, one having tetramethyethylenediamine (tmen) and the other having tetraethyethylenediamine (teen) as one of the ligands. The spectra have been recorded at BL-8 dispersive extended X-ray absorption fine structure (EXAFS) beamline at the 2.5 GeV INDUS- 2 synchrotron, RRCAT, Indore, India. The data obtained has been processed using the data analysis program Athena. The energy of the K-absorption edge, chemical shift, edge-width and shift of the principal absorption maximum in the complexes have been determined and discussed. The values of these parameters have been found to be approximately the same in both the complexes indicating that the two complexes possess similar chemical environment around the copper metal atom. The chemical shift has been utilized to estimate effective nuclear charge on the absorbing atom. The normalized EXAFS spectra have been Fourier transformed. The position of the first peak in the Fourier transform gives the value of first shell bond length, which is shorter than the actual bond length because of energy dependence of the phase factors in the sine function of the EXAFS equation. This distance is thus the phase- uncorrected bond length. Bond length has also been determined by Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. The results obtained from LSS and the Fourier transformation methods are comparable with each other, since both are phase uncorrected bond lengths.

  2. An x-ray absorption spectroscopy study of Ni-Mn-Ga shape memory alloys.

    PubMed

    Sathe, V G; Dubey, Aditi; Banik, Soma; Barman, S R; Olivi, L

    2013-01-30

    The austenite to martensite phase transition in Ni-Mn-Ga ferromagnetic shape memory alloys was studied by extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectroscopy. The spectra at all the three elements', namely, Mn, Ga and Ni, K-edges in several Ni-Mn-Ga samples (with both Ni and Mn excess) were analyzed at room temperature and low temperatures. The EXAFS analysis suggested a displacement of Mn and Ga atoms in opposite direction with respect to the Ni atoms when the compound transforms from the austenite phase to the martensite phase. The first coordination distances around the Mn and Ga atoms remained undisturbed on transition, while the second and subsequent shells showed dramatic changes indicating the presence of a modulated structure. The Mn rich compounds showed the presence of antisite disorder of Mn and Ga. The XANES results showed remarkable changes in the unoccupied partial density of states corresponding to Mn and Ni, while the electronic structure of Ga remained unperturbed across the martensite transition. The post-edge features in the Mn K-edge XANES spectra changed from a double peak like structure to a flat peak like structure upon phase transition. The study establishes strong correlation between the crystal structure and the unoccupied electronic structure in these shape memory alloys.

  3. Adsorption of mercury on lignin: combined surface complexation modeling and X-ray absorption spectroscopy studies.

    PubMed

    Lv, Jitao; Luo, Lei; Zhang, Jing; Christie, Peter; Zhang, Shuzhen

    2012-03-01

    Adsorption of mercury (Hg) on lignin was studied at a range of pH values using a combination of batch adsorption experiments, a surface complexation model (SCM) and synchrotron X-ray absorption spectroscopy (XAS). Surface complexation modeling indicates that three types of acid sites on lignin surfaces, namely aliphatic carboxylic-, aromatic carboxylic- and phenolic-type surface groups, contributed to Hg(II) adsorption. The bond distance and coordination number of Hg(II) adsorption samples at pH 3.0, 4.0 and 5.5 were obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy analysis. The results of SCM and XAS combined reveal that the predominant adsorption species of Hg(II) on lignin changes from HgCl(2)(0) to monodentate complex -C-O-HgCl and then bidentate complex -C-O-Hg-O-C- with increasing pH value from 2.0 to 6.0. The good agreement between SCM and XAS results provides new insight into understanding the mechanisms of Hg(II) adsorption on lignin.

  4. Diamond sensors and polycapillary lenses for X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ravel, B.; Attenkofer, K.; Bohon, J.; Muller, E.; Smedley, J.

    2013-10-01

    Diamond sensors are evaluated as incident beam monitors for X-ray absorption spectroscopy experiments. These single crystal devices pose a challenge for an energy-scanning experiment using hard X-rays due to the effect of diffraction from the crystalline sensor at energies which meet the Bragg condition. This problem is eliminated by combination with polycapillary lenses. The convergence angle of the beam exiting the lens is large compared to rocking curve widths of the diamond. A ray exiting one capillary from the lens meets the Bragg condition for any reflection at a different energy from the rays exiting adjacent capillaries. This serves to broaden each diffraction peak over a wide energy range, allowing linear measurement of incident intensity over the range of the energy scan. Extended X-ray absorption fine structure data are measured with a combination of a polycapillary lens and a diamond incident beam monitor. These data are of comparable quality to data measured without a lens and with an ionization chamber monitoring the incident beam intensity.

  5. Low-potential iron-sulfur centers in photosystem I: an X-ray absorption spectroscopy study.

    PubMed

    McDermott, A E; Yachandra, V K; Guiles, R D; Britt, R D; Dexheimer, S L; Sauer, K; Klein, M P

    1988-05-31

    We have measured the X-ray absorption spectra of Fe in photosystem I (PS I) preparations from spinach and a thermophilic cyanobacterium, Synechococcus sp., to characterize structures of the Fe complexes that function as electron acceptors in PS I. These acceptors include centers A and B, which are probably typical [4Fe-4S] ferredoxins, and X. The structure of X is not known, but its electron paramagnetic resonance (EPR) spectrum has generated the suggestions that it is either a [2Fe-2S] or [4Fe-4S] ferredoxin or an Fe-quinone species. The iron X-ray absorption K-edge and iron extended X-ray absorption fine structure (EXAFS) spectra reveal that essentially all of the 11-14 Fe atoms present in the reaction center are present in the form of Fe-S centers and that not more than 1 atom out of 12 could be octahedral or oxygen-coordinated Fe. This suggests that, besides A and B, additional Fe-S clusters are present which are likely to be X. Our EXAFS spectra cannot be simulated adequately by a mixture of [4Fe-4S] ferredoxins with typical bond lengths and disorder parameters because the amplitude of Fe backscattering is small; however, excellent simulations of the data are consistent with a mixture of [2Fe-2S] ferredoxins and [4Fe-4S] ferredoxins, or with unusually distorted [4Fe-4S] clusters. We presume that the [2Fe-2S] or distorted [4Fe-4S] centers are X. The X-ray absorption spectra of PS I preparations from Synechococcus and spinach are essentially indistinguishable.

  6. X-ray absorption spectroscopy study of the local environment around tungsten and molybdenum ions in tungsten-phosphate and molybdenum-phosphate glasses

    NASA Astrophysics Data System (ADS)

    Kuzmin, A.; Purans, J.

    1997-02-01

    X-ray absorption spectroscopy (XAS) was used to study the local environment around tungsten and molybdenum ions in BaO-P2O5-WO3 and CaO-P2O5-MoO3 glasses having different composition of WO3 and MoO3 oxides. The W L1,3 and Mo K edges x-ray absorption spectra were measured in transmission mode at room temperature using the synchrotron radiation emitted by the ADONE and LURE DCI storage rings, respectively. The analysis of x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) in glasses was performed in comparison with the results for a number of crystalline WO3, CaWO4, Na0.66WO3 alpha- MoO3, beta-MoO3 and amorphous a-WO3, a-MoO3 compounds. The results of the EXAFS modeling by two different methods [(1) multi-shell best-fit procedure within harmonic approximation and (2) model-independent radial distribution function approach] allowed us to extract detailed structural information on the first coordination shell of metal (W or Mo) ions. Using the obtained data together with the information given by XRD, EPR and optical spectroscopies, we propose the model of incorporation of W and Mo ions within the glass network.

  7. Determination of bimetallic architectures in nanometer-scale catalysts by combining molecular dynamics simulations with x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Timoshenko, Janis; Keller, Kayla R.; Frenkel, Anatoly I.

    2017-03-01

    Here we present an approach for the determination of an atomic structure of small bimetallic nanoparticles by combining extended X-ray absorption fine structure spectroscopy and classical molecular dynamics simulations based on the Sutton-Chen potential. The proposed approach is illustrated in the example of PdAu nanoparticles with ca 100 atoms and narrow size and compositional distributions. Using a direct modeling approach and no adjustable parameters, we were able to reproduce the size and shape of nanoparticles as well as the intra-particle distributions of atoms and metal mixing ratios and to explore the influence of these parameters on the local structure and dynamics in nanoparticles.

  8. Determination of bimetallic architectures in nanometer-scale catalysts by combining molecular dynamics simulations with x-ray absorption spectroscopy.

    PubMed

    Timoshenko, Janis; Keller, Kayla R; Frenkel, Anatoly I

    2017-03-21

    Here we present an approach for the determination of an atomic structure of small bimetallic nanoparticles by combining extended X-ray absorption fine structure spectroscopy and classical molecular dynamics simulations based on the Sutton-Chen potential. The proposed approach is illustrated in the example of PdAu nanoparticles with ca 100 atoms and narrow size and compositional distributions. Using a direct modeling approach and no adjustable parameters, we were able to reproduce the size and shape of nanoparticles as well as the intra-particle distributions of atoms and metal mixing ratios and to explore the influence of these parameters on the local structure and dynamics in nanoparticles.

  9. X-ray absorption studies of metalloprotein structure: cytochrome P-450, horseradish peroxidase, plastocyanin and laccase

    SciTech Connect

    Penner-Hahn, J.E.

    1984-03-01

    Extended x-ray absorption fine structure (EXAFS) has been developed to determine the structure of metalloproteins. EXAFS data have been collected and analysed for four states in the catalytic cycle of bacterial cytochrome P-450/sub CAM/. This data demonstrates that sulfur is retained as an axial ligand in the reduced forms of the enzyme. EXAFS and edge data have been analysed for the high-valent states of horseradish peroxidase (HRP), and for high-valent iron-porphyrin model compounds. These data provide the first direct confirmation of the presence of a ferryl Fe=O coordination in HRP and in some of the model compounds. The polarized single-crystal EXAFS spectra of plastocyanin have been measured as a function of both orientation and temperature. These data demonstrate that at room temperature the relative motions of the Cu and the S(Met) are essentially uncorrelated.

  10. A sample holder for soft x-ray absorption spectroscopy of liquids in transmission mode.

    PubMed

    Schreck, Simon; Gavrila, Gianina; Weniger, Christian; Wernet, Philippe

    2011-10-01

    A novel sample holder for soft x-ray absorption spectroscopy of liquids in transmission mode based on sample cells with x-ray transparent silicon nitride membranes is introduced. The sample holder allows for a reliable preparation of ultrathin liquid films with an adjustable thickness in the nm-μm range. This enables measurements of high quality x-ray absorption spectra of liquids in transmission mode, as will be shown for the example of liquid H(2)O, aqueous solutions of 3d-transition metal ions and alcohol-water mixtures. The fine structure of the x-ray absorption spectra is not affected by the sample thickness. No effects of the silicon nitride membranes were observed in the spectra. It is shown how an inhomogeneous thickness of the sample affects the spectra and how this can be avoided.

  11. Behavior of heptavalent technetium in sulfuric acid under α-irradiation: structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations.

    PubMed

    Denden, I; Poineau, F; Schlegel, M L; Roques, J; Solari, P Lorenzo; Blain, G; Czerwinski, K R; Essehli, R; Barbet, J; Fattahi, M

    2014-03-06

    The effect of α-radiolysis on the behavior of heptavalent technetium has been investigated in 13 and 18 M H2SO4. Irradiation experiments were performed using α-particles ((4)He(2+), E = 68 MeV) generated by the ARRONAX cyclotron. UV-visible and X-ray absorption fine structure spectroscopic studies indicate that Tc(VII) is reduced to Tc(V) under α-irradiation. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements are consistent with the presence of mononuclear technetium sulfate complexes. Experimental results and density functional calculations show the formation of [TcO(HSO4)3(H2O)(OH)](-) and/or [TcO(HSO4)3(H2O)2] and [Tc(HSO4)3(SO4)(H2O)] and/or [Tc(HSO4)3(SO4)(OH)](-) for 13 and 18 M H2SO4, respectively.

  12. Theoretical analysis of x-ray-absorption near-edge fine structure at the O and metal K edges of LaFeO{sub 3} and LaCoO{sub 3}

    SciTech Connect

    Wu, Z.Y.; Pedio, M.; Cimino, R.; Mobilio, S. |; Barman, S.R. |; Maiti, K.; Sarma, D.D. |

    1997-07-01

    We present experimental x-ray-absorption spectra at the oxygen and 3d transition-metal K edges of LaFeO{sub 3} and LaCoO{sub 3}. We interpret the experimental results in terms of detailed theoretical calculations based on multiple-scattering theory. Along with providing an understanding of the origin of various experimental features, we investigate the effects of structural distortions and the core-hole potential in determining the experimental spectral shape. The results indicate that the core-hole potential as well as many-body effects within the valence electrons do not have any strong effect on the spectra suggesting that the spectral features can be directly interpreted in terms of the electronic structure of such compounds. {copyright} {ital 1997} {ital The American Physical Society}

  13. Application of X-ray Absorption Spectroscopy to the study of nuclear structural materials

    NASA Astrophysics Data System (ADS)

    Liu, Shanshan

    One of key technologies for the next generation nuclear systems are advanced materials, including high temperature structural materials, fast neutron resistance core materials and so on. Local structure determination in these systems, which often are crystallographically intractable, is critical to gaining an understanding of their properties. In this thesis, X-ray Absorption Spectroscopy (XAS), including Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES), is used to examine the geometric and electronic structure of nuclear structural materials under varying conditions. The thesis is divided into two main sections. The first examines the structural analysis of nanostructured ferritic alloys (NFA) which are dispersion strengthened by an ultra high density of Y-Ti-O enriched nano-features, resulting in remarkable high temperature creep strength and radiation damage resistance. Titanium and Yttrium K-edge XAS shows commercial alloys MA957 and J12YWT more closely resemble the as received Fe-14Cr-3W-0.4Ti (wt. %) powders, and mechanically alloyed (MA) powders with 0.25Y2O3 (wt. %). It shows that a significant fraction of substitutional Ti remains dissolved in the (BCC) ferrite matrix. In contrast, annealed powders and hot isostatic press (HIP) consolidated alloys show high temperature heat treatments shift the Y and Ti to more oxidized states that are consistent with combinations of Y2Ti2O7 and, especially, TiO. The second section describes corrosion studies of Pb with 316L stainless steel, molybdenum and spinet (MgAl2O4) at high temperature by XAS. The corrosion of fuel cladding and structural materials by liquid lead at elevated temperatures is an issue that must be considered when designing advanced nuclear systems and high-power spallation neutron targets. The results of ex-situ studies show that a Mo substrate retained a smooth and less corroded surface than 316L stainless steel sample at elevated temperature. In

  14. Local atomic structure investigation of AlFeCuCrMgx (0.5, 1, 1.7) high entropy alloys: X-ray absorption spectroscopy study

    NASA Astrophysics Data System (ADS)

    Maulik, Ornov; Patra, N.; Bhattacharyya, D.; Jha, S. N.; Kumar, Vinod

    2017-02-01

    The present paper reports local atomic structure investigation of novel AlFeCuCrMgx (x=0.5, 1, 1.7) high entropy alloys (HEAs) produced by mechanical alloying using Fe, Cr and Cu K-edge X-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure (EXAFS) spectroscopy. XANES spectra measured at Fe and Cr K-edges resemble that of the respective pure metal foils, while the spectrum measured at Cu K-edge manifests the presence of some other phases in the as-milled alloys. The radial distribution functions (RDFs) obtained from Fourier transformation of EXAFS spectra support the formation of disordered BCC structure.

  15. Electronic and molecular structure of photoexcited [Ru(II)(bpy)3]2+ probed by picosecond X-ray absorption spectroscopy.

    PubMed

    Gawelda, Wojciech; Johnson, Melanie; de Groot, Frank M F; Abela, Rafael; Bressler, Christian; Chergui, Majed

    2006-04-19

    L(2,3) X-ray absorption spectra of aqueous [Ru(II)(bpy)3]2+ have been recorded in its ground and excited states, 50 ps after short pulse laser excitation. Significant changes in both the XANES (X-ray Near-Edge Absorption Structure) and the EXAFS (Extended X-ray Absorption Fine Structure) regions of the excited state complex are detected. The XANES line shapes have been quantitatively simulated using a crystal field multiplet code in trigonal symmetry. In addition, spectral changes in the EXAFS region of both ground and excited states are analyzed in order to extract structural parameters of their corresponding molecular structures. We obtain a Ru-N bond contraction by approximately 0.03 angstroms in the excited-state complex, as compared to the ground-state compound. This contraction results from electrostatic and polarization contributions, limited by steric constraints on the bpy ligands.

  16. An X-ray absorption spectroscopy investigation of the local atomic structure in Cu-Ni-Si alloy after severe plastic deformation and ageing

    NASA Astrophysics Data System (ADS)

    Azzeddine, H.; Harfouche, M.; Hennet, L.; Thiaudiere, D.; Kawasaki, M.; Bradai, D.; Langdon, T. G.

    2015-08-01

    The local atomic structure of Cu-Ni-Si alloy after severe plastic deformation (SPD) processing and the decomposition of supersaturated solid solution upon annealing were investigated by means of X-ray absorption spectroscopy. The coordination number and interatomic distances were obtained by analyzing experimental extend X-ray absorption fine structure data collected at the Ni K-edge. Results indicate that the environment of Ni atoms in Cu-Ni-Si alloy is strongly influenced by the deformation process. Moreover, ageing at 973 K affects strongly the atomic structure around the Ni atoms in Cu-Ni-Si deformed by equal channel angular pressing and high pressure torsion. This influence is discussed in terms of changes and decomposition features of the Cu-Ni-Si solid solution.

  17. Ultrafast time-resolved X-ray absorption spectroscopy of ferrioxalate photolysis with a laser plasma X-ray source and microcalorimeter array

    DOE PAGES

    O’Neil, Galen C.; Miaja-Avila, Luis; Joe, Young Il; ...

    2017-02-17

    The detailed pathways of photoactivity on ultrafast time scales are a topic of contemporary interest. Using a tabletop apparatus based on a laser plasma X-ray source and an array of cryogenic microcalorimeter X-ray detectors, we measured a transient X-ray absorption spectrum during the ferrioxalate photoreduction reaction. With these high-efficiency detectors, we observe the Fe K edge move to lower energies and the amplitude of the extended X-ray absorption fine structure reduce, consistent with a photoreduction mechanism in which electron transfer precedes disassociation. We provide quantitative limits on the Fe–O bond length change. Lastly, we review potential improvements to our measurementmore » technique, highlighting the future potential of tabletop X-ray science using microcalorimeter sensors.« less

  18. X-ray-absorption spectroscopy and n-body distribution functions in condensed matter. I. Theory

    NASA Astrophysics Data System (ADS)

    Filipponi, Adriano; di Cicco, Andrea; Natoli, Calogero Renzo

    1995-12-01

    The general theoretical framework underlying the GNXAS multiple-scattering (MS) data-analysis method for x-ray absorption spectroscopy (XAS) is presented. The main approximations leading to the reduction of the many-body process in that of a photoelectron scattering in an effective potential are summarized. The methods available to expand the extended x-ray-absorption fine-structure χ(k) into physically meaningful terms are described. In particular, emphasis is given to the definition of the irreducible n-body signals γ(n) that can be calculated directly by means of linear combinations of continued fractions, or by using their respective multiple-scattering series. It is found that even for an infinite system the expansion of the χ(k) signal in terms of γ(n) has a better convergence rate than the MS series. Simple expressions for performing the configurational averages of the structural signals in the presence of thermal and structural disorder are derived. These can be used for the structural analysis of molecular, crystalline, or moderately disordered systems. It is shown that in the case of highly disordered systems the expansion in terms of the γ(n) signals is the natural framework for the interpretation of the XAS signal. General equations for the ensemble-averaged χ(k) signal as a function of a series of integrals over the n-body n>~2 distribution functions gn are provided and the possible use of advanced strategies for the inversion of the structural information is suggested.

  19. Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

    USGS Publications Warehouse

    Kim, C.S.; Brown, Gordon E.; Rytuba, J.J.

    2000-01-01

    Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg-1 (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of ??25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis

  20. Polarized x-ray-absorption spectroscopy of the uranyl ion: Comparison of experiment and theory

    SciTech Connect

    Hudson, E.A.; Allen, P.G.; Terminello, L.J.; Denecke, M.A.; Reich, T.

    1996-07-01

    The x-ray linear dichroism of the uranyl ion (UO{sub 2}{sup 2+}) in uranium {ital L}{sub 3}-edge extended x-ray-absorption fine structure (EXAFS), and {ital L}{sub 1}- and {ital L}{sub 3}-edge x-ray-absorption near-edge structure (XANES), has been investigated both by experiment and theory. A striking polarization dependence is observed in the experimental XANES and EXAFS for an oriented single crystal of uranyl acetate dihydrate [UO{sub 2}(CH{sub 3}CO{sub 2}){sub 2}{center_dot}2H{sub 2}O], with the x-ray polarization vector aligned either parallel or perpendicular to the bond axis of the linear uranyl cation (O-U-O). Single-crystal results are compared to experimental spectra for a polycrystalline uranyl acetate sample and to calculations using the {ital ab} {ital initio} multiple-scattering (MS) code FEFF 6. Theoretical XANES spectra for uranyl fluoride (UO{sub 2}F{sub 2}) reproduce all the features of the measured uranyl acetate spectra. By identifying scattering paths which contribute to individual features in the calculated spectrum, a detailed understanding of the {ital L}{sub 1}-edge XANES is obtained. MS paths within the uranyl cation have a notable influence upon the XANES. The measured {ital L}{sub 3}-edge EXAFS is also influenced by MS, especially when the x-ray polarization is parallel to the uranyl species. These MS contributions are extracted from the total EXAFS and compared to calculations. The best agreement with the isolated MS signal is obtained by using nonoverlapped muffin-tin spheres in the FEFF 6 calculation. This contrasts the {ital L}{sub 1}-edge XANES calculations, in which overlapping was required for the best agreement with experiment. {copyright} {ital 1996 The American Physical Society.}

  1. Characterization of Metalloproteins by High-throughput X-ray Absorption Spectroscopy

    SciTech Connect

    W Shi; M Punta; J Bohon; J Sauder; R DMello; M Sullivan; J Toomey; D Abel; M Lippi; et al.

    2011-12-31

    High-throughput X-ray absorption spectroscopy was used to measure transition metal content based on quantitative detection of X-ray fluorescence signals for 3879 purified proteins from several hundred different protein families generated by the New York SGX Research Center for Structural Genomics. Approximately 9% of the proteins analyzed showed the presence of transition metal atoms (Zn, Cu, Ni, Co, Fe, or Mn) in stoichiometric amounts. The method is highly automated and highly reliable based on comparison of the results to crystal structure data derived from the same protein set. To leverage the experimental metalloprotein annotations, we used a sequence-based de novo prediction method, MetalDetector, to identify Cys and His residues that bind to transition metals for the redundancy reduced subset of 2411 sequences sharing <70% sequence identity and having at least one His or Cys. As the HT-XAS identifies metal type and protein binding, while the bioinformatics analysis identifies metal-binding residues, the results were combined to identify putative metal-binding sites in the proteins and their associated families. We explored the combination of this data with homology models to generate detailed structure models of metal-binding sites for representative proteins. Finally, we used extended X-ray absorption fine structure data from two of the purified Zn metalloproteins to validate predicted metalloprotein binding site structures. This combination of experimental and bioinformatics approaches provides comprehensive active site analysis on the genome scale for metalloproteins as a class, revealing new insights into metalloprotein structure and function.

  2. Quick-scanning x-ray absorption spectroscopy system with a servo-motor-driven channel-cut monochromator with a temporal resolution of 10 ms.

    PubMed

    Nonaka, T; Dohmae, K; Araki, T; Hayashi, Y; Hirose, Y; Uruga, T; Yamazaki, H; Mochizuki, T; Tanida, H; Goto, S

    2012-08-01

    We have developed a quick-scanning x-ray absorption fine structure (QXAFS) system and installed it at the recently constructed synchrotron radiation beamline BL33XU at the SPring-8. Rapid acquisition of high-quality QXAFS data was realized by combining a servo-motor-driven Si channel-cut monochromator with a tapered undulator. Two tandemly aligned monochromators with channel-cut Si(111) and Si(220) crystals covered energy ranges of 4.0-28.2 keV and 6.6-46.0 keV, respectively. The system allows the users to adjust instantly the energy ranges of scans, the starting angles of oscillations, and the frequencies. The channel-cut crystals are cooled with liquid nitrogen to enable them to withstand the high heat load from the undulator radiation. Deformation of the reflecting planes is reduced by clamping each crystal with two cooling blocks. Performance tests at the Cu K-edge demonstrated sufficiently high data quality for x-ray absorption near-edge structure and extended x-ray absorption fine-structure analyses with temporal resolutions of up to 10 and 25 ms, respectively.

  3. Evidence for core-shell nanoclusters in oxygen dispersion strengthened steels measured using X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, S.; Odette, G. R.; Segre, C. U.

    2014-02-01

    Nanostructured ferritic alloys (NFA) dispersion strengthened by an ultra high density of Y-Ti-O enriched nano-features (NF) exhibit superior creep strength and the potential for high resistance to radiation damage. However, the detailed character of the NF, that precipitate from solid solution during hot consolidation of metallic powders mechanically alloyed with Y2O3, are not well understood. In order to clarify the nature of the NF, X-ray absorption spectroscopy (XAS) technique, including X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were used to characterize the local structure of the Ti and Y atoms in both NFA powders and consolidated alloys. The powders were characterized in the as-received, as-milled and after annealing milled powders at 850, 1000 and 1150 °C. The consolidated alloys included powders hot isostatic pressed (HIPed) at 1150 °C and commercial vendor alloys, MA957 and J12YWT. The NFA XAS data were compared various Ti and Y-oxide standards. The XANES and EXAFS spectra for the annealed and HIPed powders are similar and show high temperature heat treatments shift the Y and Ti to more oxidized states that are consistent with combinations of Y2Ti2O7 and, especially, TiO. However, the MA957 and J12YWT and annealed-consolidated powder data differ. The commercial vendor alloys results more closely resemble the as-milled powder data and all show that a significant fraction of substitutional Ti remains dissolved in the (BCC) ferrite matrix.

  4. Evidence for core–shell nanoclusters in oxygen dispersion strengthened steels measured using X-ray absorption spectroscopy

    SciTech Connect

    Liu, S.; Odette, G. R.; Segre, C. U.

    2014-02-01

    Nanostructured ferritic alloys (NFA) dispersion strengthened by an ultra high density of Y–Ti–O enriched nano-features (NF) exhibit superior creep strength and the potential for high resistance to radiation damage. However, the detailed character of the NF, that precipitate from solid solution during hot consolidation of metallic powders mechanically alloyed with Y₂O₃, are not well understood. In order to clarify the nature of the NF, X-ray absorption spectroscopy (XAS) technique, including X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were used to characterize the local structure of the Ti and Y atoms in both NFA powders and consolidated alloys. The powders were characterized in the as-received, as-milled and after annealing milled powders at 850, 1000 and 1150 °C. The consolidated alloys included powders hot isostatic pressed (HIPed) at 1150 °C and commercial vendor alloys, MA957 and J12YWT. The NFA XAS data were compared various Ti and Y-oxide standards. The XANES and EXAFS spectra for the annealed and HIPed powders are similar and show high temperature heat treatments shift the Y and Ti to more oxidized states that are consistent with combinations of Y₂Ti₂O₇ and, especially, TiO. However, the MA957 and J12YWT and annealed–consolidated powder data differ. The commercial vendor alloys results more closely resemble the as-milled powder data and all show that a significant fraction of substitutional Ti remains dissolved in the (BCC) ferrite matrix.

  5. Time-dependent X-ray absorption spectroscopic (XAS) study on the transformation of zinc basic salt into bis(N-oxopyridine-2-thionato) zinc (II).

    PubMed

    Paek, Seung-Min; Jo, Won-Young; Park, Man; Choy, Jin-Ho

    2007-11-01

    Solid transchelation reaction was established for the synthesis of bis(N-oxopyridine-2-thionato) zinc (II), commonly known as zinc pyrithione (ZPT), to control particle size using zinc basic salt (ZBS) and aqueous sodium pyrithione solution. Distinguished from ZPT particles prepared by usual precipitation reaction, the obtained ZPT nanoparticles exhibited very narrow size distribution. X-ray absorption spectroscopy (XAS) at Zn K-edge was systematically examined to elucidate time-dependent local structural evolution during solid transchelation reaction. X-ray absorption near edge structure (XANES) analysis clearly revealed that local environment around zinc atoms transformed into pentahedron as reaction proceeded. Based on quantitative X-ray diffraction and XANES analysis, we made structural models. Theoretical XAS spectrum calculated with FEFF code could reproduce experimental one, suggesting that XAS analysis could be very powerful tool to probe phase transformation. Furthermore, according to extended X-ray absorption fine structure (EXAFS) fitting results, Zn-O distance in reaction products gradually increased from 1.96 to 2.07 angstroms, suggesting that zinc atoms bounded with oxygen ones in ZBS were transchelated with pyrithione ligands. This study could be a strong evidence for the usefulness of XAS to study time-dependent structural transformation of nanocrystalline materials.

  6. Ultrafast Time-Resolved X-ray Absorption Spectroscopy of Ferrioxalate Photolysis with a Laser Plasma X-ray Source and Microcalorimeter Array.

    PubMed

    O'Neil, Galen C; Miaja-Avila, Luis; Joe, Young Il; Alpert, Bradley K; Balasubramanian, Mahalingam; Sagar, D M; Doriese, William; Fowler, Joseph W; Fullagar, Wilfred K; Chen, Ning; Hilton, Gene C; Jimenez, Ralph; Ravel, Bruce; Reintsema, Carl D; Schmidt, Dan R; Silverman, Kevin L; Swetz, Daniel S; Uhlig, Jens; Ullom, Joel N

    2017-03-02

    The detailed pathways of photoactivity on ultrafast time scales are a topic of contemporary interest. Using a tabletop apparatus based on a laser plasma X-ray source and an array of cryogenic microcalorimeter X-ray detectors, we measured a transient X-ray absorption spectrum during the ferrioxalate photoreduction reaction. With these high-efficiency detectors, we observe the Fe K edge move to lower energies and the amplitude of the extended X-ray absorption fine structure reduce, consistent with a photoreduction mechanism in which electron transfer precedes disassociation. These results are compared to previously published transient X-ray absorption measurements on the same reaction and found to be consistent with the results from Ogi et al. and inconsistent with the results of Chen et al. ( Ogi , Y. ; et al. Struct. Dyn. 2015 , 2 , 034901 ; Chen , J. ; Zhang , H. ; Tomov , I. V. ; Ding , X. ; Rentzepis , P. M. Chem. Phys. Lett. 2007 , 437 , 50 - 55 ). We provide quantitative limits on the Fe-O bond length change. Finally, we review potential improvements to our measurement technique, highlighting the future potential of tabletop X-ray science using microcalorimeter sensors.

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

    SciTech Connect

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

    2016-01-21

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

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

    PubMed

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

    2013-02-07

    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.

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

    PubMed

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

    2016-05-05

    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 1000 mg L(-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.

  10. Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.

    2017-02-01

    Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

  11. In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO2

    NASA Astrophysics Data System (ADS)

    Patridge, Christopher J.; Love, Corey T.; Swider-Lyons, Karen E.; Twigg, Mark E.; Ramaker, David E.

    2013-07-01

    The local structure of nanoscale (∼10-40 nm) LiCoO2 is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO2 nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO2 metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li-Co site exchange at the surface of the nanoscale LiCoO2 as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO2.

  12. Capturing Transient Electronic and Molecular Structures in Liquids by Picosecond X-Ray Absorption Spectroscopy

    SciTech Connect

    Gawelda, W.; Pham, V. T.; El Nahhas, A.; Kaiser, M.; Zaushitsyn, Y.; Bressler, C.; Chergui, M.; Johnson, S. L.; Grolimund, D.; Abela, R.; Hauser, A.

    2007-02-02

    We describe an advanced setup for time-resolved x-ray absorption fine structure (XAFS) Spectroscopy with picosecond temporal resolution. It combines an intense femtosecond laser source synchronized to the x-ray pulses delivered into the microXAS beamline of the Swiss Light Source (SLS). The setup is applied to measure the short-lived high-spin geometric structure of photoexcited aqueous Fe(bpy)3 at room temperature.

  13. Identifying barriers to charge-carriers in the bulk and surface regions of Cu2ZnSnS4 nanocrystal films by x-ray absorption fine structures (XAFSs)

    NASA Astrophysics Data System (ADS)

    Turnbull, Matthew J.; Vaccarello, Daniel; Yiu, Yun Mui; Sham, Tsun-Kong; Ding, Zhifeng

    2016-11-01

    Solar cell performance is most affected by the quality of the light absorber layer. For thin-film devices, this becomes a two-fold problem of maintaining a low-cost design with well-ordered nanocrystal (NC) structure. The use of Cu2ZnSnS4 (CZTS) NCs as the light absorber films forms an ideal low-cost design, but the quaternary structure makes it difficult to maintain a well-ordered layer without the use of high-temperature treatments. There is little understanding of how CZTS NC structures affect the photoconversion efficiency, the charge-carriers, and therefore the performance of the device manufactured from it. To examine these relationships, the measured photoresponse from the photo-generation of charge-carrier electron-hole pairs was compared against the crystal structure, as short-range and long-range crystal orders for the films. The photoresponse simplifies the electronic properties into three basic steps that can be associated with changes in energy levels within the band structure. These changes result in the formation of barriers to charge-carrier flow. The extent of these barriers was determined using synchrotron-based X-ray absorbance fine structure to probe the individual metal centers in the film, and comparing these to molecular simulations of the ideal extended x-ray absorbance fine structure scattering. This allowed for the quantification of bond lengths, and thus an interpretation of the distortions in the crystal lattice. The various characteristics of the photoresponse were then correlated to the crystallographic order and used to gain physical insight into barriers to charge-carriers in the bulk and surface regions of CZTS films.

  14. Identifying barriers to charge-carriers in the bulk and surface regions of Cu2ZnSnS4 nanocrystal films by x-ray absorption fine structures (XAFSs).

    PubMed

    Turnbull, Matthew J; Vaccarello, Daniel; Yiu, Yun Mui; Sham, Tsun-Kong; Ding, Zhifeng

    2016-11-28

    Solar cell performance is most affected by the quality of the light absorber layer. For thin-film devices, this becomes a two-fold problem of maintaining a low-cost design with well-ordered nanocrystal (NC) structure. The use of Cu2ZnSnS4 (CZTS) NCs as the light absorber films forms an ideal low-cost design, but the quaternary structure makes it difficult to maintain a well-ordered layer without the use of high-temperature treatments. There is little understanding of how CZTS NC structures affect the photoconversion efficiency, the charge-carriers, and therefore the performance of the device manufactured from it. To examine these relationships, the measured photoresponse from the photo-generation of charge-carrier electron-hole pairs was compared against the crystal structure, as short-range and long-range crystal orders for the films. The photoresponse simplifies the electronic properties into three basic steps that can be associated with changes in energy levels within the band structure. These changes result in the formation of barriers to charge-carrier flow. The extent of these barriers was determined using synchrotron-based X-ray absorbance fine structure to probe the individual metal centers in the film, and comparing these to molecular simulations of the ideal extended x-ray absorbance fine structure scattering. This allowed for the quantification of bond lengths, and thus an interpretation of the distortions in the crystal lattice. The various characteristics of the photoresponse were then correlated to the crystallographic order and used to gain physical insight into barriers to charge-carriers in the bulk and surface regions of CZTS films.

  15. Temperature dependent soft x-ray absorption spectroscopy of liquids.

    PubMed

    Meibohm, Jan; Schreck, Simon; Wernet, Philippe

    2014-10-01

    A novel sample holder is introduced which allows for temperature dependent soft x-ray absorption spectroscopy of liquids in transmission mode. The setup is based on sample cells with x-ray transmissive silicon nitride windows. A cooling circuit allows for temperature regulation of the sample liquid between -10 °C and +50 °C. The setup enables to record soft x-ray absorption spectra of liquids in transmission mode with a temperature resolution of 0.5 K and better. Reliability and reproducibility of the spectra are demonstrated by investigating the characteristic temperature-induced changes in the oxygen K-edge x-ray absorption spectrum of liquid water. These are compared to the corresponding changes in the oxygen K-edge spectra from x-ray Raman scattering.

  16. Combined surface plasmon resonance and X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Garcia, Miguel Angel; Serrano, Aida; Rodriguez de La Fuente, Oscar; Castro, German R.

    2012-02-01

    We present a system for the excitation and measurement of surface plasmons in metallic films based on the Kretschmann-Raether configuration that can be installed in a synchrotron beamline. The device was mounted an tested in a hard X-ray Absorption beamline, BM25 Spline at ESRF. Whit this device it is possible to carry on experiments combining surface plasmon and X-ray absorption spectroscopies. The surface plasmons can be use to monitor in situ changes induced by the X-rays in the metallic films or the dielectric overlayer. Similarly, the changes in the electronic configuration of the material when surface plasmons are excited can be measured by X-ray absorption spectroscopy. The resolution of the system allows to observe changes in the signals of the order of 10-3 to 10-5 depending on the particular experiment and used configuration. The system is available for experiments at the beamline.

  17. Photoelectron and X-ray Absorption Spectroscopy Of Pu

    SciTech Connect

    Tobin, J; Chung, B; Schulze, R; Farr, J; Shuh, D

    2003-11-12

    We have performed Photoelectron Spectroscopy and X-Ray Absorption Spectroscopy upon highly radioactive samples of Plutonium at the Advanced Light Source in Berkeley, CA, USA. First results from alpha and delta Plutonium are reported as well as plans for future studies of actinide studies.

  18. Assessment of Aided Phytostabilization of Copper-Contaminated Soil by X-ray Absorption Spectroscopy and Chemical Extractions

    SciTech Connect

    J Kumpiene; M Mench; C Bes; J Fitts

    2011-12-31

    Field plots were established at a timber treatment site to evaluate remediation of Cu contaminated topsoils with aided phytostabilization. Soil containing 2600 mg kg{sup -1} Cu was amended with a combination of 5 wt% compost and 2 wt% iron grit, and vegetated. Sequential extraction was combined with extended X-ray absorption fine structure (EXAFS) spectroscopy to correlate changes in Cu distribution across five fractions with changes in the predominant Cu compounds two years after treatment in parallel treated and untreated field plots. Exchangeable Cu dominated untreated soil, most likely as Cu(II) species non-specifically bound to natural organic matter. The EXAFS spectroscopic results are consistent with the sequential extraction results, which show a major shift in Cu distribution as a result of soil treatment to the fraction bound to poorly crystalline Fe oxyhydroxides forming binuclear inner-sphere complexes.

  19. The structure of AuPd nanoalloys anchored on spherical polyelectrolyte brushes determined by X-ray absorption spectroscopy.

    PubMed

    Kaiser, Julian; Szczerba, Wojciech; Riesemeier, Heinrich; Reinholz, Uwe; Radtke, Martin; Albrecht, Martin; Lu, Yan; Ballauff, Matthias

    2013-01-01

    Well-defined and facetted bimetallic gold-palladium nanoalloys have been synthesized and anchored in spherical polyelectrolyte brushes (SPB) as composite particles (AuPd@SPB). These particles are better catalysts in aqueous phase than the pure metals. The atomistic arrangement of these nanoalloys has been analysed by extended X-ray absorption fine structure (EXAFS) spectroscopy at the Au-L3 and the Pd-K absorption edge. The samples with high amounts of gold appear as almost statistically mixed random alloys. Alloy compositions with less gold show slight enrichment of Pd at the surface of the particle. In addition, signals of non-metallic palladium appear at the Pd-K edge which indicate the presence of the Pd2+ species in addition to metallic palladium. The relation of these structural features to the catalytic activity is discussed.

  20. X-ray absorption spectroscopy and X-ray photoelectron spectroscopy studies of CaSO 4:Dy thermoluminescent phosphors

    NASA Astrophysics Data System (ADS)

    Bakshi, A. K.; Jha, S. N.; Olivi, L.; Phase, D. M.; Kher, R. K.; Bhattacharyya, D.

    2007-11-01

    Extended X-ray absorption fine structure (EXAFS) measurements have been carried out on CaSO4:Dy phosphor samples at the Dy L3 edge with synchrotron radiation. Measurements were carried out on a set of samples which were subjected to post-preparation annealing at different temperatures and for different cycles. The EXAFS data have been analysed to find the Dy-S and Dy-O bond lengths in the neighbourhood of the Dy atoms in a CaSO4 matrix. The observations from EXAFS measurements were verified with XANES and XPS techniques. On the basis of these measurements, efforts were made to explain the loss of thermoluminescence sensitivity of CaSO4:Dy phosphors after repeated cycles of annealing at 400 °C in air for 1 h.

  1. X-ray absorption structural study of a reversible, photoexcited charge-transfer state

    SciTech Connect

    Chen, L.X.; Bowman, M.K.; Norris, J.R. Univ. of Chicago, IL ); Montano, P.A. )

    1993-05-19

    Electron-transfer reactions can be accompanied by significant nuclear movements. Nuclear motion appears to be especially vital to the reversible, photoinduced charge-transfer chemistry of cyclopentadienylnickel nitrosyl (C[sub 5]H[sub 5]NiNO). Although extended X-ray absorption fine structure (EXAFS) spectroscopy has recorded photoinduced changes in the ligation of myoglobins, similar X-ray studies of electron-transfer chemistry have not been reported. Here we examine reversible, photoinduced structural changes in C[sub 5]H[sub 5]NiNO by EXAFS and propose a mechanism for the electron-transfer chemistry. This work demonstrates that EXAFS can measure distance changes accompanying photoinduced electron transfer to provide new details of the geometry of photoexcited state and suggests that electron transfer occurs in the transient, optically excited states of C[sub 5]H[sub 5]NiNO and C[sub 5]H[sub 5]NiNO[sup CT] as dictated by NO movement that produces either C[sub 5]H[sub 5]NiNO[sup CT] or C[sub 5]H[sub 5]NiNO[sup GS]. 14 refs., 2 figs.

  2. Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering

    USGS Publications Warehouse

    Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.

    2006-01-01

    Biogenic manganese oxides are common and an important source of reactive mineral surfaces in the environment that may be potentially enhanced in bioremediation cases to improve natural attenuation. Experiments were performed in which the uranyl ion, UO22+ (U(VI)), at various concentrations was present during manganese oxide biogenesis. At all concentrations, there was strong uptake of U onto the oxides. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) studies were carried out to determine the molecular-scale mechanism by which uranyl is incorporated into the oxide and how this incorporation affects the resulting manganese oxide structure and mineralogy. The EXAFS experiments show that at low concentrations (2 mol % U, >4 ??M U(VI) in solution), the presence of U(VI) affects the stability and structure of the Mn oxide to form poorly ordered Mn oxide tunnel structures, similar to todorokite. EXAFS modeling shows that uranyl is present in these oxides predominantly in the tunnels of the Mn oxide structure in a tridentate complex. Observations by XRD corroborate these results. Structural incorporation may lead to more stable U(VI) sequestration that may be suitable for remediation uses. These observations, combined with the very high uptake capacity of the Mn oxides, imply that Mn-oxidizing bacteria may significantly influence dissolved U(VI) concentrations in impacted waters via sorption and incorporation into Mn oxide biominerals. ?? 2006 American Chemical Society.

  3. Evidence for the interaction of technetium colloids with humic substances by X-ray absorption spectroscopy.

    PubMed

    Maes, A; Geraedts, K; Bruggeman, C; Vancluysen, J; Rossberg, A; Hennig, C

    2004-04-01

    Spectroscopic extended X-ray absorption fine structure (EXAFS) evidence was obtained on the chemical environment of 99Tc(IV) atoms formed upon introduction of TcO4- into four types of laboratory-scale synthetic and natural systems which mimic in situ natural reducing conditions in humic-rich geochemical environments: (a) magnetite/pyrite in synthetic groundwater in the absence of humic substances (HSs), (b) magnetite/pyrite in natural Gorleben groundwater in the presence of HSs, (c) Boom clay sediment mixed with synthetic groundwater, and (d) Gorleben sand mixed with natural Gorleben groundwater. The investigated systems obey to pH 8-9 conditions, and all measured samples show similar EXAFS spectra for Tc, which could be fitted by a hydrated TcO2 x xH2O phase. The results are interpreted as follows: upon introduction of high concentrations (millimolar to micromolar) of TcO4-to chemically reducing environments, small Tc(IV) oxidic polymers are formed, which either may aggregate into larger units (colloids) and finally precipitate or may interact in their polymeric form with (dissolved and immobile) humic substances. This latter type of interaction--Tc(IV) colloid sorption onto HSs--differs significantly from the generally accepted metal--humate complexation and therefore offers new views on the possible reaction pathways of metals and radionuclides in humic-rich environments.

  4. Progress in the Theory and Interpretation of X-ray Absorption Spectra

    NASA Astrophysics Data System (ADS)

    Rehr, J. J.

    2002-03-01

    There has been dramatic progress in recent years in the understanding of x-ray absorption spectra (XAS) [1]. For example, modern real space multiple scattering theory has yielded a quantitative treatment of the extended fine structure in XAS. Crucial in the theory is a treatment of electronic excited states including many-body effects such as inelastic losses and Debye-Waller factors. These developments have led to ab initio codes which permit an interpretation of the spectra in terms of geometrical and electronic properties of materials [2]. Indeed, the availability of such codes has revolutionized experimental investigations based on synchrotron radiation x-ray sources. Algorithmic improvements have recently made possible fast, parallel calculations of the near edge structure (XANES) [3], and approximate treatments of local field effects and many-body amplitude factors. Related techniques have been applied to several other spectroscopies, e.g., anomalous x-ray scattering, x-ray magnetic circular dichroism, and photoelectron diffraction [4]. [1] J. J. Rehr and R. C. Albers, Rev. Mod. Phys. 72, 621 (2000); [2] A. L. Ankudinov, B. Ravel, J.J. Rehr, and S. Conradson, Phys. Rev. B 58, 7565 (1998); [3] A. L. Ankudinov, C. E. Bouldin, J. J. Rehr, J. Sims, and H. Hung, Phys. Rev. B, in press (2002); [4] F. J. Garcia de Abajo, M. A. Van Hove, C. S. Fadley, Phys. Rev. B 63, 075404 (2001).

  5. Prospects for X-ray absorption with the super-bright light sources of the future.

    PubMed

    Norman, D

    2001-03-01

    The immense growth in applications of X-ray absorption spectroscopy (XAS) has been enabled by the widespread availability of intense tunable X-rays from synchrotron radiation sources. Recently, new concepts have been proposed for fourth-generation light sources, such as the SASE (self-amplified stimulated emission) X-ray free-electron lasers (XFELs) being pursued at Hamburg (TESLA) and Stanford (LCLS), and the recirculator ring (MARS) at Novosibirsk. These sources offer expected gains of many orders of magnitude in instantaneous brilliance, which will unlock opportunities for qualitatively different science. Examples of new or greatly expanded techniques in XAS could include Raman X-ray absorption fine structure (XAFS), pump-probe experiments, time-resolved XAFS and small-spot X-ray spectromicroscopy, although the limited tunability of the sources might not allow conventional XAFS measurements. Multi-photon X-ray absorption could become a new field of study. There should not be a collective stampede to these new sources, however, and it is likely that storage rings will continue to be necessary for most XAFS applications. The extreme brightness of these future light sources will present difficult challenges in instrumentation, especially detectors and sample containment. Practitioners will also have to exercise caution, because the intensity of the beam will surely destroy many samples and in some cases there will be so many photons absorbed per atom that XAFS will be impossible.

  6. Substitution behavior of x(Na0.5K0.5)NbO3-(1 - x)BaTiO3 ceramics for multilayer ceramic capacitors by a near edge x-ray absorption fine structure analysis

    NASA Astrophysics Data System (ADS)

    Ha, Jooyeon; Ryu, Jiseung; Lee, Heesoo

    2014-06-01

    The doping effect of (Na0.5K0.5)NbO3 (NKN) as alternatives for rare-earth elements on the electrical properties of BaTiO3 has been investigated, in terms of their substitution behavior. The dielectric constant of a specimen with x = 0.05 was about 79% higher than that of pure BaTiO3, and the temperature coefficient of capacitance was satisfied by the X7R specification. The specimen with x = 0.05 showed the lowest tetragonality among the four compositions and had a fine grain size of <2 μm. Although the addition of NKN decreased the specimen's tetragonality, the electrical properties were enhanced by the formation of defect dipoles and conduction electrons, which resulted from an acceptor and donor substitution behavior. Through O K-edge near edge x-ray absorption fine structure spectroscopy, the practical substitution behavior was defined by the change in Ti 3d orbital states. The energy separation of the Ti 3d orbitals was more apparent with the specimen of x = 0.05, which is related to the donor level from the donor substitution of Nb5+ ion for Ti-sites. Therefore, the simultaneous substitution of Na+/K+ and Nb5+ ions into BaTiO3 can improve dielectric properties, based on the charge-transfer process.

  7. A method for normalization of X-ray absorption spectra

    SciTech Connect

    Weng, T.-C.; Waldo, G.S.; Penner-Hahn, J.E.

    2010-07-20

    Accurate normalization of X-ray absorption data is essential for quantitative analysis of near-edge features. A method, implemented as the program MBACK, to normalize X-ray absorption data to tabulated mass absorption coefficients is described. Comparison of conventional normalization methods with MBACK demonstrates that the new normalization method is not sensitive to the shape of the background function, thus allowing accurate comparison of data collected in transmission mode with data collected using fluorescence ion chambers or solid-state fluorescence detectors. The new method is shown to have better reliability and consistency and smaller errors than conventional normalization methods. The sensitivity of the new normalization method is illustrated by analysis of data collected during an equilibrium titration.

  8. In-Plane Structure of Underpotentially Deposited Copper on Gold (111) Determined by Surface EXAFS (Extended X-Ray Absorption Fine Structure).

    DTIC Science & Technology

    1988-01-28

    D-Al 263 INN-PLANE STRUCTURE OF UNDERPOTENTIALLY DEPOSITED COPPER /. ON GOLD (Iii) DET (U) PUERTO RICO UNIV RIO PIEDRAS DEPT OF PHVS I CS 0 R...051-0776 TECHNICAL REPORT #33 In-Plane Structure of Underpotentially Deposited Copper on Gold (111) Determined by Surface EXAFS by O.R. Melroy*, M.G...Strueture of Underpotentially Deposited Copper on Gold ( 11) determincd hv Surface EXAFS 0. R. Melroy*, N1. G. Samant, G. L. Borges. and J. G. Gordon

  9. In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO{sub 2}

    SciTech Connect

    Patridge, Christopher J.; Swider-Lyons, Karen E.; Twigg, Mark E.; Ramaker, David E.

    2013-07-15

    The local structure of nanoscale (∼10–40 nm) LiCoO{sub 2} is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO{sub 2} nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO{sub 2} metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li–Co site exchange at the surface of the nanoscale LiCoO{sub 2} as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO{sub 2}. - Graphical abstract: Electrochemical cycling of Li-ion batteries has strong impact on the structure and integrity of the cathode active material particularly near the surface/electrolyte interface. In developing a new method, we have used in-situ X-ray absorption spectroscopy during electrochemical cycling of nanoscale LiCoO{sub 2} to track changes during charge and discharge and between subsequent cycles. Using difference spectra, several small changes in Co-O bond length, Co-O and Co-Co coordination, and site exchange between Co and Li sites can be tracked. These methods show promise as a new technique to better understand processes which lead to capacity fade and loss in Li-ion batteries. - Highlights: • A new method is developed to understand capacity fade in Li-ion battery cathodes. • Structural changes are tracked during Li intercalation/deintercalation of LiCoO{sub 2}. • Surface structural changes are emphasized using nanoscale-LiCoO{sub 2} and difference spectra. • Full multiple

  10. Chloride ligation in inorganic manganese model compounds relevant to Photosystem II studied using X-ray absorption spectroscopy

    PubMed Central

    Pizarro, Shelly A.; Visser, Hendrik; Cinco, Roehl M.; Robblee, John H.; Pal, Samudranil; Mukhopadhyay, Sumitra; Mok, Henry J.; Sauer, Kenneth; Wieghardt, Karl; Armstrong, William H.

    2014-01-01

    Chloride ions are essential for proper function of the photosynthetic oxygen-evolving complex (OEC) of Photosystem II (PS II). Although proposed to be directly ligated to the Mn cluster of the OEC, the specific structural and mechanistic roles of chloride remain unresolved. This study utilizes X-ray absorption spectroscopy (XAS) to characterize the Mn–Cl interaction in inorganic compounds that contain structural motifs similar to those proposed for the OEC. Three sets of model compounds are examined; they possess core structures MnIV3O4X (X = Cl, F, or OH) that contain a di-μ-oxo and two mono-μ-oxo bridges or MnIV2O2X (X = Cl, F, OH, OAc) that contain a di-μ-oxo bridge. Each set of compounds is examined for changes in the XAS spectra that are attributable to the replacement of a terminal OH or F ligand, or bridging OAc ligand, by a terminal Cl ligand. The X-ray absorption near edge structure (XANES) shows changes in the spectra on replacement of OH, OAc, or F by Cl ligands that are indicative of the overall charge of the metal atom and are consistent with the electronegativity of the ligand atom. Fourier transforms (FTs) of the extended X-ray absorption fine structure (EXAFS) spectra reveal a feature that is present only in compounds where chloride is directly ligated to Mn. These FT features were simulated using various calculated Mn–X interactions (X = O, N, Cl, F), and the best fits were found when a Mn–Cl interaction at a 2.2–2.3 Å bond distance was included. There are very few high-valent Mn halide complexes that have been synthesized, and it is important to make such a comparative study of the XANES and EXAFS spectra because they have the potential for providing information about the possible presence or absence of halide ligation to the Mn cluster in PS II. PMID:14758524

  11. X-ray absorption spectroscopy on the calcium cofactor to the manganese cluster in photosynthetic oxygen evolution

    SciTech Connect

    Cinco, Roehl M.

    1999-12-01

    Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH2OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees ± 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese cluster in PS II and a family of synthetic manganese complexes containing the distorted cubane [Mn4O3X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn4O3Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The EXAFS method detects the small changes in the core structures as X is varied in this series, and serves to exclude these distorted cubanes of C3v symmetry as a topological model for the Mn catalytic cluster. The sulfur K-edge x-ray absorption near-edge structure (XANES) spectra for the amino acids cysteine, methionine, their corresponding oxidized forms cystine and methionine sulfoxide, and

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

    SciTech Connect

    Prasoetsopha, Natkrita; Pinitsoontorn, Supree; Bootchanont, Atipong; Kidkhunthod, Pinit; Srepusharawoot, Pornjuk; Kamwanna, Teerasak; Amornkitbamrung, Vittaya; Kurosaki, Ken; Yamanaka, Shinsuke

    2013-08-15

    Polycrystalline Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+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 Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+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 Ca{sub 2}CoO{sub 3} (rocksalt, RS) layer rather than in the CoO{sub 2} layer. Variation in the thermoelectric properties as a function of Fe concentration was attributed to charge transfer between the CoO{sub 2} 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 CoO{sub 2} layer; (d) with magnetic moment and (e) without magnetic moment. Highlights: • Synthesis, structural studies, and thermoelectric properties of Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+δ}. • Direct evidence for the local structure of the Fe ions in the Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+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

  13. 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

    SciTech Connect

    Murphy, M. W.; Yiu, Y. M. Sham, T. K.; Ward, M. J.; Liu, L.; Hu, Y.; Zapien, J. A.; Liu, Yingkai

    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.

  14. X-ray absorption spectroscopy proves the trigonal-planar sulfur-only coordination of copper(I) with high-affinity tripodal pseudopeptides.

    PubMed

    Jullien, Anne-Solène; Gateau, Christelle; Kieffer, Isabelle; Testemale, Denis; Delangle, Pascale

    2013-09-03

    A series of tripodal ligands L derived from nitrilotriacetic acid (NTA) and extended by three converging metal-binding cysteine chains were previously found to bind selectively copper(I) both in vitro and in vivo. The ligands L(1) (ester) and L(2) (amide) were demonstrated to form copper(I) species with very high affinities, close to that reported for the metal-sequestering metallothioneins (MTs; log K(Cu-MT) ≈ 19). Here, an in-depth study by Cu K-edge X-ray absorption spectroscopy (XAS) was performed to completely characterize the copper(I) coordination sphere in the complexes, previously evidenced by other physicochemical analyses. The X-ray absorption near-edge structure (XANES) spectra shed light on the equilibrium between a mononuclear complex and a cluster for both L(1) (ester) and L(2) (amide). The exclusive symmetric CuS3 geometry adopted in the mononuclear complexes (Cu-S ≈ 2.23 Å) was clearly demonstrated by extended X-ray absorption fine structure (EXAFS) analyses. The EXAFS analyses also proved that the clusters are organized on a symmetric CuS3 core (Cu-S ≈ 2.26 Å) and interact with three nearby copper atoms (Cu---Cu ≈ 2.7 Å), consistent with the Cu6S9-type clusters previously characterized by pulsed gradient spin echo NMR spectroscopy. XAS data obtained for other architectures based on the NTA template (L(3) acid, L(4) without a functionalized carbonyl group, etc.) demonstrated the formation of polymetallic species only, which evidence the necessity of the proximal ester or amide group to stabilize the CuS3 mononuclear species. Finally, XAS was demonstrated to be a powerful method to quantify the equilibrium between the two copper(I) environments evidenced with L(1) and L(2) at different copper concentrations and to determine the equilibrium constants between these two complexes.

  15. In situ x-ray absorption spectroscopy study of tin anode nanomaterials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Pelliccione, Christopher J.

    Tin is an attractive alternative to replace traditional carbon based anodes in lithium-ion batteries (LIBs) due to the nearly three-fold increase in theoretical capacity over carbon. However, metallic tin suffers from volumetric expansion of the crystal structure during initial lithium insertion that quickly degrades the material and reduces the performance of the battery. Various techniques have been previously investigated with the goal of suppressing this destructive expansion by incorporating oxygen or a lithium-inactive metal into the tin to provide structural support and mitigate volumetric expansion. These materials show increased capacity retention compared to metallic tin, but still suffer from capacity fading. The nature of these structural degradations must be fully understood to permit engineering of materials that avoid these destructive tendencies and can be considered as viable options for LIBs. In situ X-ray absorption spectroscopy (XAS) measurements were acquired on Sn, SnO2, Sn3O2(OH) 2, Cu6Sn5 and Ni3Sn4 nanoparticle anodes for LIBs. Accompanying the electrochemical characterization conducted on each material, the local atomic structure was modeled as a function of potential during the first charge and also as a function of charged/discharged states for several cycles. The extended X-ray absorption fine structure (EXAFS) theoretical modeling included the first unambiguous observation of Sn-Li coordination numbers and atomic distances in tin-based anode materials. From correlating the electrochemical performance to the EXAFS analysis, the long-term capacity retention of tin-based anodes is dependent on the structural deformations that occur during the first charge. The conversion of oxygen to amorphous Li2O, and the network that it forms, has a dramatic effect on the kinetics of the system and the stability of the local metallic tin structure.

  16. X-ray absorption studies of uranium sorption on mineral substrates

    SciTech Connect

    Hudson, E.A.; Terminello, L.J.; Viani, B.E.

    1994-11-01

    Uranium L{sub 3}-edge x-ray absorption spectra have been measured for uranium-mineral sorption systems. An expansible layer silicate, vermiculite, was treated to obtain a collapsed and non-expanding phase, thereby limiting access to the interior cation exchange sites. Samples were prepared by exposing the finely powdered mineral, in the natural and modified form, to aqueous solutions of uranyl chloride. EXAFS spectra of the encapsulated samples were measured at the Stanford Synchrotron Radiation Laboratory. Results indicate that the uranyl ion possesses a more symmetric local structure within the interlayer regions of vermiculite than on the external surfaces.

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

    PubMed Central

    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-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs. RHE produces a disordered Mn3II,III,IIIO4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs. RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed MnIII,IV oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3II,III,IIIO4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the MnIII,IV oxide, rather than Mn3II,III,IIIO4, is the phase pertinent to the observed OER activity. PMID:23758050

  18. Orientation of the oxygen-evolving manganese complex in a photosystem II membrane preparation: an X-ray absorption spectroscopy study.

    PubMed

    Mukerji, I; Andrews, J C; DeRose, V J; Latimer, M J; Yachandra, V K; Sauer, K; Klein, M P

    1994-08-16

    X-ray absorption spectroscopy has been performed on oriented photosystem II membrane particles isolated from spinach. Structural features of the tetranuclear Mn cluster and the orientation of the cluster with respect to the lipid bilayer were determined in both the S1 and S2 states of the Kok cycle. Variation of the sample orientation with respect to the X-ray e-vector yields highly dichroic K-edge and extended X-ray absorption fine structure spectra (EXAFS), indicative of an asymmetric tetranuclear cluster. Mn-Mn vectors at 2.72 and 3.38 A can be resolved from these measurements using quantitative analysis. The 2.72-A vector, consisting of at least two component vectors, is oriented at an average angle of 60 degrees +/- 7 degrees to the membrane normal, with an average of 1.1 +/- 0.1 interactions per Mn atom. The 3.38-A vector, most probably an average of two vectors, makes an angle of 43 degrees +/- 10 degrees with respect to the membrane normal, with an average of 0.45 +/- 0.07 backscatterer per Mn atom. Upon advance to the S2 state, the orientation of these vectors and the average numbers of backscatterers are approximately invariant. Analysis of more subtle features of the EXAFS reveals changes accompanying this S-state advance that are consistent with the oxidation of Mn during this transition. However, the dominant structural features of the oxygen-evolving complex remain constant in the S1 and S2 states. The structure of the Mn complex and the orientation of the complex in the membrane within the context of dichroism of the X-ray absorption data are discussed.

  19. Structure of the manganese complex of photosystem II upon removal of the 33-kilodalton extrinsic protein: an X-ray absorption spectroscopy study.

    PubMed

    Cole, J L; Yachandra, V K; McDermott, A E; Guiles, R D; Britt, R D; Dexheimer, S L; Sauer, K; Klein, M P

    1987-09-22

    The structure of the Mn complex of photosystem II (PSII) was studied by X-ray absorption spectroscopy. Oxygen-evolving spinach PSII membranes containing 4-5 Mn/PSII were treated with 0.8 M CaCl2 to extract the 33-, 24-, and 16-kilodalton (kDa) extrinsic membrane proteins. Mn was not released by this treatment, but subsequent incubation at low Cl- concentration generated preparations containing 2 Mn/PSII. The Mn X-ray absorption K-edge spectrum of the CaCl2-washed preparation containing 4 Mn/PSII is very similar to spectrum of native PSII, indicating that the oxidation states and ligand symmetry of the Mn complex in these preparations are not significantly different. The Mn extended X-ray absorption fine structure (EXAFS) of CaCl2-washed PSII fits to a Mn neighbor at approximately 2.75 A and two shells of N or O at approximately 1.78 and approximately 1.92 A. These distances are similar to those we have previously reported for native PSII preparations [Yachandra, V. K., Guiles, R. D., McDermott, A. E., Cole, J. L., Britt, R. D., Dexheimer, S. L., Sauer, K., & Klein, M. P. (1987) Biochemistry (following paper in this issue)] and are indicative of an oxo-bridged Mn complex. Our results demonstrate that the structure of the Mn complex is largely unaffected by removal of 33-, 24-, and 16-kDa extrinsic proteins, do not provide ligands to Mn. The Mn K-edge spectrum of the CaCl2-washed sample containing 2 Mn/PSII has a dramatically altered shape, and the edge inflection point is shifted to lower energy. The position of the edge is consistent with a Mn oxidation state of +3.(ABSTRACT TRUNCATED AT 250 WORDS)

  20. Determining the Uncertainty of X-Ray Absorption Measurements

    PubMed Central

    Wojcik, Gary S.

    2004-01-01

    X-ray absorption (or more properly, x-ray attenuation) techniques have been applied to study the moisture movement in and moisture content of materials like cement paste, mortar, and wood. An increase in the number of x-ray counts with time at a location in a specimen may indicate a decrease in moisture content. The uncertainty of measurements from an x-ray absorption system, which must be known to properly interpret the data, is often assumed to be the square root of the number of counts, as in a Poisson process. No detailed studies have heretofore been conducted to determine the uncertainty of x-ray absorption measurements or the effect of averaging data on the uncertainty. In this study, the Poisson estimate was found to adequately approximate normalized root mean square errors (a measure of uncertainty) of counts for point measurements and profile measurements of water specimens. The Poisson estimate, however, was not reliable in approximating the magnitude of the uncertainty when averaging data from paste and mortar specimens. Changes in uncertainty from differing averaging procedures were well-approximated by a Poisson process. The normalized root mean square errors decreased when the x-ray source intensity, integration time, collimator size, and number of scanning repetitions increased. Uncertainties in mean paste and mortar count profiles were kept below 2 % by averaging vertical profiles at horizontal spacings of 1 mm or larger with counts per point above 4000. Maximum normalized root mean square errors did not exceed 10 % in any of the tests conducted. PMID:27366627

  1. Correlation of X-Ray Absorption Parameters with Schultz index

    NASA Astrophysics Data System (ADS)

    Kekre, Pravin A.; Khatri, Sunil; Mishra, A.; Joshi, K. P.

    2012-05-01

    A novel application of topological Index in estimating some X-ray parameters is described. X-Ray Absorption parameters (Chemical Shift and Effective Charge) are correlated with Schultz index. Some Cobalt (II) complexes were used to establish this type of correlation. The result have indicated that the chemical shift and effective charge are sensitive to the topological structure of coordinating ligand moieties. The topological understanding of molecular properties can lead to the development of new areas of present and future interest. i.e. designing of new drugs, tracking the effects of pollutants in environment and the prediction of carcinogenicity of a molecule.

  2. Applications of X-ray absorption spectroscopy and low temperature XMCD to metalloproteins

    SciTech Connect

    Christiansen, J.H. |

    1996-01-01

    The author has used the extended X-ray absorption fine structure (EXAFS) and ultra-low temperature X-ray magnetic circular dichroism (XMCD) to study the environments of the metal sites in metalloproteins. EXAFS has been used to study the Zn site in spinach carbonic anhydrase. The EXAFS, in parallel with site directed mutagenesis studies, indicate that the active site Zn is in a cys-cys-his-H{sub 2}O environment, very different from the mammalian carbonic anhydrase active site. Nitrogenase, the primary enzyme in biological nitrogen fixation, contains two complex metal clusters of unique structure. EXAFS studies at the Fe and Mo K-edges of nitrogenase solutions and crystals yielded information about the various metal-metal distances in these two clusters. The author assigned 4 Fe and 3 Mo interactions >4 {angstrom}. Single crystal Mo K-edge EXAFS then found a very long Fe-Fe distance of {approximately}5.1 {angstrom}. These distances were then used to further refine the proposed crystallographic models to their highest accuracy yet. Studies were carried further by examining nitrogenas in oxidized and reduced forms--states for which there is no crystallographic information. Small structural changes were observed and an EXAFS model was put forth that attempts to deconvolute the EXAFS distances of the two metal clusters. Nitrogenase Apo I, a genetic mutant of nitrogenase which is though to contain only one of the two different metal clusters, was also examined using EXAFS. These studies showed results consistent with current models, yet the metal clusters were very disordered. Finally, ultra-low temperature methods were used to further the development of XMCD as a technique for studying biological systems. Experiments were performed on the copper in plastocyanin. Data was collected that definitively proves that the sample surface was at 0.55 {+-} 0.05 K. This result opens the door to further study of more complex biological metal clusters.

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

    PubMed

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

    2014-11-12

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

  4. Fluorescence X-ray absorption spectroscopy using a Ge pixel array detector: application to high-temperature superconducting thin-film single crystals.

    PubMed

    Oyanagi, H; Tsukada, A; Naito, M; Saini, N L; Lampert, M O; Gutknecht, D; Dressler, P; Ogawa, S; Kasai, K; Mohamed, S; Fukano, A

    2006-07-01

    A Ge pixel array detector with 100 segments was applied to fluorescence X-ray absorption spectroscopy, probing the local structure of high-temperature superconducting thin-film single crystals (100 nm in thickness). Independent monitoring of pixel signals allows real-time inspection of artifacts owing to substrate diffractions. By optimizing the grazing-incidence angle theta and adjusting the azimuthal angle phi, smooth extended X-ray absorption fine structure (EXAFS) oscillations were obtained for strained (La,Sr)2CuO4 thin-film single crystals grown by molecular beam epitaxy. The results of EXAFS data analysis show that the local structure (CuO6 octahedron) in (La,Sr)2CuO4 thin films grown on LaSrAlO4 and SrTiO3 substrates is uniaxially distorted changing the tetragonality by approximately 5 x 10(-3) in accordance with the crystallographic lattice mismatch. It is demonstrated that the local structure of thin-film single crystals can be probed with high accuracy at low temperature without interference from substrates.

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

    SciTech Connect

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

    2003-10-01

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

  6. Simultaneous surface plasmon resonance and x-ray absorption spectroscopy

    SciTech Connect

    Serrano, A.; Rodriguez de la Fuente, O.; Collado, V.; Rubio-Zuazo, J.; Castro, G. R.; Monton, C.; Garcia, M. A.

    2012-08-15

    We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10{sup -3} to 10{sup -5}, depending on the particular experiment.

  7. Imide photodissociation investigated by X-ray absorption spectroscopy.

    PubMed

    Johnson, Phillip S; Cook, Peter L; Liu, Xiaosong; Yang, Wanli; Bai, Yiqun; Abbott, Nicholas L; Himpsel, F J

    2012-06-21

    X-ray absorption spectroscopy is used to investigate the photodissociation of the imides PMDI (pyromellitic diimide) and SSMCC (sulfosuccinimidyl 4-(N-maleimidomethyl) cyclohexane-1-carboxylate). PMDI contains only one type of imide, and its photodissociation can be explained by a simple conversion from imide to a mix of imine and nitrile after desorption of the oxygens from the imide. SSMCC contains two different imides. One reacts like PMDI, the other in a more complex multistep process. Eventually, N(2) is formed in the bulk of the sample at high radiation density. The sequence of reactions is inferred from the π* peaks in total electron yield and fluorescence yield absorption spectra at the N 1s and O 1s edges. First-order rate equations are used to model the evolution of the peak areas versus radiation dose.

  8. Investigating DNA Radiation Damage Using X-Ray Absorption Spectroscopy

    PubMed Central

    Czapla-Masztafiak, Joanna; Szlachetko, Jakub; Milne, Christopher J.; Lipiec, Ewelina; Sá, Jacinto; Penfold, Thomas J.; Huthwelker, Thomas; Borca, Camelia; Abela, Rafael; Kwiatek, Wojciech M.

    2016-01-01

    The biological influence of radiation on living matter has been studied for years; however, several questions about the detailed mechanism of radiation damage formation remain largely unanswered. Among all biomolecules exposed to radiation, DNA plays an important role because any damage to its molecular structure can affect the whole cell and may lead to chromosomal rearrangements resulting in genomic instability or cell death. To identify and characterize damage induced in the DNA sugar-phosphate backbone, in this work we performed x-ray absorption spectroscopy at the P K-edge on DNA irradiated with either UVA light or protons. By combining the experimental results with theoretical calculations, we were able to establish the types and relative ratio of lesions produced by both UVA and protons around the phosphorus atoms in DNA. PMID:27028640

  9. X-ray absorption variability in NGC 4507

    NASA Astrophysics Data System (ADS)

    Marinucci, Andrea; Risaliti, Guido; Wang, Junfeng; Bianchi, Stefano; Elvis, Martin; Matt, Giorgio; Nardini, Emanuele; Braito, Valentina

    2013-03-01

    We present a complete spectral analysis of an XMM-Newton and Chandra campaign of the obscured AGN in NGC 4507, consisting of six observations spanning a period of six months, ranging from 2010 June to December. We detect strong absorption variability on time-scales between 1.5 and 4 months, suggesting that the obscuring material consists of gas clouds at parsec-scale distance. The lack of significant variability on shorter time-scales suggests that this event is not due to absorption by broad-line region (BLR) clouds, which was instead found in other studies of similar sources. This shows that a single, universal structure of the absorber (either BLR clouds, or the parsec-scale torus) is not enough to reproduce the observed complexity of the X-ray absorption features of this AGN.

  10. Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

    SciTech Connect

    Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; Li, Jing; Stach, Eric A.; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S.; Takeuchi, Kenneth J.; Marschilok, Amy C.

    2016-06-06

    Copper ferrite, CuFe2 O 4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2 O 4. A phase pure tetragonal CuFe2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(II) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(III) cations to octahedral positions previously occupied by copper(II). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

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

    SciTech Connect

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

    2016-03-01

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

  12. Magnetic and structural properties of Fe/Pd multilayers studied by magnetic x-ray dichroism and x-ray absorption spectroscopy

    SciTech Connect

    Mini, S.M. |; Fullerton, E.E.; Sowers, C.H.; Fontaine, A.; Pizzini, S.; Bommannavar, A.S.; Traverse, A.; Baudelet, F.

    1994-12-01

    The results of magnetic circular x-ray dichroism (MCXD) measurements and extended x-ray absorption fine structure measurements (EXAFS) of the Fe K-edges of textured Fe(110)/Pd(111) multilayers are reported. The EXAFS results indicates that the iron in the system goes from bcc to a more densely packed system as the thickness of the iron layer is decreased. The magnetic properties were measured by SQUID magnetometry from 5-350 K. For all the samples, the saturation magnetization was significantly enhanced over the bulk values indicating the interface Pd atoms are polarized by the Fe layer. The enhancement corresponds to a moment of {approx}2.5{mu}{sub B} per interface Pd atom.

  13. The irradiation of ammonia ice studied by near edge x-ray absorption spectroscopy

    SciTech Connect

    Parent, Ph.; Bournel, F.; Lasne, J.; Laffon, C.; Carniato, S.; Lacombe, S.; Strazzulla, G.; Gardonio, S.; Lizzit, S.; Kappler, J.-P.; Joly, L.

    2009-10-21

    A vapor-deposited NH{sub 3} ice film irradiated at 20 K with 150 eV photons has been studied with near-edge x-ray absorption fine structure (NEXAFS) spectroscopy at the nitrogen K-edge. Irradiation leads to the formation of high amounts (12%) of molecular nitrogen N{sub 2}, whose concentration as a function of the absorbed energy has been quantified to 0.13 molecule/eV. The stability of N{sub 2} in solid NH{sub 3} has been also studied, showing that N{sub 2} continuously desorbs between 20 and 95 K from the irradiated ammonia ice film. Weak concentrations (<1%) of other photoproducts are also detected. Our NEXAFS simulations show that these features own to NH{sub 2}, N{sub 2}H{sub 2}, and N{sub 3}{sup -}.

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

    SciTech Connect

    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.

  15. Uranium and thorium sorption on minerals studied by x-ray absorption spectroscopy

    SciTech Connect

    Hudson, E.A.; Terminello, L.J.; Viani, B.E.

    1995-12-01

    Several actinide-mineral sorption systems were studied by uranium and thorium L{sub 3}-edge x-ray absorption spectroscopy. A series of layer silicate minerals, including micas, were selected for their systematic variations in surface structure, e.g. degree of permanent negative charge on the basal planes. An expansible layer silicate, vermiculite, was treated to provide several different interlayer spacings, allowing variations in the accessibility of interior cation exchange sites. The finely powdered minerals were exposed to aqueous solutions of uranyl chloride or thorium chloride. Analysis of the EXAFS and XANES spectra indicates the influence of the mineral substrate upon the local structure of the bound actinide species. Trends in the data are interpreted based upon the known variations in mineral structure.

  16. Deactivation Mechanisms of Ni-Based Tar Reforming Catalysts As Monitored by X-ray Absorption Spectroscopy

    SciTech Connect

    Yung, Matthew M.; Kuhn, John N.

    2010-12-06

    Deactivation mechanisms of alumina-supported, Ni-based catalysts for tar reforming in biomass-derived syngas were evaluated using extended X-ray absorption fine structure (EXAFS) spectroscopy. Catalysts were characterized before and after catalytic reaction cycles and regeneration procedures, which included oxidation by a mixture of steam and air, and reduction in hydrogen. Qualitative analysis of the EXAFS spectra revealed that oxidation of a portion of the Ni in the catalysts to form an oxide phase and/or a sulfide phase were likely scenarios that led to catalyst deactivation with time-on-stream and with increased reaction cycles. Deactivation through carbon deposition, phosphorus poisoning, or changes in particle size were deemed as unlikely causes. Quantitative analysis of the EXAFS spectra indicated sulfur poisoning occurred with time-on-stream, and the contaminating species could not be completely removed during the regeneration protocols. The results also verified that Ni-containing oxide phases (most likely a spinel also containing Mg and Al) formed and contributed to the deactivation. This study validates the need for developing catalyst systems that will protect Ni from sulfur poisoning and oxide formation at elevated reaction and regeneration temperatures.

  17. Deactivation mechanisms of Ni-based tar reforming catalysts as monitored by X-ray absorption spectroscopy.

    PubMed

    Yung, Matthew M; Kuhn, John N

    2010-11-02

    Deactivation mechanisms of alumina-supported, Ni-based catalysts for tar reforming in biomass-derived syngas were evaluated using extended X-ray absorption fine structure (EXAFS) spectroscopy. Catalysts were characterized before and after catalytic reaction cycles and regeneration procedures, which included oxidation by a mixture of steam and air, and reduction in hydrogen. Qualitative analysis of the EXAFS spectra revealed that oxidation of a portion of the Ni in the catalysts to form an oxide phase and/or a sulfide phase were likely scenarios that led to catalyst deactivation with time-on-stream and with increased reaction cycles. Deactivation through carbon deposition, phosphorus poisoning, or changes in particle size were deemed as unlikely causes. Quantitative analysis of the EXAFS spectra indicated sulfur poisoning occurred with time-on-stream, and the contaminating species could not be completely removed during the regeneration protocols. The results also verified that Ni-containing oxide phases (most likely a spinel also containing Mg and Al) formed and contributed to the deactivation. This study validates the need for developing catalyst systems that will protect Ni from sulfur poisoning and oxide formation at elevated reaction and regeneration temperatures.

  18. Large-Area Chemically Modified Graphene Films: Electrophoretic Deposition and Characterization by Soft X-ray Absorption Spectroscopy

    SciTech Connect

    Lee, V.; Whittaker, L; Jaye, C; Baroudi, K; Fischer, D; Banerjee, S

    2009-01-01

    A facile, rapid, and scalable electrophoretic deposition approach is developed for the fabrication of large-area chemically derived graphene films on conductive substrates based on the electrophoretic deposition of graphene oxide and reduced graphene oxide components. Two distinctive approaches for fabricating conformal graphene films are developed. In the first approach, graphene oxide sheets are electrophoretically deposited from an aqueous solution after the oxidation of graphite to graphite oxide and the subsequent exfoliation of graphite oxide to graphene oxide. Next, the graphene oxide films are reduced via dip-coating in an aqueous solution of hydrazine. In the second approach, graphene oxide is reduced to graphene nanosheets in a strongly alkaline solution and the reduced graphene sheets are directly electrophoretically deposited onto conductive substrates. The film thickness can be modified by the deposition time and the obtained films span several square millimeters in area. Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is used to study the surface chemistry, electronic band structure, and degree of alignment of the electrophoretically deposited films. Polarized NEXAFS measurements verify the presence of epoxide surface functionalities on the graphene basal planes and indicate significant recovery of extended p-bonded networks upon defunctionalization by hydrazine treatment. These measurements further indicate significantly improved alignment of the graphene sheet components of the films parallel to the substrate surface when defunctionalization is performed prior to electrophoretic deposition.

  19. Orientation and electronic structure of ion exchanged dye molecules on mica: An X-ray absorption study

    SciTech Connect

    Fischer, D.; Caseri, W.R.; Haehner, G.

    1998-02-15

    Dye molecules are frequently used to determine the specific surface area and the ion exchange capacity of high-surface-area materials such as mica. The organic molecules are often considered to be planar and to adsorb in a flat orientation. In the present study the authors have investigated the orientation and electronic structure of crystal violet (CV) and malachite green (MG) on muscovite mica, prepared by immersing the substrates for extended periods into aqueous solutions of the dyes of various concentrations. The K{sup +} ions of the mica surface are replaced by the organic cations via ion exchange. X-ray photoelectron spectroscopy reveals that only one amino group is involved in the interaction of CV and MG with the muscovite surface, i.e., certain resonance structures are abolished upon adsorption. With near edge X-ray absorption fine structure spectroscopy a significant tilt angle with respect to the surface was found for all investigated species. A flat orientation, as has often been proposed before, can effectively be ruled out. Hence, results are in marked contrast to the often quoted orientation and suggest that the specific surface areas determined with dyes may, in general, be overestimated.

  20. X-ray Absorption Spectroscopy of the Rare Earth orthophosphates

    SciTech Connect

    Shuh, D.K.; Terminello, L.J.; Boatner, L.A.; Abraham, M.M.

    1993-06-01

    X-ray Absorption Spectroscopy (XAS) of the Rare Earth (RE) 3d levels yields sharp peaks near the edges as a result of strong, quasi-atomic 3d{sup 10}4f{sup n} {yields} 3d-{sup 9}4f{sup n+1} transitions and these transitions exhibit a wealth of spectroscopic features. The XAS measurements of single crystal REPO{sub 4} (RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er) at the 3d edge were performed in the total yield mode at beam line 8-2 at the Stanford Synchrotron Radiation Laboratory (SSRL). The XAS spectra of the RE ions in the orthophosphate matrix generally resemble the XAS of the corresponding RE metal. This is not unexpected and emphasizes the major contribution of the trivalent state to the electronic transitions at the RE 3d edges. These spectra unequivocally identify the transitions originating from well-characterized RE cores and correlate well with previous theoretical investigations.

  1. Reactions of Highly Uniform Zeolite H-Supported Rhodium Complexes: Transient Characterization by Infrared and X-ray Absorption Spectroscopies

    SciTech Connect

    Ogino, I.; Gates, B

    2010-01-01

    A zeolite H-{beta}-supported mononuclear rhodium diethene complex (Rh(C{sub 2}H{sub 4}){sub 2}{l_brace}O{sub 2}Al{r_brace}, where the braces indicate a part of the zeolite) was formed by the reaction of Rh(acac)({eta}{sub 2}-C{sub 2}H{sub 4}){sub 2} (acac = acetylacetonate, C{sub 5}H{sub 7}O{sub 2}{sup -}) with the zeolite. Transient characterization of the sample by X-ray absorption near edge structure (XANES) and infrared (IR) spectroscopies (combined with mass spectrometry of the effluent gas) while the sample was in contact with flowing CO indicates a simple stoichiometric conversion of the supported metal complex into another species, identified by the spectra as the zeolite-supported rhodium gem-dicarbonyl (Rh(CO){sub 2}{l_brace}O{sub 2}Al{r_brace}). The sharpness of the v{sub CO} bands in the IR spectrum indicates a high degree of uniformity of the supported rhodium gem-dicarbonyl, and isosbestic points in the XANES spectra as the transformation was occurring imply that the rhodium diethene complex was also highly uniform. Spectra similarly show that treatment of the supported rhodium gem-dicarbonyl with flowing C{sub 2}H{sub 4} resulted in another stoichiometrically simple transformation, giving a species suggested to be Rh(C{sub 2}H{sub 4})(CO){sub 2}{l_brace}O{sub 2}Al{r_brace}. The intermediate was ultimately transformed when the sample was purged with helium into another highly uniform supported species, inferred on the basis of IR spectra to be Rh(C{sub 2}H{sub 4})(CO){l_brace}O{sub 2}Al{r_brace}. Extended X-ray absorption fine structure spectra characterizing the supported rhodium diethene complex and the species formed from it show how the Rh-O bond distance at the Rh-support interface varied in response to the changes in the ligands bonded to the rhodium.

  2. Simulation of X-ray absorption spectra with orthogonality constrained density functional theory†

    PubMed Central

    Derricotte, Wallace D.; Evangelista, Francesco A.

    2015-01-01

    Orthogonality constrained density functional theory (OCDFT) is a variational time-independent approach for the computation of electronic excited states. In this work we extend OCDFT to compute core-excited states and generalize the original formalism to determine multiple excited states. Benchmark computations on a set of 13 small molecules and 40 excited states show that unshifted OCDFT/B3LYP excitation energies have a mean absolute error of 1.0 eV. Contrary to time-dependent DFT, OCDFT excitation energies for first- and second-row elements are computed with near-uniform accuracy. OCDFT core excitation energies are insensitive to the choice of the functional and the amount of Hartree–Fock exchange. We show that OCDFT is a powerful tool for the assignment of X-ray absorption spectra of large molecules by simulating the gas-phase near-edge spectrum of adenine and thymine. PMID:25690350

  3. Studies on the Structural Transformation of Pt Clusters with Adsorbed Hydrogen on α-Al2O3(0001) Using Multiple Scattering Approach to Pt L3-edge Polarized X-Ray Absorption Near Edge Structure Spectra for the Pt Cluster

    NASA Astrophysics Data System (ADS)

    Ohtani, Kunihiro

    1998-03-01

    The X-ray absorption near edge structure (XANES) or the Extended X-ray absorption fine structure (EXAFS) study with polarization dependence is useful for determining the structures of the metal clusters. We have calculated Pt L3-edge XANES spectra for various structures of Pt clusters with adsorbed hydrogen, such as the one-layer-thick raft, and the hemispherical and spherical structures on α-Al2O3(0001), using the full multiple scattering approach. Comparison of the calculated results with the experimental results have yielded important information. With an increase in the spherically symmetric character of Pt clusters, the influence of Pt-support interaction on the XANES spectra decreases, that is, the hydrogen-Pt interaction plays a dominant role in such cases. We expect that Pt clusters with the one-layer-thick raft, or hemispherical structures are on the top site of surface oxygen atoms.

  4. Synthesis and reactivity of dimethyl gold complexes supported on MgO: characterization by infrared and X-ray absorption spectroscopies.

    PubMed

    Guzman, Javier; Anderson, Bruce G; Vinod, C P; Ramesh, Kanaparthi; Niemantsverdriet, J W; Gates, Bruce C

    2005-04-12

    Dimethyl gold complexes bonded to partially dehydroxylated MgO powder calcined at 673 K were synthesized by adsorption of Au(CH3)2(acac) (acac is C5H7O2) from n-pentane solution. The synthesis and subsequent decomposition of the complexes by treatment in He or H2 were characterized with diffuse reflectance Fourier transform infrared (DRIFT), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies. The XANES results identify Au(III) in the supported complexes, and the EXAFS and DRIFTS data indicate mononuclear dimethyl gold complexes as the predominant surface gold species, consistent with the lack of Au-Au contributions in the EXAFS spectrum and the presence of nu(as)(CH3) and nu(s)(CH3) bands in the IR spectrum. EXAFS data show that each complex is bonded to two oxygen atoms of the MgO surface at an Au-O distance of 2.16 angstroms. The DRIFT spectra show that reaction of Au(CH3)2(acac) with MgO at room temperature also formed Mg(acac)2 and H(acac) species on the support. Treatment of the dimethyl gold complexes in He or H2 at increasing temperatures varying from 373 to 573 K removed CH3 ligands and caused aggregation forming zerovalent gold nanoclusters of increasing size, ultimately with an average diameter of about 30 angstroms. Analysis of the gas-phase products during the genesis of the gold clusters indicated formation of CH4 (consistent with removal of CH3 groups) and CO2 at 473-573 K, associated with decomposition of the organic ligands derived from acac species. O2 and CO2 were also formed in the decomposition of ubiquitous carbonates present on the surface of the MgO support.

  5. Determination of the local structure of CsBi4-xPbxTe6 (x = 0, 0.5) by X-ray absorption spectroscopy.

    PubMed

    Wakita, Takanori; Paris, Eugenio; Mizokawa, Takashi; Hacisalihoglu, Muammer Yasin; Terashima, Kensei; Okazaki, Hiroyuki; Proux, Olivier; Kieffer, Isabelle; Lahera, Eric; Del Net, William; Olivi, Luca; Takano, Yoshihiko; Muraoka, Yuji; Yokoya, Takayoshi; Saini, Naurang L

    2016-09-14

    We have studied the local structure and valence electronic unoccupied states of thermoelectric CsBi4Te6 and superconducting CsBi3.5Pb0.5Te6 (Tc ∼ 3 K) by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) measurements. The Bi-L3 edge EXAFS reveals wide Bi-Te distance distribution for both compounds indicating complex atomic arrangements in the studied system. The mean square relative displacements (MSRDs) of the Bi-Te bond distances appear largely increased in Pb substituted system due to larger overall local disorder, however, one of the Bi-Te bonds shows a reduced disorder. On the other hand, the Bi-L3 edge XANES is hardly affected by Pb substitution while the Te-L1 edge XANES reveals increased density of unoccupied Te 5p states. This suggests that the carriers introduced by the Pb substitution in CsBi4-xPbxTe6 preferentially goes on Te sites. Similarly, the Cs-L3 edge XANES also shows small changes due to Pb-substitution and reduced local disorder indicated by the reduced width of the Cs-L3 edge white line. We have also shown that the X-ray photoemission spectroscopy (XPS) measurements on various electronic core levels are in a qualitative agreement with the XANES results. These findings are consistent with carrier doping and a reduced disorder in one direction to be likely factors to drive the thermoelectric CsBi4Te6 into a bulk superconductor by Pb-substitution in CsBi4-xPbxTe6.

  6. Temperature and high-pressure dependent x-ray absorption of SmNiO3 at the Ni K and Sm L3 edges

    NASA Astrophysics Data System (ADS)

    Massa, Néstor E.; Ramos, Aline Y.; Tolentino, Helio C. N.; Sousa-Neto, Narcizo M.; Fonseca, Jairo, Jr.; Alonso, José Antonio

    2015-12-01

    We report on x-ray absorption near-edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) measurements of SmNiO3 from 20 K to 600 K and up to 38 GPa at the Ni K and Sm L3 edges. A multiple component pre-Ni K edge tail is understood, originating from 1 s transitions to 3d-4p states while a post-edge shoulder increases distinctively smoothly, at about the insulator to metal phase transition (TIM), due to the reduction of electron-phonon interactions as the Ni 3d and O 2p band overlap triggers the metallic phase. This effect is concomitant with pressure-induced Ni-O-Ni angle increments toward more symmetric Ni3+ octahedra of the rhombohedral R¯3c space group. Room temperature pressure-dependent Ni white line peak energies have an abrupt ˜3.10 ± 0.04 GPa valence discontinuity from non-equivalent Ni3+δ + Ni3-δ charge disproportionate net unresolved absorber turning at ˜TIM into Ni3+ of the orthorhombic Pbnm metal oxide phase. At 20 K the overall white line response, still distinctive at TIM ˜8.1 ± 0.6 GPa is much smoother due to localization. Octahedral bond contraction up to 38 GPa and at 300 K and 20 K show breaks in its monotonic increase at the different structural changes. The Sm L3 edge does not show distinctive behaviors either at 300 K or 20 K up to about 35 GPa but the perovskite Sm cage, coordinated to eight oxygen atoms, undergoes strong uneven bond contractions at intermediate pressures where we found the coexistence of octahedral and rhombohedral superexchange angle distortions. We found that the white line pressure-dependent anomaly may be used as an accurate alternative for delineating pressure-temperature phase diagrams.

  7. Polarized X-ray absorption spectroscopy of metal ions in minerals

    NASA Astrophysics Data System (ADS)

    Waychunas, G. A.; Brown, G. E.

    1990-12-01

    We have made use of the nearly complete linear polarization of synchrotron radiation to study the polarization dependence of X-ray absorption near-edge structure (XANES) and extended fine structure (EXAFS) in oriented single crystals of gillespite (BaFe2+ Si4O10; Fe2 + in square-planar coordination, point symmetry C 4), anatase (TiO2; Ti4+ in octahedral coordination, point symmetry D 2d), and epidote (Ca2(Al, Fe3+)3SiO4)3(OH); Fe3+ in distorted octahedral coordination, point symmetry ( C s). For gillespite, the Fe K-XANES spectrum varies strongly with E-vector orientation of the incident X-ray beam. When the E-vector lies in the plane of the FeO4 group (i.e., perpendicular to the c-axis), multiple-scattering features at 7127 and 7131 eV intensify, whereas when the E-vector is perpendicular to the plane of the FeO4 group (i.e., parallel to the c-axis), a strongly-polarized 1 s to 4p bound state transition occurs at 7116 eV and a localized continuum resonance occurs at 7122 eV. The Fe-K-EXAFS spectrum of gillespite is also highly polarization dependent. When the E-vector is perpendicular to c, all four nearest-neighbor oxygens around Fe2+ contribute to the EXAFS signal; when E is parallel to c, the EXAFS signal from nearest-neighbors is reduced by at least 86%. The unpolarized Ti K-XANES spectrum of anatase has three relatively strong pre-edge features at 4967.1, 4969.9, and 4972.7 eV which have resisted definitive interpretation in past studies. The lowest energy feature has a strong xy polarization dependence, suggesting a large amount of 4 p x,y character, and it is also very sharp, indicating a well-defined transition energy. Both of these observations are consistent with an excitonic state with a binding energy of 2.8 eV. The two higher energy features, which are characteristic of octahedrally-coordinated Ti4+, show little polarization dependence and are probably due to 1 s to 3 d bound-state transitions, with a small degree of np character in the final state

  8. Correlation between structure and magnetic spin state of the manganese cluster in the oxygen-evolving complex of photosystem II in the S2 state: determination by X-ray absorption spectroscopy.

    PubMed

    Liang, W; Latimer, M J; Dau, H; Roelofs, T A; Yachandra, V K; Sauer, K; Klein, M P

    1994-04-26

    The structure of the manganese cluster in the S2 state with the g approximately 4 EPR signal (S2-g4 state) generated by 130 K illumination of photosystem II (PSII) membranes prepared from spinach has been investigated by X-ray absorption spectroscopy. The Mn X-ray absorption K-edge spectra of the S2-g4 state not only show a shift of the inflection point to higher energy from the S1 state but also reveal a different edge shape from that of the S2 state with the multiline signal (S2-MLS state). Extended X-ray absorption fine structure (EXAFS) studies of the Mn K-edge show that the structure of the Mn cluster in the S2-g4 state is distinctly different from those in the S2-MLS or S1 states. In the S2-g4 state, the second shell of back-scatters from the Mn absorber is found to contain two Mn-Mn distances of 2.73 and 2.85 A. We interpret this to indicate the presence of two nonequivalent di-mu-oxo-bridged Mn binuclear structures in the Mn cluster of the S2-g4 state. The third shell of the S2-g4 state at about 3.3 A also contains increased heterogeneity. By contrast, very little distance disorder was found to exist in the second shell of the S1 or S2-MLS states. A mechanism is proposed to explain these results in the context of our model for the Mn cluster and the EPR properties of the Mn complex in the S2 state.

  9. Comparison of the structure of the manganese complex in the S1 and S2 states of the photosynthetic O2-evolving complex: an x-ray absorption spectroscopy study.

    PubMed

    Yachandra, V K; Guiles, R D; McDermott, A E; Cole, J L; Britt, R D; Dexheimer, S L; Sauer, K; Klein, M P

    1987-09-22

    A Mn-containing enzyme complex is involved in the oxidation of H2O to O2 in algae and higher plants. X-ray absorption spectroscopy is well suited for studying the structure and function of Mn in this enzyme complex. Results of X-ray K-edge and extended X-ray absorption fine structure (EXAFS) studies of Mn in the S1 and S2 states of the photosynthetic O2-evolving complex in photosystem II preparations from spinach are presented in this paper. The S2 state was prepared by illumination at 190 K or by illumination at 277 K in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU); these are protocols that limit the photosystem II reaction center to one turnover. Both methods produce an S2 state characterized by a multiline electron paramagnetic resonance (EPR) signal. An additional protocol, illumination at 140 K, produces as a state characterized by the g = 4.1 EPR signal. We have previously observed a shift to higher energy in the X-ray absorption K-edge energy of Mn upon advancement from the dark-adapted S1 state to the S2 state produced by illumination at 190 K [Goodin, D. B., Yachandra, V. K., Britt, R. D., Sauer, K., & Klein, M. P. (1984) Biochim. Biophys. Acta 767, 209-216]. The Mn K-edge spectrum of the 277 K illuminated sample is similar to that produced at 190 K, indicating that the S2 state is similar when produced at 190 or 277 K.(ABSTRACT TRUNCATED AT 250 WORDS)

  10. Interstellar dust grain composition from high-resolution X-ray absorption edge structure

    NASA Astrophysics Data System (ADS)

    Corrales, Lia

    2016-06-01

    X-ray light is sufficient to excite electrons from n=1 (K-shell) and n=2 (L-shell) energy levels of neutral interstellar metals, causing a sharp increase in the absorption cross-section. Near the ionization energy, the shape of the photoelectric absorption edge depends strongly on whether the atom is isolated or bound in molecules or minerals (dust). With high resolution X-ray spectroscopy, we can directly measure the state of metals and the mineral composition of dust in the interstellar medium. In addition, the scattering contribution to the X-ray extinction cross-section can be used to gauge grain size, shape, and filling factor. In order to fully take advantage of major advances in high resolution X-ray spectroscopy, lab measurements of X-ray absorption fine structure (XAFS) from suspected interstellar minerals are required. Optical constants derived from the absorption measurements can be used with Mie scattering or anomalous diffraction theory in order to model the full extinction cross-sections from the interstellar medium. Much like quasar spectra are used to probe other intergalactic gas, absorption spectroscopy of Galactic X-ray binaries and bright stars will yield key insights to the mineralogy and evolution of dust grains in the Milky Way.

  11. X-ray absorption studies of uranium sorption on mineral substrates

    SciTech Connect

    Hudson, E.A.; Terminello, L.J.; Viani, B.E.; Reich, T.; Bucher, J.J.; Shuh, D.K.; Edelstein, N.M.

    1995-09-01

    Aqueous transport of actinides in the geosphere can be significantly retarded by sorption and/or precipitation upon mineral surfaces. Despite the importance of this effect to environmental remediation efforts and nuclear waste repository design, there is only limited direct knowledge about the microscopic nature of the actinide-mineral interaction. Here, uranium L{sub 3}-edge x-ray absorption spectra have been measured for uranium-mineral sorption systems. An expansible layer silicate, vermiculite, was treated to obtain a collapsed phase, thereby limiting access to the interior cation exchange sites. Samples were prepared by exposing the finely powdered mineral, in the natural and modified form, to aqueous solutions of uranyl chloride. EXAFS spectra of the encapsulated samples were measured at the Stanford Synchrotron Radiation Laboratory. Results indicate that the uranyl ion possesses a more symmetric local structure for the natural vermiculite than for the collapsed form, suggesting structural differences between uranyl species within the interlayer regions of vermiculite and on the external surfaces.

  12. Effects of domain size on x-ray absorption spectra of boron nitride doped graphenes

    NASA Astrophysics Data System (ADS)

    Li, Xin; Hua, Weijie; Wang, Bo-Yao; Pong, Way-Faung; Glans, Per-Anders; Guo, Jinghua; Luo, Yi

    2016-08-01

    Doping is an efficient way to open the zero band gap of graphene. The control of the dopant domain size allows us to tailor the electronic structure and the properties of the graphene. We have studied the electronic structure of boron nitride doped graphenes with different domain sizes by simulating their near-edge X-ray absorption fine structure (NEXAFS) spectra at the N K-edge. Six different doping configurations (five quantum dot type and one phase-separated zigzag-edged type) were chosen, and N K-edge NEXAFS spectra were calculated with large truncated cluster models by using the density functional theory with hybrid functional and the equivalent core hole approximation. The opening of the band gap as a function of the domain size is revealed. We found that nitrogens in the dopant boundary contribute a weaker, red-shifted π* peak in the spectra as compared to those in the dopant domain center. The shift is related to the fact that these interfacial nitrogens dominate the lowest conduction band of the system. Upon increasing the domain size, the ratio of interfacial atom decreases, which leads to a blue shift of the π* peak in the total NEXAFS spectra. The spectral evolution agrees well with experiments measured at different BN-dopant concentrations and approaches to that of a pristine h-BN sheet.

  13. Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

    DOE PAGES

    Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

    2016-06-06

    Copper ferrite, CuFe2 O 4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2 O 4. A phase pure tetragonal CuFe2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-raymore » absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(II) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(III) cations to octahedral positions previously occupied by copper(II). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

  14. Formation of a Manganese Tricarbonyl on the MgO Surface from Mn[subscript 2](CO)[subscript 10]: Characterization by Infrared, Electron Paramagnetic Resonance, and X-ray Absorption Spectroscopies

    SciTech Connect

    Khabuanchalad, Supattra; Wittayakun, Jatuporn; Lobo-Lapidus, Rodrigo J.; Stoll, Stefan; Britt, R. David; Gates, Bruce C.

    2010-12-07

    The goal of this work was to prepare structurally well-defined manganese complexes on high-area MgO powder by vapor deposition of Mn{sub 2}(CO){sub 10}. The supported species were characterized by infrared (IR), electron paramagnetic resonance (EPR), and X-ray absorption spectroscopies. The results show that when the manganese loading of the sample was 3.0 wt %, most of the Mn{sub 2}(CO){sub 10} was physisorbed, but when the loadings were less, chemisorbed species predominated, being formed by adsorption of Mn{sub 2}(CO){sub 10} on hydroxyl groups on the MgO surface. Treatment of samples containing 1.0 wt % Mn with O{sub 2} at room temperature resulted in oxidation of the manganese and the formation of surface species that are well represented as the d{sup 4} complex Mn(CO){sub 3}(Os){sub 3} (where O{sub s} is surface oxygen of MgO), as indicated by IR and extended X-ray absorption fine structure (EXAFS) spectra. The EXAFS data show Mn-C, C{triple_bond}O, and Mn-O{sub s} bond lengths as 1.90, 1.43, and 1.98 {angstrom}, respectively.

  15. Platinum Inhibits Low-Temperature Dry Lean Methane Combustion through Palladium Reduction in Pd-Pt/Al2 O3 : An In Situ X-ray Absorption Study.

    PubMed

    Nassiri, Hanieh; Lee, Kee-Eun; Hu, Yongfeng; Hayes, Robert E; Scott, Robert W J; Semagina, Natalia

    2017-01-18

    Palladium-platinum bimetallic catalysts supported on alumina with palladium/platinum molar ratios ranging from 0.25 to 4 are studied in dry lean methane combustion in the temperature range of 200 to 500 °C. Platinum addition decreases the catalyst activity, which cannot be explained by the decrease in dispersion or the structure sensitivity of the reaction. In situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy measurements have been conducted for monometallic Pd, Pt, and 2:1 Pd-Pt catalysts. Monometallic palladium is fully oxidized in the full temperature range, whereas platinum addition promotes palladium reduction, even in a reactive oxidizing environment. The Pd/PdO weight ratio in bimetallic Pd-Pt 2:1 catalysts decreases from 98/2 to 10/90 in the 200-500 °C temperature range under the reaction conditions. Thus, platinum promotes the formation of the reduced palladium phase with a significantly lower activity than that of oxidized palladium. The study sheds light on the effect of platinum on the state of the active palladium surface under low-temperature dry lean methane combustion conditions, which is important for methane-emission control devices.

  16. Simulation of X-ray absorption spectra with orthogonality constrained density functional theory.

    PubMed

    Derricotte, Wallace D; Evangelista, Francesco A

    2015-06-14

    Orthogonality constrained density functional theory (OCDFT) [F. A. Evangelista, P. Shushkov and J. C. Tully, J. Phys. Chem. A, 2013, 117, 7378] is a variational time-independent approach for the computation of electronic excited states. In this work we extend OCDFT to compute core-excited states and generalize the original formalism to determine multiple excited states. Benchmark computations on a set of 13 small molecules and 40 excited states show that unshifted OCDFT/B3LYP excitation energies have a mean absolute error of 1.0 eV. Contrary to time-dependent DFT, OCDFT excitation energies for first- and second-row elements are computed with near-uniform accuracy. OCDFT core excitation energies are insensitive to the choice of the functional and the amount of Hartree-Fock exchange. We show that OCDFT is a powerful tool for the assignment of X-ray absorption spectra of large molecules by simulating the gas-phase near-edge spectrum of adenine and thymine.

  17. Chemical shifts of K-X-ray absorption edges on copper in different compounds by X-ray absorption spectroscopy (XAS) with Synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Joseph, D.; Basu, S.; Jha, S. N.; Bhattacharyya, D.

    2012-03-01

    Cu K X-ray absorption edges were measured in compounds such as CuO, Cu(CH3CO2)2, Cu(CO3)2, and CuSO4 where Cu is present in oxidation state of 2+, using the energy dispersive EXAFS beamline at INDUS-2 Synchrotron radiation source at RRCAT, Indore. Energy shifts of ˜4-7 eV were observed for Cu K X-ray absorption edge in the above compounds compared to its value in elemental copper. The difference in the Cu K edge energy shifts in the different compounds having same oxidation state of Cu shows the effect of different chemical environments surrounding the cation in the above compounds. The above chemical effect has been quantitatively described by determining the effective charges on Cu cations in the above compounds.

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

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

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

  19. Low-dimensional systems investigated by x-ray absorption spectroscopy: a selection of 2D, 1D and 0D cases

    NASA Astrophysics Data System (ADS)

    Mino, Lorenzo; Agostini, Giovanni; Borfecchia, Elisa; Gianolio, Diego; Piovano, Andrea; Gallo, Erik; Lamberti, Carlo

    2013-10-01

    Over the last three decades low-dimensional systems have attracted increasing interest both from the fundamental and technological points of view due to their unique physical and chemical properties. X-ray absorption spectroscopy (XAS) is a powerful tool for the characterization of such kinds of systems, owing to its chemical selectivity and high sensitivity in interatomic distance determination. Moreover, XAS does not require long-range ordering, that is usually absent in low-dimensional systems. Finally, this technique can simultaneously provide information on electronic and local structural properties of the nanomaterials, significantly contributing to clarify the relation between their atomic structure and their peculiar physical properties. This review provides a general introduction to XAS, discussing the basic theory of the technique, the most used detection modes, the related experimental setups and some complementary relevant characterization techniques (diffraction anomalous fine structure, extended energy-loss fine structure, pair distribution function, x-ray emission spectroscopy, high-energy resolution fluorescence detected XAS and x-ray Raman scattering). Subsequently, a selection of significant applications of XAS to two-, one- and zero-dimensional systems will be presented. The selected low-dimensional systems include IV and III-V semiconductor films, quantum wells, quantum wires and quantum dots; carbon-based nanomaterials (epitaxial graphene and carbon nanotubes); metal oxide films, nanowires, nanorods and nanocrystals; metal nanoparticles. Finally, the future perspectives for the application of XAS to nanostructures are discussed.

  20. Ab-initio method for X-ray absorption spectra simulation of hydride molecular ions

    NASA Astrophysics Data System (ADS)

    Puglisi, Alessandra; Sisourat, Nicolas; Carniato, Stéphane

    2017-03-01

    Soft X-ray absorption spectra of molecular ions are important data for the modeling and understanding of laboratory and astrophysical plasma. In this work, we present an ab-initio method, based on the Configuration Interaction (CI) approach, for the calculations of energy positions and oscillator strengths of X-ray absorption spectra. Furthermore, we investigate the effects of the choice of the nature and number of spin-orbitals used in the CI expansion on the spectra. The method is applied on three hydride molecular ions, namely CH+, OH+ and SiH+. However, the approach proposed here is general and may thus be applied to any kind of molecular ions.

  1. X-ray absorption imaging of Hg vapour in a ceramic metal-halide lamp using synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Curry, J. J.; Adler, H. G.; MacPhee, A.; Narayanan, S.; Wang, J.

    2004-08-01

    The diagnostic technique of x-ray absorption imaging of Hg vapour in high-intensity discharge lamps has been extended. X-ray absorption imaging has been used previously to determine the time-averaged absolute Hg density (Curry J J, Sakai M and Lawler J E 1998 J. Appl. Phys. 84 3066). Now, using an intensified charge-coupled device detector and synchrotron radiation, time-resolved measurements have been made. Although no significant time-dependence was seen as a function of the electrical phase for an electronically ballasted lamp, real-time observations were made of the decaying Hg density during the cool-down period. The cold-spot temperature in a 150 W ceramic lamp containing Hg and rare-earth iodides decreased with a time constant of 48.4 s following arc extinction. The primary limitation to the sensitivity of these measurements has been identified, and methods for overcoming this limitation in future work are proposed. Other aspects of the technique are also discussed.

  2. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    PubMed

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order.

  3. Urban Airborne Lead: X-Ray Absorption Spectroscopy Establishes Soil as Dominant Source

    PubMed Central

    Pingitore, Nicholas E.; Clague, Juan W.; Amaya, Maria A.; Maciejewska, Beata; Reynoso, Jesús J.

    2009-01-01

    Background Despite the dramatic decrease in airborne lead over the past three decades, there are calls for regulatory limits on this potent pediatric neurotoxin lower even than the new (2008) US Environmental Protection Agency standard. To achieve further decreases in airborne lead, what sources would need to be decreased and what costs would ensue? Our aim was to identify and, if possible, quantify the major species (compounds) of lead in recent ambient airborne particulate matter collected in El Paso, TX, USA. Methodology/Principal Findings We used synchrotron-based XAFS (x-ray absorption fine structure) to identify and quantify the major Pb species. XAFS provides molecular-level structural information about a specific element in a bulk sample. Pb-humate is the dominant form of lead in contemporary El Paso air. Pb-humate is a stable, sorbed complex produced exclusively in the humus fraction of Pb-contaminated soils; it also is the major lead species in El Paso soils. Thus such soil must be the dominant source, and its resuspension into the air, the transfer process, providing lead particles to the local air. Conclusions/Significance Current industrial and commercial activity apparently is not a major source of airborne lead in El Paso, and presumably other locales that have eliminated such traditional sources as leaded gasoline. Instead, local contaminated soil, legacy of earlier anthropogenic Pb releases, serves as a long-term reservoir that gradually leaks particulate lead to the atmosphere. Given the difficulty and expense of large-scale soil remediation or removal, fugitive soil likely constrains a lower limit for airborne lead levels in many urban settings. PMID:19340295

  4. Site- and phase-selective x-ray absorption spectroscopy based on phase-retrieval calculation

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Tomoya; Fukuda, Katsutoshi; Matsubara, Eiichiro

    2017-03-01

    Understanding the chemical state of a particular element with multiple crystallographic sites and/or phases is essential to unlocking the origin of material properties. To this end, resonant x-ray diffraction spectroscopy (RXDS) achieved through a combination of x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) techniques can allow for the measurement of diffraction anomalous fine structure (DAFS). This is expected to provide a peerless tool for electronic/local structural analyses of materials with complicated structures thanks to its capability to extract spectroscopic information about a given element at each crystallographic site and/or phase. At present, one of the major challenges for the practical application of RXDS is the rigorous determination of resonant terms from observed DAFS, as this requires somehow determining the phase change in the elastic scattering around the absorption edge from the scattering intensity. This is widely known in the field of XRD as the phase problem. The present review describes the basics of this problem, including the relevant background and theory for DAFS and a guide to a newly-developed phase-retrieval method based on the logarithmic dispersion relation that makes it possible to analyze DAFS without suffering from the intrinsic ambiguities of conventional iterative-fitting. Several matters relating to data collection and correction of RXDS are also covered, with a final emphasis on the great potential of powder-sample-based RXDS (P-RXDS) to be used in various applications relevant to practical materials, including antisite-defect-type electrode materials for lithium-ion batteries.

  5. Site- and phase-selective x-ray absorption spectroscopy based on phase-retrieval calculation.

    PubMed

    Kawaguchi, Tomoya; Fukuda, Katsutoshi; Matsubara, Eiichiro

    2017-03-22

    Understanding the chemical state of a particular element with multiple crystallographic sites and/or phases is essential to unlocking the origin of material properties. To this end, resonant x-ray diffraction spectroscopy (RXDS) achieved through a combination of x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) techniques can allow for the measurement of diffraction anomalous fine structure (DAFS). This is expected to provide a peerless tool for electronic/local structural analyses of materials with complicated structures thanks to its capability to extract spectroscopic information about a given element at each crystallographic site and/or phase. At present, one of the major challenges for the practical application of RXDS is the rigorous determination of resonant terms from observed DAFS, as this requires somehow determining the phase change in the elastic scattering around the absorption edge from the scattering intensity. This is widely known in the field of XRD as the phase problem. The present review describes the basics of this problem, including the relevant background and theory for DAFS and a guide to a newly-developed phase-retrieval method based on the logarithmic dispersion relation that makes it possible to analyze DAFS without suffering from the intrinsic ambiguities of conventional iterative-fitting. Several matters relating to data collection and correction of RXDS are also covered, with a final emphasis on the great potential of powder-sample-based RXDS (P-RXDS) to be used in various applications relevant to practical materials, including antisite-defect-type electrode materials for lithium-ion batteries.

  6. X-ray absorption spectroscopy identifies calcium-uranyl-carbonate complexes at environmental concentrations.

    SciTech Connect

    Kelly, S. D.; Kemner, K. M.; Brooks, S. C.; Biosciences Division; ORNL

    2007-01-01

    Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO{sub 2}-CO{sub 3} complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO{sub 2}-CO{sub 3} complex. Such a complex might exist even at high calcium concentrations, as some UO{sub 2}-CO{sub 3} complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 {micro}M uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO{sub 2}-CO{sub 3} complex to approximately 0.6 and enables spectroscopic identification of the Na-UO{sub 2}-CO{sub 3} complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations.

  7. X-ray Absorption Spectroscopy Identifies Calcium-Uranyl-Carbonate Complexes at Environmental Concentrations

    SciTech Connect

    Kelly, Shelly D; Kemner, Kenneth M; Brooks, Scott C

    2007-01-01

    Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO2-CO3 complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO2-CO3 complex. Such a complex might exist even at high calcium concentrations, as some UO2-CO3 complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 lM uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO2-CO3 complex to approximately 0.6 and enables spectroscopic identification of the Na-UO2-CO3 complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations.

  8. Status of the X-Ray Absorption Spectroscopy (XAS) Beamline at the Australian Synchrotron

    NASA Astrophysics Data System (ADS)

    Glover, C.; McKinlay, J.; Clift, M.; Barg, B.; Boldeman, J.; Ridgway, M.; Foran, G.; Garret, R.; Lay, P.; Broadbent, A.

    2007-02-01

    We present herein the current status of the X-ray Absorption Spectroscopy (XAS) Beamline at the 3 GeV Australian Synchrotron. The optical design and performance, details of the insertion device (Wiggler), end station capabilities and construction and commissioning timeline are given.

  9. Sequential electronic and structural transitions in VO2 observed using X-ray absorption spectromicroscopy.

    PubMed

    Kumar, Suhas; Strachan, John Paul; Pickett, Matthew D; Bratkovsky, Alexander; Nishi, Yoshio; Williams, R Stanley

    2014-11-26

    The popular dual electronic and structural transitions in VO2 are explored using X-ray absorption spectromicroscopy with high spatial and spectral resolutions. It is found that during both heating and cooling, the electronic transition always precedes the structural Peierls transition. Between the two transitions, there are intermediate states that are spectrally isolated here.

  10. High Pressure X-ray Absorption Studies on Correlated-Electron Systems

    SciTech Connect

    Cornelius, Andrew L.

    2016-08-26

    This project used high pressure to alter the electron-electron and electron-lattice interactions in rare earth and actinide compounds. Knowledge of these properties is the starting points for a first-principles understanding of electronic and electronically related macroscopic properties. The research focused on a systematic study of x-ray absorption measurements on rare earth and actinide compounds.

  11. Ligand effects on the X-ray absorption of a nickel porphyrin complex: a simulation study

    NASA Astrophysics Data System (ADS)

    Campbell, Luke; Tanaka, Satoshi; Mukamel, Shaul

    2004-04-01

    We present a simulation of the X-ray absorption near-edge spectrum (XANES) of the metal porphyrin NiTPP (nickel tetraphenylporphyrin) and investigate the changes to the spectrum caused by adding piperidine ligands to the metal atom. The main features in the experimental spectrum (Chen et al., Science 292 (2001) 262) are interpreted in terms of changes in the electronic structure.

  12. LISA: the Italian CRG beamline for x-ray Absorption Spectroscopy at ESRF

    NASA Astrophysics Data System (ADS)

    d'Acapito, F.; Trapananti, A.; Puri, A.

    2016-05-01

    LISA is the acronym of Linea Italiana per la Spettroscopia di Assorbimento di raggi X (Italian beamline for X-ray Absorption Spectroscopy) and is the upgrade of the former GILDA beamline installed on the BM08 bending magnet port of European Synchrotron Radiation Facility (ESRF). Within this contribution a full description of the project is provided.

  13. Applications of “Tender” Energy (1-5 keV) X-ray Absorption Spectroscopy in Life Sciences

    SciTech Connect

    Northrup, Paul; Leri, Alessandra; Tappero, Ryan

    2016-02-15

    The “tender” energy range of 1 to 5 keV, between the energy ranges of most “hard” (>5 keV) and “soft” (<1 keV) synchrotron X-ray facilities, offers some unique opportunities for synchrotron-based X-ray absorption fine structure spectroscopy in life sciences. In particular the K absorption edges of Na through Ca offer opportunities to study local structure, speciation, and chemistry of many important biological compounds, structures and processes. This is an area of largely untapped science, in part due to a scarcity of optimized facilities. Such measurements also entail unique experimental challenges. Lastly, this brief review describes the technique, its experimental challenges, recent progress in development of microbeam measurement capabilities, and several highlights illustrating applications in life sciences.

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

    SciTech Connect

    Sano, Keiji; Niibe, Masahito; Kawakami, Retsuo; Nakano, Yoshitaka

    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. Electron-vibron coupling in halogenated acenaphthenequinone upon O K-edge soft x-ray absorption

    SciTech Connect

    Schmidt, Norman; Fink, Rainer H.; Clark, Tim; Urquhart, Stephen G.

    2011-10-14

    We present high resolution oxygen K near-edge x-ray absorption spectra of the acenaphthenequinone (ANQ) derivative 3,8-dibromo-5,6-dichloro-ANQ (Br{sub 2}Cl{sub 2}-ANQ). The spectral features exhibit an almost identical vibronic fine structure compared to that shown by ANQ. The unequal distances of the vibronic levels as derived from the least-squares fit analysis of the vibronic progressions allows us to determine the anharmonicity of the excited state potentials involved. We conclude that a single vibrational progression couples to the resonant excitation of O 1s core electrons preferentially. Comparison of the two ANQ derivatives gives a clear indication that the vibronic mode corresponds to a C=O stretching mode, rather than coupling to a C-H mode as suggested previously. These conclusions are supported by density functional theory calculations.

  16. Applications of “Tender” Energy (1-5 keV) X-ray Absorption Spectroscopy in Life Sciences

    DOE PAGES

    Northrup, Paul; Leri, Alessandra; Tappero, Ryan

    2016-02-15

    The “tender” energy range of 1 to 5 keV, between the energy ranges of most “hard” (>5 keV) and “soft” (<1 keV) synchrotron X-ray facilities, offers some unique opportunities for synchrotron-based X-ray absorption fine structure spectroscopy in life sciences. In particular the K absorption edges of Na through Ca offer opportunities to study local structure, speciation, and chemistry of many important biological compounds, structures and processes. This is an area of largely untapped science, in part due to a scarcity of optimized facilities. Such measurements also entail unique experimental challenges. Lastly, this brief review describes the technique, its experimental challenges,more » recent progress in development of microbeam measurement capabilities, and several highlights illustrating applications in life sciences.« less

  17. Speciation and site occupancy of uranium in strontium orthosilicate by photoluminescence and X-ray absorption spectroscopy: A combined experimental and theoretical approach.

    PubMed

    Gupta, Santosh K; Yadav, A K; Nigam, Sandeep; Jha, S N; Mazumder, C; Bhattacharya, D; Thulasidas, S K

    2015-12-05

    Identifying the oxidation state and coordination geometry of radioactive element like uranium is important to fully understand its toxicology and other harmful effect in environment. Strontium orthosilicate is taken as a model compound for that. Strontium silicate doped with 1.0 mol% of U has been synthesized using sol-gel method and characterized using X-ray diffraction (XRD), time resolved fluorescence spectroscopy (TRFS) and extended X-ray absorption fine structure (EXAFS). Uranium exhibits multiple oxidation state and each one of them is having characteristics luminescence is an interesting dopant from structural point of view. TRFS is used to investigate the oxidation state and coordination behavior of uranium in Sr2SiO4. From TRFS measurement it was observed that uranium stabilizes in +6 oxidation state in the form of uranyl ion. Based on luminescence lifetime and EXAFS studies it was inferred that uranyl is stabilized on both 9- and 10-coordinated strontium polyhedra but majority occupies relatively asymmetric 9-coordinated Sr sites. This is further confirmed using theoretical measurement.

  18. Structural characterization of zinc(II) chloride in aqueous solution and in the protic ionic liquid ethyl ammonium nitrate by x-ray absorption spectroscopy.

    PubMed

    D'Angelo, Paola; Zitolo, Andrea; Ceccacci, Francesca; Caminiti, Ruggero; Aquilanti, Giuliana

    2011-10-21

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the species and structures existing in a series of ZnCl(2)-H(2)O-NaCl solutions with different chloride/zinc ratios and in a solution of ZnCl(2) in the protic ionic liquid ethyl ammonium nitrate (EAN). The average coordination numbers and distances of zinc species were determined from the analysis of the EXAFS data. In aqueous solution the number of chloride ions tightly bounded to Zn(2+) is significantly related to the chloride/zinc ratio, and no inner complex formation between Zn(2+) and Cl(-) ions has been detected for low ZnCl(2) concentration (0.1 and 0.2 M). Conversely, in the same concentration range (0.13 M) the ZnCl(2) species do not dissociate in EAN and the Zn(2+) first coordination shell has two chloride ions and is completed by two oxygen atoms of the nitrate anion. The results of this investigation show that notwithstanding the existence of similar characteristics between EAN and water, the solvation properties of the two solvents are markedly different.

  19. The Structure of Nickel Chloride in the Ionic Liquid 1-Ethyl-3-methyl Imidazolium Chloride/Aluminum Chloride: X-ray Absorption Spectroscopy

    SciTech Connect

    D Roeper; K Pandya; G Cheek; W OGrady

    2011-12-31

    The structure of anhydrous nickel chloride in the ionic liquid 1-ethyl-3-methyl imidazolium chloride and aluminum chloride has been investigated with extended X-ray absorption fine structure (EXAFS) in both Lewis acid and Lewis base solutions. The EXAFS data of NiCl{sub 2} {center_dot} 6H{sub 2}O crystals were also recorded and analyzed to demonstrate the difference file technique. The difference file technique is used to obtain the structural information for the very closely spaced coordination shells of chloride and oxygen in NiCl{sub 2} {center_dot} 6H{sub 2}O and they are found to agree very closely with the X-ray diffraction data. The difference file technique is then used to analyze the nickel chloride in the ionic liquid solutions. Even though anhydrous NiCl{sub 2} is more soluble in the basic solution than in the acidic solution, the EXAFS data show a single coordination of four chlorides in a tetrahedron around the nickel atom in the basic solution. In a weak acid solution, there are six chlorides in a single octahedral coordination shell around the nickel. However, in a strong acid solution, in addition to the octahedral chloride-coordination shell, there is a second coordination shell of eight aluminum atoms in the form of a simple cube.

  20. Cadmium Chemical Form in Mine Waste Materials by X-ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Diacomanolis, V.; Ng, J. C.; Sadler, R.; Harris, H. H.; Nomura, M.; Noller, B. N.

    2010-06-01

    This study examines the molecular form of cadmium (Cd) present in mine wastes by X-ray Absorption Spectroscopy (XAS; Cd>20 mg/kg) using the K-edge of Cd at the Photon Factory Advanced Ring (PF-AR), NW10A beam line at KEK-Tsukuba-Japan. Mine waste materials and zinc concentrate were analyzed for Cd by ICPMS prior to undertaking XAS (range 21-452 mg/kg). Model compounds (CdO, Cd(OH)2, CdCO3, Cdacetate, CdS, Cdstearate, CdDEDTC) and samples were examined in solid form at 20 K. The XANES spectra showed similar E max values for both model compounds and samples. The EXAFS showed that Cd-S in CdS, gives a flatter spectrum in the extended region compared to Cd-O found with CdCO3, CdO and Cd Stearate. Linear combination fitting with model Cd compounds did not give clear assignments of composition, indicating that more detailed EXAFS spectra is required as mineral forms containing Cd were present rather than simple Cd compounds such as CdCO3. The Cd bond for a single shell model in mine waste sample matrices appears to be either Cd-O or Cd-S, or a combination of both. Comparison of molecular data from the XAS studies with bioaccessibility data giving a prediction of bioavailability for mine waste materials provides useful information about the significance of the cadmium form as a contaminant for health risk assessment purposes.

  1. Coordination chemistry and hydrolysis of Fe(III) in a peat humic acid studied by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Karlsson, Torbjörn; Persson, Per

    2010-01-01

    The speciation of iron (Fe) in soils, sediments and surface waters is highly dependent on chemical interactions with natural organic matter (NOM). However, the molecular structure and hydrolysis of the Fe species formed in association with NOM is still poorly described. In this study extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination chemistry and hydrolysis of Fe(III) in solution of a peat humic acid (5010-49,200 μg Fe g -1 dry weight, pH 3.0-7.2). Data were analyzed by both conventional EXAFS data fitting and by wavelet transforms in order to facilitate the identification of the nature of backscattering atoms. Our results show that Fe occurs predominantly in the oxidized form as ferric ions and that the speciation varies with pH and Fe concentration. At low Fe concentrations (5010-9920 μg g -1; pH 3.0-7.2) mononuclear Fe(III)-NOM complexes completely dominates the speciation. The determined bond distances for the Fe(III)-NOM complexes are similar to distances obtained for Fe(III) complexed by desferrioxamine B and oxalate indicating the formation of a five-membered chelate ring structure. At higher Fe concentrations (49,200 μg g -1; pH 4.2-6.9) we detect a mixture of mononuclear Fe(III)-NOM complexes and polymeric Fe(III) (hydr)oxides with an increasing amount of Fe(III) (hydr)oxides at higher pH. However, even at pH 6.9 and a Fe concentration of 49,200 μg g -1 our data indicates that a substantial amount of the total Fe (>50%) is in the form of organic complexes. Thus, in environments with significant amounts of organic matter organic Fe complexes will be of great importance for the geochemistry of Fe. Furthermore, the formation of five-membered chelate ring structures is in line with the strong complexation and limited hydrolytic polymerization of Fe(III) in our samples and also agrees with EXAFS derived structures of Fe(III) in organic soils.

  2. X-ray absorption spectroscopy on the basis of hybrid X-pinch radiation

    SciTech Connect

    Tilikin, I. N. Shelkovenko, T. A.; Pikuz, S. A.; Knapp, P. F.; Hammer, D. A.

    2015-07-15

    Results of experiments on X-ray absorption spectroscopy carried out at the BIN (270 kA, 100 ns) and XP (450 kA, 45 ns) facilities are presented. Continuum radiation of a Mo hybrid X-pinch was used as probing radiation, against which absorption lines of the plasma of exploded Al wires placed in the return current circuit of a hybrid X-pinch, as well as in a two- and four-wire array, were observed. The experiments have demonstrated that the radiation of a hybrid X-pinch hot spot can be used as probing radiation for X-ray absorption spectroscopy and that, in many parameters, such a source surpasses those on the basis of laser-produced plasma. The plasma parameters in arrays made of two and four Al wires were studied experimentally.

  3. Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy

    SciTech Connect

    Schwanke, C.; Lange, K. M.; Golnak, R.; Xiao, J.

    2014-10-15

    A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl{sub 2} aqueous solution by X-ray absorption and emission spectroscopy is presented.

  4. Electronic structure of warm dense copper studied by ultrafast x-ray absorption spectroscopy.

    PubMed

    Cho, B I; Engelhorn, K; Correa, A A; Ogitsu, T; Weber, C P; Lee, H J; Feng, J; Ni, P A; Ping, Y; Nelson, A J; Prendergast, D; Lee, R W; Falcone, R W; Heimann, P A

    2011-04-22

    We use time-resolved x-ray absorption spectroscopy to investigate the unoccupied electronic density of states of warm dense copper that is produced isochorically through the absorption of an ultrafast optical pulse. The temperature of the superheated electron-hole plasma, which ranges from 4000 to 10 000 K, was determined by comparing the measured x-ray absorption spectrum with a simulation. The electronic structure of warm dense copper is adequately described with the high temperature electronic density of state calculated by the density functional theory. The dynamics of the electron temperature is consistent with a two-temperature model, while a temperature-dependent electron-phonon coupling parameter is necessary.

  5. X-ray absorption spectroscopy on the basis of hybrid X-pinch radiation

    NASA Astrophysics Data System (ADS)

    Tilikin, I. N.; Shelkovenko, T. A.; Pikuz, S. A.; Knapp, P. F.; Hammer, D. A.

    2015-07-01

    Results of experiments on X-ray absorption spectroscopy carried out at the BIN (270 kA, 100 ns) and XP (450 kA, 45 ns) facilities are presented. Continuum radiation of a Mo hybrid X-pinch was used as probing radiation, against which absorption lines of the plasma of exploded Al wires placed in the return current circuit of a hybrid X-pinch, as well as in a two- and four-wire array, were observed. The experiments have demonstrated that the radiation of a hybrid X-pinch hot spot can be used as probing radiation for X-ray absorption spectroscopy and that, in many parameters, such a source surpasses those on the basis of laser-produced plasma. The plasma parameters in arrays made of two and four Al wires were studied experimentally.

  6. Oxygen, Neon, and Iron X-Ray Absorption in the Local Interstellar Medium

    NASA Technical Reports Server (NTRS)

    Gatuzz, Efrain; Garcia, Javier; Kallman, Timothy R.; Mendoza, Claudio

    2016-01-01

    We present a detailed study of X-ray absorption in the local interstellar medium by analyzing the X-ray spectra of 24 galactic sources obtained with the Chandra High Energy Transmission Grating Spectrometer and the XMM-Newton Reflection Grating Spectrometer. Methods. By modeling the continuum with a simple broken power-law and by implementing the new ISMabs X-ray absorption model, we have estimated the total H, O, Ne, and Fe column densities towards the observed sources. Results. We have determined the absorbing material distribution as a function of source distance and galactic latitude longitude. Conclusions. Direct estimates of the fractions of neutrally, singly, and doubly ionized species of O, Ne, and Fe reveal the dominance of the cold component, thus indicating an overall low degree of ionization. Our results are expected to be sensitive to the model used to describe the continuum in all sources.

  7. Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy.

    PubMed

    Schwanke, C; Golnak, R; Xiao, J; Lange, K M

    2014-10-01

    A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl2 aqueous solution by X-ray absorption and emission spectroscopy is presented.

  8. Oxygen, neon, and iron X-ray absorption in the local interstellar medium

    NASA Astrophysics Data System (ADS)

    Gatuzz, Efraín; García, Javier A.; Kallman, Timothy R.; Mendoza, Claudio

    2016-04-01

    Aims: We present a detailed study of X-ray absorption in the local interstellar medium by analyzing the X-ray spectra of 24 galactic sources obtained with the Chandra High Energy Transmission Grating Spectrometer and the XMM-Newton Reflection Grating Spectrometer. Methods: By modeling the continuum with a simple broken power-law and by implementing the new ISMabs X-ray absorption model, we have estimated the total H, O, Ne, and Fe column densities towards the observed sources. Results: We have determined the absorbing material distribution as a function of source distance and galactic latitude-longitude. Conclusions: Direct estimates of the fractions of neutrally, singly, and doubly ionized species of O, Ne, and Fe reveal the dominance of the cold component, thus indicating an overall low degree of ionization. Our results are expected to be sensitive to the model used to describe the continuum in all sources.

  9. Randic and Schultz molecular topological indices and their correlation with some X-ray absorption parameters

    NASA Astrophysics Data System (ADS)

    Khatri, Sunil; Kekre, Pravin A.; Mishra, Ashutosh

    2016-10-01

    The properties of a molecular system are affected by the topology of molecule. Therefore many studies have been made where the various physic-chemical properties are correlated with the topological indices. These studies have shown a very good correlation demonstrating the utility of the graph theoretical approach. It is, therefore, very natural to expect that the various physical properties obtained by the X-ray absorption spectra may also show correlation with the topological indices. Some complexes were used to establish correlation between topological indices and some X-ray absorption parameters like chemical shift. The chemical shift is on the higher energy side of the metal edge in these complexes. The result obtained in these studies shows that the topological indices of organic molecule acting as a legands can be used for estimating edge shift theoretically.

  10. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    DOE PAGES

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; ...

    2015-03-02

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also presentmore » data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.« less

  11. X-ray absorption in neon modulated by a strong laser pulse

    NASA Astrophysics Data System (ADS)

    Hertlein, M. P.; Glover, T. E.; Allison, T. K.; van Tilborg, J.; Rude, B. S.; Belkacem, A.; Southworth, S. H.; Kanter, E. P.; Krässig, B.; Varma, H. R.; Santra, R.; Young, L.

    2009-11-01

    We have measured the absorption of x-rays in neon gas in the presence of a strong laser pulse. The femtosecond x-rays were tuned to energies near the neon 1s-3p resonance, and the laser intensity of 1013 W/cm2 was below the intensity required to alone ionize neon. We observed strong modification of the x-ray absorption when the neon was subjected to laser light that was temporally overlapped with the x-rays.

  12. X-ray absorption spectroscopy beyond the core-hole lifetime

    SciTech Connect

    Haemaelaeinen, K.; Hastings, J.B.; Siddons, D.P.; Berman, L.

    1992-01-01

    A new technique to overcome the core-hole lifetime broadening in x-ray absorption spectroscopy is presented. It utilizes a high resolution fluorescence spectrometer which can be used to analyze the fluorescence photon energy with better resolution than the natural lifetime width. Furthermore, the high resolution spectrometer can also be used to select the final state in the fluorescence process which can offer spin selectivity even without long range magnetic order in the sample.

  13. X-ray absorption spectroscopy beyond the core-hole lifetime

    SciTech Connect

    Haemaelaeinen, K.; Hastings, J.B.; Siddons, D.P.; Berman, L.

    1992-10-01

    A new technique to overcome the core-hole lifetime broadening in x-ray absorption spectroscopy is presented. It utilizes a high resolution fluorescence spectrometer which can be used to analyze the fluorescence photon energy with better resolution than the natural lifetime width. Furthermore, the high resolution spectrometer can also be used to select the final state in the fluorescence process which can offer spin selectivity even without long range magnetic order in the sample.

  14. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    PubMed Central

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; Cromer, C. L.; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-01-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments. PMID:26798792

  15. Atomic structure of machined semiconducting chips: An x-ray absorption spectroscopy study

    SciTech Connect

    Paesler, M.; Sayers, D.

    1988-12-01

    X-ray absorption spectroscopy (XAS) has been used to examine the atomic structure of chips of germanium that were produced by single point diamond machining. It is demonstrated that although the local (nearest neighbor) atomic structure is experimentally quite similar to that of single crystal specimens information from more distant atoms indicates the presence of considerable stress. An outline of the technique is given and the strength of XAS in studying the machining process is demonstrated.

  16. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    SciTech Connect

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; Cromer, C. L.; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-03-02

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

  17. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy.

    PubMed

    Miaja-Avila, L; O'Neil, G C; Uhlig, J; Cromer, C L; Dowell, M L; Jimenez, R; Hoover, A S; Silverman, K L; Ullom, J N

    2015-03-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼10(6) photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10(7) laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

  18. X-ray absorption study of ceria nanorods promoting the disproportionation of hydrogen peroxide.

    PubMed

    Wu, Tai-Sing; Zhou, Yunyun; Sabirianov, Renat F; Mei, Wai-Ning; Soo, Yun-Liang; Cheung, Chin Li

    2016-04-11

    A quasi in situ X-ray absorption study demonstrated that the disproportionation of hydrogen peroxide (H2O2) promoted by ceria nanorods was associated with a reversible Ce(3+)/Ce(4+) reaction and structural transformations in ceria. The direction of this reversible reaction was postulated to depend on the H2O2 concentration and the fraction of Ce(3+) species in ceria nanorods.

  19. Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

    NASA Astrophysics Data System (ADS)

    Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

    2016-10-01

    We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

  20. Determining crystal phase purity in c-BP through X-ray absorption spectroscopy.

    PubMed

    Huber, S P; Medvedev, V V; Gullikson, E; Padavala, B; Edgar, J H; van de Kruijs, R W E; Bijkerk, F; Prendergast, D

    2017-02-02

    We employ X-ray absorption near-edge spectroscopy at the boron K-edge and the phosphorus L2,3-edge to study the structural properties of cubic boron phosphide (c-BP) samples. The X-ray absorption spectra are modeled from first-principles within the density functional theory framework using the excited electron core-hole (XCH) approach. A simple structural model of a perfect c-BP crystal accurately reproduces the P L2,3-edge, however it fails to describe the broad and gradual onset of the B K-edge. Simulations of the spectroscopic signatures in boron 1s excitations of intrinsic point defects and the hexagonal BP crystal phase show that these additions to the structural model cannot reproduce the broad pre-edge of the experimental spectrum. Calculated formation enthalpies show that, during the growth of c-BP, it is possible that amorphous boron phases can be grown in conjunction with the desired boron phosphide crystalline phase. In combination with experimental and theoretically obtained X-ray absorption spectra of an amorphous boron structure, which have a similar broad absorption onset in the B K-edge spectrum as the cubic boron phosphide samples, we provide evidence for the presence of amorphous boron clusters in the synthesized c-BP samples.

  1. Undistorted X-ray Absorption Spectroscopy Using s-Core-Orbital Emissions.

    PubMed

    Golnak, Ronny; Xiao, Jie; Atak, Kaan; Unger, Isaak; Seidel, Robert; Winter, Bernd; Aziz, Emad F

    2016-05-12

    Detection of secondary emissions, fluorescence yield (FY), or electron yield (EY), originating from the relaxation processes upon X-ray resonant absorption has been widely adopted for X-ray absorption spectroscopy (XAS) measurements when the primary absorption process cannot be probed directly in transmission mode. Various spectral distortion effects inherent in the relaxation processes and in the subsequent transportation of emitted particles (electron or photon) through the sample, however, undermine the proportionality of the emission signals to the X-ray absorption coefficient. In the present study, multiple radiative (FY) and nonradiative (EY) decay channels have been experimentally investigated on a model system, FeCl3 aqueous solution, at the excitation energy of the Fe L-edge. The systematic comparisons between the experimental spectra taken from various decay channels, as well as the comparison with the theoretically simulated Fe L-edge XA spectrum that involves only the absorption process, indicate that the detection of the Fe 3s → 2p partial fluorescence yield (PFY) gives rise to the true Fe L-edge XA spectrum. The two key characteristics generalized from this particular decay channel-zero orbital angular momentum (i.e., s orbital) and core-level emission-set a guideline for obtaining undistorted X-ray absorption spectra in the future.

  2. Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics.

    PubMed

    Neville, Simon P; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S

    2016-10-14

    We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L(2) method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

  3. Comparison of the structure of the manganese complex in the S/sub 1/ and S/sub 2/ state of the photosynthetic O/sub 2/-evolving complex: an X-ray absorption spectroscopy study

    SciTech Connect

    Yachandra, V.K.; Guiles, R.D.; McDermott, A.E.; Cole, J.L.; Britt, R.D.; Dexheimer, S.L.; Sauer, K.; Klein, M.P.

    1987-09-22

    A Mn-containing enzyme complex is involved in the oxidation of H/sub 2/O to O/sub 2/ in algae and higher plants. X-ray absorption spectroscopy is well suited for studying the structure and function of Mn in this enzyme complex. Results of X-ray K-edge and extended X-ray absorption fine structure (EXAFS) studies of Mn in the S/sub 1/ and S/sub 2/ states of the photosynthetic O/sub 2/-evolving complex in photosystem II preparations from spinach are presented in this paper. The S/sub 2/ state was prepared by illumination at 190 K or by illumination at 277 K in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU); these are protocols that limit the photosystem II reaction center to one turnover. Both methods produce an S/sub 2/ state characterized by a multiline electron paramagnetic resonance (EPR) signal. An additional protocol, illumination at 140 K, produces a state characterized by the g = 4.1 EPR signal. The authors have previously observed a shift to higher energy in the X-ray absorption K-edge energy of Mn upon advancement from the dark-adapted S/sub 1/ state to the S/sub 2/ state produced by illumination at 190 K. The Mn K-edge spectrum of the 277 K illuminated sample is similar to that produced at 190 K, indicating that the S/sub 2/ state is similar when produced at 190 or 277 K. A similar edge shape and an edge shift of the same magnitude are seen for the 140 K illuminated sample. These results indicate that the g = 4.1 signal arises from oxidation of the Mn complex and that the structural differences between the species responsible for the g = 4.1 signal and the multiline EPR signal are subtle. They conclude from the edge and EXAFS studies that the light-induced S/sub 1/ to S/sub 2/ transition at 190 K or at 277 K involves a change in the oxidation state of Mn with no EXAFS-detectable change in the coordination of Mn in the O/sub 2/-evolving complex.

  4. The S0 state of photosystem II induced by hydroxylamine: differences between the structure of the manganese complex in the S0 and S1 states determined by X-ray absorption spectroscopy.

    PubMed

    Guiles, R D; Yachandra, V K; McDermott, A E; Cole, J L; Dexheimer, S L; Britt, R D; Sauer, K; Klein, M P

    1990-01-16

    Hydroxylamine at low concentrations causes a two-flash delay in the first maximum flash yield of oxygen evolved from spinach photosystem II (PSII) subchloroplast membranes that have been excited by a series of saturating flashes of light. Untreated PSII membrane preparations exhibit a multiline EPR signal assigned to a manganese cluster and associated with the S2 state when illuminated at 195 K, or at 273 K in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU). We used the extent of suppression of the multiline EPR signal observed in samples illuminated at 195 K to determine the fraction of PSII reaction centers set back to a hydroxylamine-induced S0-like state, which we designate S0*. The manganese K-edge X-ray absorption edges for dark-adapted PSII preparations with or without hydroxylamine are virtually identical. This indicates that, despite its high binding affinity to the oxygen-evolving complex (OEC) in the dark, hydroxylamine does not reduce chemically the manganese cluster within the OEC in the dark. After a single turnover of PSII, a shift to lower energy is observed in the inflection of the Mn K-edge of the manganese cluster. We conclude that, in the presence of hydroxylamine, illumination causes a reduction of the OEC, resulting in a state resembling S0. This lower Mn K-edge energy of S0*, relative to the edge of S1, implies the storage and stabilization of an oxidative equivalent within the manganese cluster during the S0----S1 state transition. An analysis of the extended X-ray absorption fine structure (EXAFS) of the S0* state indicates that a significant structural rearrangement occurs between the S0* and S1 states. The X-ray absorption edge position and the structure of the manganese cluster in the S0* state are indicative of a heterogeneous mixture of formal valences of manganese including one Mn(II) which is not present in the S1 state.

  5. Micro-X-ray absorption near edge structure spectroscopy investigations of baroque tin-amalgam mirrors at BESSY using a capillary focusing system

    NASA Astrophysics Data System (ADS)

    Bartoll, J.; Röhrs, S.; Erko, A.; Firsov, A.; Bjeoumikhov, A.; Langhoff, N.

    2004-10-01

    An elliptically shaped glass monocapillary with a spatial resolution of 5 μm has been used for the fine focusing of the pre-focused X-ray beam produced by the graded-crystal monochromator beamline, KMC-2. The flux density gain of 50 was experimentally measured. The microprobe has been used in the energy range of 3.5-15 keV. Micro-X-ray fluorescence analysis (μXFA) and micro-X-ray absorption near edge structure spectroscopy (μXANES) measurements on test samples and investigations of baroque tin-amalgam mirrors were done.

  6. SYNCHROTRON RADIATION, FREE ELECTRON LASER, APPLICATION OF NUCLEAR TECHNOLOGY, ETC.: A new cell for X-ray absorption spectroscopy study under high pressure

    NASA Astrophysics Data System (ADS)

    Zheng, Li-Rong; Che, Rong-Zheng; Liu, Jing; Du, Yong-Hua; Zhou, Ying-Li; Hu, Tian-Dou

    2009-08-01

    X-ray absorption fine structure (XAFS) spectroscopy is a powerful technique for the investigation of the local environment around selected atoms in condensed matter. XAFS under pressure is an important method for the synchrotron source. We design a cell for a high pressure XAFS experiment. Sintered boron carbide is used as the anvils of this high pressure cell in order to obtain a full XAFS spectrum free from diffraction peaks. In addition, a hydraulic pump was adopted to make in-suit pressure modulation. High quality XAFS spectra of ZrH2 under high pressure (up to 13 GPa) were obtained by this cell.

  7. Operando soft X-ray absorption spectroscopic study on a solid oxide fuel cell cathode during electrochemical oxygen reduction.

    PubMed

    Nakamura, Takashi; Oike, Ryo; Kimura, Yuta; Tamenori, Yusuke; Kawada, Tatsuya; Amezawa, Koji

    2017-03-16

    Operando soft X-ray absorption spectroscopic technique, which could analyze electronic structures of the electrode materials at elevated temperature and controlled atmosphere under electrochemical polarization, was established and its availability was demonstrated by investigating electronic structural changes of an La2NiO4+d dense film electrode during electrochemical oxygen reduction reaction. Clear O K-edge and Ni L-edge X-ray absorption spectra could be obtained below 773 K in fully atmospheric pressure of 100 ppm O2-He, 0.1% O2-He and 1% O2-He gas mixtures. By the PO2 change and the application of electrical potential, considerable spectral changes were observed in O K-edge X-ray absorption spectra while only small spectral changes were observed in Ni L-edge X-ray absorption spectra. Pre-edge peak of the O K-edge X-ray absorption spectra, which reflects the unoccupied pDOS of Ni3d-O2p hybridization, increased/deceased with cathodic/anodic polarization, respectively. The electronic structural changes of the outermost orbital of the electrode material due to electrochemical polarization were successfully confirmed by the operando X-ray absorption spectroscopy developed in this study.

  8. Small copper clusters studied by x-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Oyanagi, H.; Sun, Z. H.; Jiang, Y.; Uehara, M.; Nakamura, H.; Yamashita, K.; Orimoto, Y.; Zhang, L.; Lee, C.; Fukano, A.; Maeda, H.

    2012-04-01

    The local structure of copper nanoparticles grown in organic solution by reducing Cu(II) hexafluoroacetylacetonate [Cu(hfac)2] was studied as-grown by the Cu K-edge x-ray absorption near-edge structure (XANES). Comparison of the experimental XANES spectra with reference materials indicated small copper clusters are formed by ligand-exchange with oleylamine and subsequent reducing by diphenylsilane. The multiple-scattering (MS) calculation for various model clusters consisting of 13-135 atoms suggests that small (13-19 atom) Cu clusters are stabilized without a large deformation.

  9. Electronic structure measurements of metal-organic solar cell dyes using x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, Phillip S.

    The focus of this thesis is twofold: to report the results of X-ray absorption studies of metal-organic dye molecules for dye-sensitized solar cells and to provide a basic training manual on X-ray absorption spectroscopy techniques and data analysis. The purpose of our research on solar cell dyes is to work toward an understanding of the factors influencing the electronic structure of the dye: the choice of the metal, its oxidation state, ligands, and cage structure. First we study the effect of replacing Ru in several common dye structures by Fe. First-principles calculations and X-ray absorption spectroscopy at the C 1s and N 1s edges are combined to investigate transition metal dyes in octahedral and square planar N cages. Octahedral molecules are found to have a downward shift in the N 1s-to-pi* transition energy and an upward shift in C 1s-to-pi* transition energy when Ru is replaced by Fe, explained by an extra transfer of negative charge from Fe to the N ligands compared to Ru. For the square planar molecules, the behavior is more complex because of the influence of axial ligands and oxidation state. Next the crystal field parameters for a series of phthalocyanine and porphyrins dyes are systematically determined using density functional calculations and atomic multiplet calculations with polarization-dependent X-ray absorption spectra. The polarization dependence of the spectra provides information on orbital symmetries which ensures the determination of the crystal field parameters is unique. A uniform downward scaling of the calculated crystal field parameters by 5-30% is found to be necessary to best fit the spectra. This work is a part of the ongoing effort to design and test new solar cell dyes. Replacing the rare metal Ru with abundant metals like Fe would be a significant advance for dye-sensitized solar cells. Understanding the effects of changing the metal centers in these dyes in terms of optical absorption, charge transfer, and electronic

  10. Metal release in metallothioneins induced by nitric oxide: X-ray absorption spectroscopy study.

    PubMed

    Casero, Elena; Martín-Gago, José A; Pariente, Félix; Lorenzo, Encarnación

    2004-12-01

    Metallothioneins (MTs) are low molecular weight proteins that include metal ions in thiolate clusters. The capability of metallothioneins to bind different metals has suggested their use as biosensors for different elements. We study here the interaction of nitric oxide with rat liver MTs by using in situ X-ray absorption spectroscopy techniques. We univocally show that the presence of NO induces the release of Zn atoms from the MT structure to the solution. Zn ions transform in the presence of NO from a tetrahedral four-fold coordinated environment in the MT into a regular octahedral six-fold coordinated state, with interatomic distances compatible with those of Zn solvated in water.

  11. Determination of the melting temperature of palladium nanoparticles by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Vlasenko, V. G.; Podsukhina, S. S.; Kozinkin, A. V.; Zubavichus, Ya. V.

    2016-02-01

    The anharmonicity parameters of the interatomic potential in ~4-nm palladium nanoparticles deposited on poly(tetra)fluoroethylene microgranules 0.2-0.5 μm in average size were studied by X-ray absorption spectroscopy from an analysis of temperature-dependent EXAFS Pd K edges. The parameters of the interatomic potential obtained were used to calculate melting temperature T melt = 1591 K and Debye temperature ΘD = 257 K of palladium nanoparticles; these temperatures are significantly lower than those in metallic palladium: 277 K and 1825 K, respectively.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. X-Ray Absorption Spectroscopy of Cuprous-Thiolate Clusters in Saccharomyces Cerevisiae Metallothionein

    SciTech Connect

    Zhang, L.; Pickering, I.J.; Winge, D.R.; George, G.N.

    2009-05-28

    Copper (Cu) metallothioneins are cuprous-thiolate proteins that contain multimetallic clusters, and are thought to have dual functions of Cu storage and Cu detoxification. We have used a combination of X-ray absorption spectroscopy (XAS) and density-functional theory (DFT) to investigate the nature of Cu binding to Saccharomyces cerevisiae metallothionein. We found that the XAS of metallothionein prepared, containing a full complement of Cu, was quantitatively consistent with the crystal structure, and that reconstitution of the apo-metallothionein with stoichiometric Cu results in the formation of a tetracopper cluster, indicating cooperative binding of the Cu ions by the metallothionein.

  14. Disentangling atomic-layer-specific x-ray absorption spectra by Auger electron diffraction spectroscopy

    NASA Astrophysics Data System (ADS)

    Matsui, Fumihiko; Matsushita, Tomohiro; Kato, Yukako; Hashimoto, Mie; Daimon, Hiroshi

    2009-11-01

    In order to investigate the electronic and magnetic structures of each atomic layer at subsurface, we have proposed a new method, Auger electron diffraction spectroscopy, which is the combination of x-ray absorption spectroscopy (XAS) and Auger electron diffraction (AED) techniques. We have measured a series of Ni LMM AED patterns of the Ni film grown on Cu(001) surface for various thicknesses. Then we deduced a set of atomic-layer-specific AED patterns in a numerical way. Furthermore, we developed an algorithm to disentangle XANES spectra from different atomic layers using these atomic-layer-specific AED patterns. Surface and subsurface core level shift were determined for each atomic layer.

  15. Local structure of indium oxynitride from x-ray absorption spectroscopy

    SciTech Connect

    T-Thienprasert, J.; Onkaw, D.; Rujirawat, S.; Limpijumnong, S.; Nukeaw, J.; Sungthong, A.; Porntheeraphat, S.; Singkarat, S.

    2008-08-04

    Synchrotron x-ray absorption near edge structures (XANES) measurements of In L{sub 3} edge is used in conjunction with first principles calculations to characterize rf magnetron sputtered indium oxynitride at different O contents. Good agreement between the measured and the independently calculated spectra are obtained. Calculations show that the XANES spectra of this alloy are sensitive to the coordination numbers of the In atoms, i.e., fourfold for indium nitride-like structures and sixfold for indium oxide-like structures, but not to the substitution of nearest neighbor N by O or vice versa.

  16. The energy calibration of x-ray absorption spectra using multiple-beam diffraction

    SciTech Connect

    Hagelstein, M.; Cunis, S. ); Frahm, R. ); Rabe, P. )

    1992-01-01

    A new method for calibrating the energy scale of x-ray absorption spectra from an energy dispersive spectrometer has been developed. Distinct features in the diffracted intensity of the curved silicon crystal monochromator have been assigned to multiple-beam diffraction. The photon energies of these structures can be calculated if the precise spacing of the diffracting planes and the orientation of the crystal relative to the incident synchrotron radiation are known. The evaluation of Miller indices of operative reflections and the calculation of the corresponding photon energy is presented. The assignment of operative reflexes is simplified if the monochromator crystal can be rotated around the main diffracting vector {bold H}.

  17. L-edge X-ray absorption studies of neptunium compounds

    NASA Astrophysics Data System (ADS)

    Bertram, S.; Kaindl, G.; Jové, J.; Pagès, M.

    1989-06-01

    The x-ray absorption near-edge structure (XANES) at the Np-L thresholds was investigated for Np compounds with formal valencies III to VII. At LIII, single and double-peaked white lines are observed corresponding to different final states that are populated through core excitation and 5f/ligand hybridization. For the non-metallic Np compounds studied, the weighted mean values of the LIII-XANES shifts relative to NpO2 exhibit a clear correlation with the isomer shifts of the 59-keV Mössbauer resonance of 237Np.

  18. Observing heme doming in myoglobin with femtosecond X-ray absorption spectroscopy

    DOE PAGES

    Levantino, M.; Lemke, H. T.; Schirò, G.; ...

    2015-07-01

    We report time-resolved X-ray absorption measurements after photolysis of carbonmonoxy myoglobin performed at the LCLS X-ray free electron laser with nearly 100 fs (FWHM) time resolution. Data at the Fe K-edge reveal that the photoinduced structural changes at the heme occur in two steps, with a faster (~70 fs) relaxation preceding a slower (~400 fs) one. We tentatively attribute the first relaxation to a structural rearrangement induced by photolysis involving essentially only the heme chromophore and the second relaxation to a residual Fe motion out of the heme plane that is coupled to the displacement of myoglobin F-helix.

  19. Extension to Low Energies (<7keV) of High Pressure X-Ray Absorption Spectroscopy

    SciTech Connect

    Itie, J.-P.; Flank, A.-M.; Lagarde, P.; Idir, M.; Polian, A.; Couzinet, B.

    2007-01-19

    High pressure x-ray absorption has been performed down to 3.6 keV, thanks to the new LUCIA beamline (SLS, PSI) and to the use of perforated diamonds or Be gasket. Various experimental geometries are proposed, depending on the energy of the edge and on the concentration of the studied element. A few examples will be presented: BaTiO3 at the titanium K edge, Zn0.95 Mn0.05O at the manganese K edge, KCl at the potassium K edge.

  20. X-ray absorption in GaGdN: A study of local structure

    NASA Astrophysics Data System (ADS)

    Martínez-Criado, G.; Sancho-Juan, O.; Garro, N.; Sans, J. A.; Cantarero, A.; Susini, J.; Roever, M.; Mai, D.-D.; Bedoya-Pinto, A.; Malindretos, J.; Rizzi, A.

    2008-07-01

    In this study, we report on the incorporation of dilute Gd amounts into GaN films grown by molecular beam epitaxy. A combination of x-ray fluorescence with x-ray absorption spectroscopic techniques enabled us to examine not only the distribution of rare earth atoms in the GaN matrix but also the short-range structural order. Our results show Gd atoms in a trivalent state with tetrahedral coordination, thus substituting Ga in the wurtzite GaN structure.

  1. An x-ray absorption spectroscopy study of Cd binding onto a halophilic archaeon

    NASA Astrophysics Data System (ADS)

    Showalter, Allison R.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Bunker, Bruce A.

    2016-05-01

    X-ray absorption spectroscopy (XAS) and cadmium (Cd) isotherm experiments determine how Cd adsorbs to the surface of halophilic archaeon Halobacterium noricense. This archaeon, isolated from the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico could be involved with the transport of toxic metals stored in the transuranic waste in the salt mine. The isotherm experiments show that adsorption is relatively constant across the tolerable pH range for H. noricense. The XAS results indicate that Cd adsorption occurs predominately via a sulfur site, most likely sulfhydryl, with the same site dominating all measured pH values.

  2. In-situ x-ray absorption study of copper films in ground watersolutions

    SciTech Connect

    Kvashnina, K.O.; Butorin, S.M.; Modin, A.; Soroka, I.; Marcellini, M.; Nordgren, J.; Guo, J.-H.; Werme, L.

    2007-10-29

    This study illustrates how the damage from copper corrosion can be reduced by modifying the chemistry of the copper surface environment. The surface modification of oxidized copper films induced by chemical reaction with Cl{sup -} and HCO{sub 3}{sup -} in aqueous solutions was monitored by in situ X-ray absorption spectroscopy. The results show that corrosion of copper can be significantly reduced by adding even a small amount of sodium bicarbonate. The studied copper films corroded quickly in chloride solutions, whereas the same solution containing 1.1 mM HCO{sub 3}{sup -} prevented or slowed down the corrosion processes.

  3. Ab Initio Molecular Dynamics of Uranium Incorporated in Goethite (α-FeOOH): Interpretation of X-ray Absorption Spectroscopy of Trace Polyvalent Metals.

    PubMed

    Kerisit, Sebastien; Bylaska, Eric J; Massey, Michael S; McBriarty, Martin E; Ilton, Eugene S

    2016-11-21

    Incorporation of economically or environmentally consequential polyvalent metals into iron (oxyhydr)oxides has applications in environmental chemistry, remediation, and materials science. A primary tool for characterizing the local coordination environment of such metals, and therefore building models to predict their behavior, is extended X-ray absorption fine structure spectroscopy (EXAFS). Accurate structural information can be lacking yet is required to constrain and inform data interpretation. In this regard, ab initio molecular dynamics (AIMD) was used to calculate the local coordination environment of minor amounts of U incorporated in the structure of goethite (α-FeOOH). U oxidation states (VI, V, and IV) and charge compensation schemes were varied. Simulated trajectories were used to calculate the U LIII-edge EXAFS function and fit experimental EXAFS data for U incorporated into goethite under reducing conditions. Calculations that closely matched the U EXAFS of the well-characterized mineral uraninite (UO2), and constrained the S0(2) parameter to be 0.909, validated the approach. The results for the U-goethite system indicated that U(V) substituted for structural Fe(III) in octahedral uranate coordination. Charge balance was achieved by the loss of one structural proton coupled to addition of one electron into the solid (-1 H(+), +1 e(-)). The ability of AIMD to model higher energy states thermally accessible at room temperature is particularly relevant for protonated systems such as goethite, where proton transfers between adjacent octahedra had a dramatic effect on the calculated EXAFS. Vibrational effects as a function of temperature were also estimated using AIMD, allowing separate quantification of thermal and configurational disorder. In summary, coupling AIMD structural modeling and EXAFS experiments enables modeling of the redox behavior of polyvalent metals that are incorporated in conductive materials such as iron (oxyhydr)oxides, with

  4. Probing the presence of multiple metal-metal bonds in technetium chlorides by X-ray absorption spectroscopy: implications for synthetic chemistry.

    PubMed

    Poineau, Frederic; Johnstone, Erik V; Forster, Paul M; Ma, Longzou; Sattelberger, Alfred P; Czerwinski, Kenneth R

    2012-09-03

    The cesium salts of [Tc(2)X(8)](3-) (X = Cl, Br), the reduction product of (n-Bu(4)N)[TcOCl(4)] with (n-Bu(4)N)BH(4) in THF, and the product obtained from reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C have been characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. For the [Tc(2)X(8)](3-) anions, the Tc-Tc separations found by EXAFS spectroscopy (2.12(2) Å for both X = Cl and Br) are in excellent agreement with those found by single-crystal X-ray diffraction (SCXRD) measurements (2.117[4] Å for X = Cl and 2.1265(1) Å for X = Br). The Tc-Tc separation found by EXAFS in these anions is slightly shorter than those found in the [Tc(2)X(8)](2-) anions (2.16(2) Å for X = Cl and Br). Spectroscopic and SCXRD characterization of the reduction product of (n-Bu(4)N)[TcOCl(4)] with (n-Bu(4)N)BH(4) are consistent with the presence of dinuclear species that are related to the [Tc(2)Cl(8)](n-) (n = 2, 3) anions. From these results, a new preparation of (n-Bu(4)N)(2)[Tc(2)Cl(8)] was developed. Finally, EXAFS characterization of the product obtained from reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C indicates the presence of amorphous α-TcCl(3). The Tc-Tc separation (i.e., 2.46(2) Å) measured in this compound is consistent with the presence of Tc═Tc double bonds in the [Tc(3)](9+) core.

  5. Silver in geological fluids from in situ X-ray absorption spectroscopy and first-principles molecular dynamics

    NASA Astrophysics Data System (ADS)

    Pokrovski, Gleb S.; Roux, Jacques; Ferlat, Guillaume; Jonchiere, Romain; Seitsonen, Ari P.; Vuilleumier, Rodolphe; Hazemann, Jean-Louis

    2013-04-01

    The molecular structure and stability of species formed by silver in aqueous saline solutions typical of hydrothermal settings were quantified using in situ X-ray absorption spectroscopy (XAS) measurements, quantum-chemical modeling of near-edge absorption spectra (XANES) and extended fine structure spectra (EXAFS), and first-principles molecular dynamics (FPMD). Results show that in nitrate-bearing acidic solutions to at least 200 °C, silver speciation is dominated by the hydrated Ag+ cation surrounded by 4-6 water molecules in its nearest coordination shell with mean Ag-O distances of 2.32 ± 0.02 Å. In NaCl-bearing acidic aqueous solutions of total Cl concentration from 0.7 to 5.9 mol/kg H2O (m) at temperatures from 200 to 450 °C and pressures to 750 bar, the dominant species are the di-chloride complex AgCl2- with Ag-Cl distances of 2.40 ± 0.02 Å and Cl-Ag-Cl angle of 160 ± 10°, and the tri-chloride complex AgCl32- of a triangular structure and mean Ag-Cl distances of 2.60 ± 0.05 Å. With increasing temperature, the contribution of the tri-chloride species decreases from ˜50% of total dissolved Ag in the most concentrated solution (5.9m Cl) at 200 °C to less than 10-20% at supercritical temperatures for all investigated solutions, so that AgCl2- becomes by far the dominant Ag-bearing species at conditions typical of hydrothermal-magmatic fluids. Both di- and tri-chloride species exhibit outer-sphere interactions with the solvent as shown by the detection, using FPMD modeling, of H2O, Cl-, and Na+ at distances of 3-4 Å from the silver atom. The species fractions derived from XAS and FPMD analyses, and total AgCl(s) solubilities, measured in situ in this work from the absorption edge height of XAS spectra, are in accord with thermodynamic predictions using the stability constants of AgCl2- and AgCl32- from Akinfiev and Zotov (2001) and Zotov et al. (1995), respectively, which are based on extensive previous AgCl(s) solubility measurements. These data

  6. Reactivity of Chromium(III) Nutritional Supplements in Biological Media: An X-Ray Absorption Spectroscopic Study

    SciTech Connect

    Nguyen, A.; Mulyani, I.; Levina, A.; Lay, P.A.

    2009-05-22

    Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3]+ (A), [Cr(pic)3] (pic) = 2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4]+ (CrCl3 {center_dot} 6H2O; C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of a library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid/protein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I.; Levina, A.; Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3].

  7. Reactivity of chromium(III) nutritional supplements in biological media: an X-ray absorption spectroscopic study.

    PubMed

    Nguyen, Annie; Mulyani, Irma; Levina, Aviva; Lay, Peter A

    2008-05-19

    Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3](+) (A), [Cr(pic)3] (pic=2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4](+) (CrCl3.6H2O; C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of a library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid/protein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I.; Levina, A.; Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3].

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

    SciTech Connect

    Ravalia, Ashish; Vagadia, Megha; Solanki, P. S.; Shah, N. A.; Kuberkar, D. G.; Gautam, S.; Chae, K. H.; Asokan, K.

    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.

  9. Quantitative Phase Composition of TiO2-Coated Nanoporous-Au Monoliths by X-ray Absorption Spectroscopy and Correlations to Catalytic

    DOE PAGES

    Bagge-Hansen, Michael; Wichmann, Andre; Wittstock, Arne; ...

    2014-02-03

    Porous titania/metal composite materials have many potential applications in the fields of green catalysis, energy harvesting, and storage in which both the overall morphology of the nanoporous host material and the crystallographic phase of the titania (TiO 2) guest determine the material’s performance. New insights into the structure–function relationships of these materials were obtained by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy that, for example, provides quantitative crystallographic phase composition from ultrathin, nanostructured titania films, including sensitivity to amorphous components. We demonstrate that crystallographic phase, morphology, and catalytic activity of TiO 2-functionalized nanoporous gold (np-Au) can be controlled by amore » simple annealing procedure (T < 1300 K). The material was prepared by atomic layer deposition of ~2 nm thick TiO2 on millimeter-sized samples of np-Au (40–50 nm mean ligament size) and catalytically investigated with respect to aerobic CO oxidation. Moreover, the annealing-induced changes in catalytic activity are correlated with concurrent morphology and phase changes as provided by cross-sectional scanning electron microscopy, transmission electron microscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy.« less

  10. Quantitative Phase Composition of TiO2-Coated Nanoporous-Au Monoliths by X-ray Absorption Spectroscopy and Correlations to Catalytic

    SciTech Connect

    Bagge-Hansen, Michael; Wichmann, Andre; Wittstock, Arne; Lee, Jonathan R. I.; Ye, Jianchao; Willey, Trevor M.; Kuntz, Joshua D.; van Buuren, Tony; Biener, Juergen; Baumer, Marcus; Biener, Monika M.

    2014-02-03

    Porous titania/metal composite materials have many potential applications in the fields of green catalysis, energy harvesting, and storage in which both the overall morphology of the nanoporous host material and the crystallographic phase of the titania (TiO 2) guest determine the material’s performance. New insights into the structure–function relationships of these materials were obtained by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy that, for example, provides quantitative crystallographic phase composition from ultrathin, nanostructured titania films, including sensitivity to amorphous components. We demonstrate that crystallographic phase, morphology, and catalytic activity of TiO 2-functionalized nanoporous gold (np-Au) can be controlled by a simple annealing procedure (T < 1300 K). The material was prepared by atomic layer deposition of ~2 nm thick TiO2 on millimeter-sized samples of np-Au (40–50 nm mean ligament size) and catalytically investigated with respect to aerobic CO oxidation. Moreover, the annealing-induced changes in catalytic activity are correlated with concurrent morphology and phase changes as provided by cross-sectional scanning electron microscopy, transmission electron microscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy.

  11. Interface of x-ray absorption package (XRAP) with ANSYS code

    SciTech Connect

    Wang, Zhibi; Kuzay, T.M.

    1996-03-01

    To analyze and design beamline components for third-generation synchrotron radiation facilities, knowledge of the heat load or the heat generation rate of x-rays absorbed inside different materials is needed. The absorption depends on their frequency, penetration depth, and the absorption material. X-rays Absorption Package (XRAP) is software which can generate an x-ray spectrum for bending magnets and insertion devices at synchrotron radiation facilities. XRAP can calculate the x-ray absorption distribution in geometric space and in frequency space. For a two dimensional structure, it can also perform heat transfer and thermal stress analyses. However, for cases such as a beamline component with a complex geometry or x-ray penetration effect, three dimensional analysis using a finite element method is needed. In these cases, XRAP can interface with a finite element code, such as ANSYS, to provide precise heat-load distribution inside a medium. XRAP can be executed interactively with its own graphical user interface, and it can be invoked within ANSYS to generate heat loads for heat transfer analysis. Other sources such as lasers, etc., can also be implemented similarly. This paper will present in detail the implementation of the interface of XRAP with ANSYS, and cases will be presented to illustrate this.

  12. Evolution of silver nanoparticles in the rat lung investigated by X-ray absorption spectroscopy

    SciTech Connect

    Davidson, R. Andrew; Anderson, Donald S.; Van Winkle, Laura S.; Pinkerton, Kent E.; Guo, T.

    2014-12-16

    Following a 6-h inhalation exposure to aerosolized 20 and 110 nm diameter silver nanoparticles, lung tissues from rats were investigated with X-ray absorption spectroscopy, which can identify the chemical state of silver species. Lung tissues were processed immediately after sacrifice of the animals at 0, 1, 3, and 7 days post exposure and the samples were stored in an inert and low-temperature environment until measured. We found that it is critical to follow a proper processing, storage and measurement protocol; otherwise only silver oxides are detected after inhalation even for the larger nanoparticles. The results of X-ray absorption spectroscopy measurements taken in air at 85 K suggest that the dominating silver species in all the postexposure lung tissues were metallic silver, not silver oxide, or solvated silver cations. The results further indicate that the silver nanoparticles in the tissues were transformed from the original nanoparticles to other forms of metallic silver nanomaterials and the rate of this transformation depended on the size of the original nanoparticles. Furthermore, we found that 20 nm diameter silver nanoparticles were significantly modified after aerosolization and 6-h inhalation/deposition, whereas larger, 110 nm diameter nanoparticles were largely unchanged. Over the seven-day postexposure period the smaller 20 nm silver nanoparticles underwent less change in the lung tissue than the larger 110 nm silver nanoparticles. In contrast, silica-coated gold nanoparticles did not undergo any modification processes and remained as the initial nanoparticles throughout the 7-day study period.

  13. Molybdenum speciation in uranium mine tailings using X-ray absorption spectroscopy.

    PubMed

    Essilfie-Dughan, Joseph; Pickering, Ingrid J; Hendry, M Jim; George, Graham N; Kotzer, Tom

    2011-01-15

    Uranium (U) mill tailings in northern Saskatchewan, Canada, contain elevated concentrations of molybdenum (Mo). The potential for long-term (>10,000 years) mobilization of Mo from the tailings management facilities to regional groundwater systems is an environmental concern. To assist in characterizing long-term stability, X-ray absorption spectroscopy was used to define the chemical (redox and molecular) speciation of Mo in tailings samples from the Deilmann Tailings Management Facility (DTMF) at the Key Lake operations of Cameco Corporation. Comparison of Mo K near-edge X-ray absorption spectra of tailings samples and reference compounds of known oxidation states indicates Mo exists mainly as molybdate (+6 oxidation state). Principal component analysis of tailings samples spectra followed by linear combination fitting using spectra of reference compounds indicates that various proportions of NiMoO(4) and CaMoO(4) complexes, as well as molybdate adsorbed onto ferrihydrite, are the Mo species present in the U mine tailings. Tailings samples with low Fe/Mo (<708) and high Ni/Mo (>113) molar ratios are dominated by NiMoO(4), whereas those with high Fe/Mo (>708) and low Ni/Mo (<113) molar ratios are dominated by molybdate adsorbed onto ferrihydrite. This suggests that the speciation of Mo in the tailings is dependent in part on the chemistry of the original ore.

  14. X-ray absorption spectroscopy (XAS) of toxic metal mineral transformations by fungi.

    PubMed

    Fomina, Marina; Charnock, John; Bowen, Andrew D; Gadd, Geoffrey M

    2007-02-01

    Fungi can be highly efficient biogeochemical agents and accumulators of soluble and particulate forms of metals. This work aims to understand some of the physico-chemical mechanisms involved in toxic metal transformations focusing on the speciation of metals accumulated by fungi and mycorrhizal associations. The amorphous state or poor crystallinity of metal complexes within biomass and relatively low metal concentrations make the determination of metal speciation in biological systems a challenging problem but this can be overcome by using synchrotron-based element-specific X-ray absorption spectroscopy (XAS) techniques. In this research, we have exposed fungi and ectomycorrhizas to a variety of copper-, zinc- and lead-containing minerals. X-ray absorption spectroscopy studies revealed that oxygen ligands (phosphate, carboxylate) played a major role in toxic metal coordination within the fungal and ectomycorrhizal biomass during the accumulation of mobilized toxic metals. Coordination of toxic metals within biomass depended on the fungal species, initial mineral composition, the nitrogen source, and the physiological state/age of the fungal mycelium.

  15. Femtosecond X-ray absorption study of electron localization in photoexcited anatase TiO2

    PubMed Central

    Santomauro, F. G.; Lübcke, A.; Rittmann, J.; Baldini, E.; Ferrer, A.; Silatani, M.; Zimmermann, P.; Grübel, S.; Johnson, J. A.; Mariager, S. O.; Beaud, P.; Grolimund, D.; Borca, C.; Ingold, G.; Johnson, S.L.; Chergui, M.

    2015-01-01

    Transition metal oxides are among the most promising solar materials, whose properties rely on the generation, transport and trapping of charge carriers (electrons and holes). Identifying the latter’s dynamics at room temperature requires tools that combine elemental and structural sensitivity, with the atomic scale resolution of time (femtoseconds, fs). Here, we use fs Ti K-edge X-ray absorption spectroscopy (XAS) upon 3.49 eV (355 nm) excitation of aqueous colloidal anatase titanium dioxide nanoparticles to probe the trapping dynamics of photogenerated electrons. We find that their localization at Titanium atoms occurs in <300 fs, forming Ti3+ centres, in or near the unit cell where the electron is created. We conclude that electron localization is due to its trapping at pentacoordinated sites, mostly present in the surface shell region. The present demonstration of fs hard X-ray absorption capabilities opens the way to a detailed description of the charge carrier dynamics in transition metal oxides. PMID:26437873

  16. Time-resolved X-ray Absorption Spectroscopy for Electron Transport Study in Warm Dense Gold

    NASA Astrophysics Data System (ADS)

    Lee, Jong-Won; Bae, Leejin; Engelhorn, Kyle; Heimann, Philip; Ping, Yuan; Barbrel, Ben; Fernandez, Amalia; Beckwith, Martha Anne; Cho, Byoung-Ick; GIST Team; IBS Team; LBNL Collaboration; SLAC Collaboration; LLNL Collaboration

    2015-11-01

    The warm dense Matter represents states of which the temperature is comparable to Fermi energy and ions are strongly coupled. One of the experimental techniques to create such state in the laboratory condition is the isochoric heating of thin metal foil with femtosecond laser pulses. This concept largely relies on the ballistic transport of electrons near the Fermi-level, which were mainly studied for the metals in ambient conditions. However, they were barely investigated in warm dense conditions. We present a time-resolved x-ray absorption spectroscopy measured for the Au/Cu dual layered sample. The front Au layer was isochorically heated with a femtosecond laser pulse, and the x-ray absorption changes around L-edge of Cu, which was attached on the backside of Au, was measured with a picosecond resolution. Time delays between the heating of the `front surface' of Au layer and the alternation of x-ray spectrum of Cu attached on the `rear surface' of Au indicate the energetic electron transport mechanism through Au in the warm dense conditions. IBS (IBS-R012-D1) and the NRF (No. 2013R1A1A1007084) of Korea.

  17. Femtosecond X-ray absorption study of electron localization in photoexcited anatase TiO2.

    PubMed

    Santomauro, F G; Lübcke, A; Rittmann, J; Baldini, E; Ferrer, A; Silatani, M; Zimmermann, P; Grübel, S; Johnson, J A; Mariager, S O; Beaud, P; Grolimund, D; Borca, C; Ingold, G; Johnson, S L; Chergui, M

    2015-10-06

    Transition metal oxides are among the most promising solar materials, whose properties rely on the generation, transport and trapping of charge carriers (electrons and holes). Identifying the latter's dynamics at room temperature requires tools that combine elemental and structural sensitivity, with the atomic scale resolution of time (femtoseconds, fs). Here, we use fs Ti K-edge X-ray absorption spectroscopy (XAS) upon 3.49 eV (355 nm) excitation of aqueous colloidal anatase titanium dioxide nanoparticles to probe the trapping dynamics of photogenerated electrons. We find that their localization at Titanium atoms occurs in <300 fs, forming Ti(3+) centres, in or near the unit cell where the electron is created. We conclude that electron localization is due to its trapping at pentacoordinated sites, mostly present in the surface shell region. The present demonstration of fs hard X-ray absorption capabilities opens the way to a detailed description of the charge carrier dynamics in transition metal oxides.

  18. Evolution of Silver Nanoparticles in the Rat Lung Investigated by X-ray Absorption Spectroscopy

    PubMed Central

    2015-01-01

    Following a 6-h inhalation exposure to aerosolized 20 and 110 nm diameter silver nanoparticles, lung tissues from rats were investigated with X-ray absorption spectroscopy, which can identify the chemical state of silver species. Lung tissues were processed immediately after sacrifice of the animals at 0, 1, 3, and 7 days post exposure and the samples were stored in an inert and low-temperature environment until measured. We found that it is critical to follow a proper processing, storage and measurement protocol; otherwise only silver oxides are detected after inhalation even for the larger nanoparticles. The results of X-ray absorption spectroscopy measurements taken in air at 85 K suggest that the dominating silver species in all the postexposure lung tissues were metallic silver, not silver oxide, or solvated silver cations. The results further indicate that the silver nanoparticles in the tissues were transformed from the original nanoparticles to other forms of metallic silver nanomaterials and the rate of this transformation depended on the size of the original nanoparticles. We found that 20 nm diameter silver nanoparticles were significantly modified after aerosolization and 6-h inhalation/deposition, whereas larger, 110 nm diameter nanoparticles were largely unchanged. Over the seven-day postexposure period the smaller 20 nm silver nanoparticles underwent less change in the lung tissue than the larger 110 nm silver nanoparticles. In contrast, silica-coated gold nanoparticles did not undergo any modification processes and remained as the initial nanoparticles throughout the 7-day study period. PMID:25517690

  19. Strontium localization in bone tissue studied by X-ray absorption spectroscopy.

    PubMed

    Frankær, Christian Grundahl; Raffalt, Anders Christer; Stahl, Kenny

    2014-02-01

    Strontium has recently been introduced as a pharmacological agent for the treatment and prevention of osteoporosis. We determined the localization of strontium incorporated into bone matrix from dogs treated with Sr malonate by X-ray absorption spectroscopy. A new approach for analyzing the X-ray absorption spectra resulted in a compositional model and allowed the relative distribution of strontium in the different bone components to be estimated. Approximately 35-45% of the strontium present is incorporated into calcium hydroxyapatite (CaHA) by substitution of some of the calcium ions occupying highly ordered sites, and at least 30% is located at less ordered sites where only the first solvation shell is resolved, suggesting that strontium is surrounded by only oxygen atoms similar to Sr(2+) in solution. Strontium was furthermore shown to be absorbed in collagen in which it obtains a higher structural order than when present in serum but less order than when it is incorporated into CaHA. The total amount of strontium in the samples was determined by inductively coupled plasma mass spectrometry, and the amount of Sr was found to increase with increasing dose levels and treatment periods, whereas the relative distribution of strontium among the different components appears to be independent of treatment period and dose level.

  20. Effects of spatially heterogeneous porosity on matrix diffusion as investigated by X-ray absorption imaging

    NASA Astrophysics Data System (ADS)

    Tidwell, Vincent C.; Meigs, Lucy C.; Christian-Frear, Tracy; Boney, Craig M.

    2000-03-01

    High-resolution X-ray absorption imaging was used to investigate the effects of spatially heterogeneous porosity on matrix diffusion. Experiments were performed on four, centimeter-scale slabs of Culebra dolomite taken from the Waste Isolation Pilot Plant (WIPP) site. These tests involved the diffusion of potassium iodide into a single edge of each brine-saturated rock slab, while X-ray absorption imaging was used to measure the two-dimensional relative concentration distribution at different times during the experiment. X-ray imaging was also used to measure the heterogeneous, two-dimensional porosity distribution of each rock slab. The resulting high-resolution data provide unique insight into the spatially varying diffusion characteristics of each heterogeneous rock sample, which traditional methods such as through-diffusion experiments cannot. In these tests, significant variations in the diffusion coefficient were calculated over the relatively small length (centimeter) and time scales (months) investigated. Results also indicated that these variations were related to the heterogeneous porosity characteristics of each rock sample. Not only were the diffusion coefficients found to depend on the magnitude of the porosity but also on its spatial distribution. Specifically, the geometry, position, and orientation of the heterogeneous porosity features populating each rock slab appeared to influence the diffusion characteristics.

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

    NASA Astrophysics Data System (ADS)

    Osorio, A. G.; Bergmann, C. P.

    2015-10-01

    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.

  2. High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell

    SciTech Connect

    Hong, X.; Newville, M.; Prakapenka, V.B.; Rivers, M.L.; Sutton, S.R.

    2009-07-31

    We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over a small angular range of DAC orientation, e.g., within {+-}3{sup o} relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO{sub 2} recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO{sub 2} glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO{sub 2} glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.

  3. Monopeptide versus Monopeptoid: Insights on Structure and Hydration of Aqueous Alanine and Sarcosine via X-ray Absorption Spectroscopy

    SciTech Connect

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

    2009-11-19

    Despite the obvious significance, the aqueous interactions of peptides remain incompletely understood. Their synthetic analogues called peptoids (poly-N-substituted glycines), have recently emerged as a promising biomimetic material, particularly due to their robust secondary structure and resistance to denaturation. We describe comparative near-edge x-ray absorption fine structure (NEXAFS) spectroscopy studies of aqueous sarcosine, the simplest peptoid, and alanine, its peptide isomer, interpreted by density functional theory calculations. The sarcosine nitrogen K-edge spectrum is blue-shifted with respect to that of alanine, in agreement with our calculations; we conclude that this shift results primarily from the methyl group substitution on the nitrogen of sarcosine. Our calculations indicate that the nitrogen K-edge spectrum of alanine differs significantly between dehydrated and hydrated scenarios, while that of the sarcosine zwitterion is less affected by hydration. In contrast, the computed sarcosine spectrum is greatly impacted by conformational variations, while the alanine spectrum is not. This relates to a predicted solvent dependence for alanine, as compared to sarcosine. Additionally, we show the theoretical nitrogen K-edge spectra to be sensitive to the degree of hydration, indicating that experimental X-ray spectroscopy may be able to distinguish between bulk and partial hydration, such as found in confined environments near proteins and in reverse micelles.

  4. Structure of the manganese complex of photosystem II upon removal of the 33-kilodalton extrinsic protein: an X-ray absorption spectroscopy study

    SciTech Connect

    Cole, J.L.; Yachandra, V.K.; McDermott, A.E.; Guiles, R.D.; Britt, R.D.; Dexheimer, S.L.; Sauer, K.; Klein, M.P.

    1987-09-22

    The structure of the Mn complex of photosystem II (PSII) was studied by X-ray absorption spectroscopy. Oxygen-evolving spinach PSII membranes containing 4-5 Mn/PSII were treated with 0.8 M CaCl/sub 2/ to extract the 33-, 24-, and 16-kilodalton (kDa) extrinsic membrane proteins. Mn was not released by this treatment, but subsequent incubation at low Cl/sup -/ concentration generated preparations containing 2 Mn/PSII. The Mn X-ray absorption K-edge spectrum of the CaCl/sub 2/-washed preparation containing 4 Mn/PSII is very similar to the spectrum of native PSII, indicating that the oxidation states and ligand symmetry of the Mn complex in these preparations are not significantly different. The Mn extended X-ray absorption find structure (EXAFS) of CaCl/sub 2/-washed PSII fits to a Mn neighbor at approx. 2.75 A and two shells of N or O at approx. 1.78 and approx. 1.92 A. The results demonstrate that the structure of the Mn complex is largely unaffected by removal of 33-, 24-, and 16-kDa extrinsic proteins, and thus these proteins do not provide ligands to Mn. The Mn K-edge spectrum of the CaCl/sub 2/-washed sample containing 2 Mn/PSII has a dramatically altered shape, and the edge infection point is shifted to lower energy. The position of the edge is consistent with a Mn oxidation state of +3. The Mn EXAFS of this preparation is also quite different and cannot be simulated by using the parameters for the native Mn complex. Thus the structure of the Mn complex is disrupted upon depletion of half of the Mn.

  5. Investigation of surface structure with X-ray absorption and electron emission spectroscopies

    NASA Astrophysics Data System (ADS)

    Pauli, Mark Daniel

    The use of electron spectromicroscopy for the study of the chemical composition and electronic properties of surfaces, overlayers, and interfaces has become widely accepted. Improvements to the optics of instruments such as the X-ray photo electron emission microscope have pushed spectroscopic microscopies into the realm of very high spatial resolution, at and below 1 micrometer [1]. Coupled with the high spectral resolution available from third generation synchrotron sources, this spatial resolution allows the measurement of micro-X-ray absorption near-edge spectra in addition to the more typical electron emission spectra and diffraction patterns. Complementary to the experimental developments is the development of improved theoretical methods for computational modeling of X-ray absorption and emission spectroscopies. In the field of tribochemistry, zinc dialkyl dithiophosphate (ZDDP) has long been a topic of much study. ZDDP is widely used as an anti-wear additive in engine oils and there is interest in determining the decomposition products of ZDDP that provide this protection against friction. An analysis of X-ray absorption near-edge spectra of thermal films from ZDDP samples is presented, including a comparison of the Zinc L-edge spectra with model calculations [2]. It was found essential to carry out self-consistent calculations of the electronic structure for the modeling. For the techniques of electron diffraction, a new method for a full multiple-scattering calculation of diffraction patterns from crystals with two-dimensional periodicity parallel to the surface is presented [3]. The calculation makes use of Helmholtz's reciprocity principle to compute the path-reversed process of the back propagation of a photoelectron from the position of a distant detector to that of the emitting atom. Early application is demonstrated with simulations of 64 eV M2,3VV and 914 eV L 2,3VV Auger electron diffraction from a Cu(001) surface. The functionality of the path

  6. Mn K-edge X-ray absorption studies of oxo- and hydroxo-manganese(IV) complexes: experimental and theoretical insights into pre-edge properties.

    PubMed

    Leto, Domenick F; Jackson, Timothy A

    2014-06-16

    Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [Mn(II)(Cl)2(Me2EBC)], [Mn(IV)(OH)2(Me2EBC)](2+), and [Mn(IV)(O)(OH)(Me2EBC)](+), which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [Mn(IV)(O)(OH)(Me2EBC)](+) revealed Mn-O scatterers at 1.71 and 1.84 Å and Mn-N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [Mn(II)(Cl)2(Me2EBC)] and [Mn(IV)(OH)2(Me2EBC)](2+) are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn-O(H) distances and pre-edge peak areas of Mn(IV)═O and Mn(IV)-OH complexes, but this trend was strongly modulated by the Mn(IV) coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn-O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal Mn(IV)═O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn═O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn═O σ* molecular orbital (MO) but also show intense transitions to 3dx(2)-y(2) and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal Mn(IV)═O adducts. These results underscore the importance of

  7. Mn K-Edge X-ray Absorption Studies of Oxo- and Hydroxo-manganese(IV) Complexes: Experimental and Theoretical Insights into Pre-Edge Properties

    PubMed Central

    2015-01-01

    Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [MnII(Cl)2(Me2EBC)], [MnIV(OH)2(Me2EBC)]2+, and [MnIV(O)(OH)(Me2EBC)]+, which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [MnIV(O)(OH)(Me2EBC)]+ revealed Mn–O scatterers at 1.71 and 1.84 Å and Mn–N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [MnII(Cl)2(Me2EBC)] and [MnIV(OH)2(Me2EBC)]2+ are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn–O(H) distances and pre-edge peak areas of MnIV=O and MnIV–OH complexes, but this trend was strongly modulated by the MnIV coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn–O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal MnIV=O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn=O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn=O σ* molecular orbital (MO) but also show intense transitions to 3dx2–y2 and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal MnIV=O adducts. These results underscore the importance of reporting experimental pre-edge areas

  8. Cost and sensitivity of restricted active-space calculations of metal L-edge X-ray absorption spectra.

    PubMed

    Pinjari, Rahul V; Delcey, Mickaël G; Guo, Meiyuan; Odelius, Michael; Lundberg, Marcus

    2016-02-15

    The restricted active-space (RAS) approach can accurately simulate metal L-edge X-ray absorption spectra of first-row transition metal complexes without the use of any fitting parameters. These characteristics provide a unique capability to identify unknown chemical species and to analyze their electronic structure. To find the best balance between cost and accuracy, the sensitivity of the simulated spectra with respect to the method variables has been tested for two models, [FeCl6 ](3-) and [Fe(CN)6 ](3-) . For these systems, the reference calculations give deviations, when compared with experiment, of ≤1 eV in peak positions, ≤30% for the relative intensity of major peaks, and ≤50% for minor peaks. When compared with these deviations, the simulated spectra are sensitive to the number of final states, the inclusion of dynamical correlation, and the ionization potential electron affinity shift, in addition to the selection of the active space. The spectra are less sensitive to the quality of the basis set and even a double-ζ basis gives reasonable results. The inclusion of dynamical correlation through second-order perturbation theory can be done efficiently using the state-specific formalism without correlating the core orbitals. Although these observations are not directly transferable to other systems, they can, together with a cost analysis, aid in the design of RAS models and help to extend the use of this powerful approach to a wider range of transition metal systems.

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

    PubMed

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

    2013-12-28

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

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

    SciTech Connect

    Aquilanti, G.; Trapananti, A.; Pascarelli, S.; Minicucci, M.; Principi, E.; Liscio, F.; Twarog, A.

    2007-10-01

    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.

  11. X-Ray absorption spectroscopy investigation of 1-alkyl-3-methylimidazolium bromide salts

    SciTech Connect

    D'Angelo, Paola; Zitolo, Andrea; Migliorati, Valentina; Bodo, Enrico; Caminiti, Ruggero; Aquilanti, Giuliana; Hazemann, Jean Louis; Testemale, Denis; Mancini, Giordano

    2011-08-21

    X-ray absorption spectroscopy (XAS) has been used to unveil the bromide ion local coordination structure in 1-alkyl-3-methylimidazolium bromide [C{sub n}mim]Br ionic liquids (ILs) with different alkyl chains. The XAS spectrum of 1-ethyl-3-methylimidazolium bromide has been found to be different from those of the other members of the series, from the butyl to the decyl derivatives, that have all identical XAS spectra. This result indicates that starting from 1-buthyl-3-methylimidazolium bromide the local molecular arrangement around the bromide anion is the same independently from the length of the alkyl chain, and that the imidazolium head groups in the liquid ILs with long alkyl chains assume locally the same orientation as in the [C{sub 4}mim]Br crystal. With this study we show that the XAS technique is an effective direct tool for unveiling the local structural arrangements around selected atoms in ILs.

  12. Thomson Thick X-Ray Absorption in a Broad Absorption Line Quasar, PG 0946+301.

    PubMed

    Mathur; Green; Arav; Brotherton; Crenshaw; deKool; Elvis; Goodrich; Hamann; Hines; Kashyap; Korista; Peterson; Shields; Shlosman; van Breugel W; Voit

    2000-04-20

    We present a deep ASCA observation of a broad absorption line quasar (BALQSO) PG 0946+301. The source was clearly detected in one of the gas imaging spectrometers, but not in any other detector. If BALQSOs have intrinsic X-ray spectra similar to normal radio-quiet quasars, our observations imply that there is Thomson thick X-ray absorption (NH greater, similar1024 cm-2) toward PG 0946+301. This is the largest column density estimated so far toward a BALQSO. The absorber must be at least partially ionized and may be responsible for attenuation in the optical and UV. If the Thomson optical depth toward BALQSOs is close to 1, as inferred here, then spectroscopy in hard X-rays with large telescopes like XMM would be feasible.

  13. Studies of Y-Ba-Cu-O single crystals by x-ray absorption spectroscopy

    SciTech Connect

    Krol, A.; Ming, Z.H.; Kao, Y.H.; Nuecker, N.; Roth, G.; Fink, J.; Smith, G.C.; Erband, A.; Mueller-Vogt, G.; Karpinski, J.; Kaldis, E.; Schoenmann, K.

    1992-02-01

    The symmetry and density of unoccupied states of YBa{sub 2}Cu{sub 3}O{sub 7} YBa{sub 2}Cu{sub 4}O{sub 8} have been investigated by orientation dependent x-ray absorption spectroscopy on the O 1s edge using a bulk-sensitive fluorescence-yield-detection method. It has been found that the O 2p holes are distributed equally between the CuO{sub 2} planes and CuO chains and that the partial density of unoccupied O 2p states in the CuO{sub 2} planes are identical in both systems investigated. The upper Hubbard band has been observed in the planes but not in the chains in both systems. 18 refs.

  14. Calibration and analysis of spatially resolved x-ray absorption spectra from a nonuniform plasma

    NASA Astrophysics Data System (ADS)

    Knapp, P. F.; Hansen, S. B.; Pikuz, S. A.; Shelkovenko, T. A.; Hammer, D. A.

    2012-07-01

    We report here the calibration and analysis techniques used to obtain spatially resolved density and temperature measurements of a pair of imploding aluminum wires from x-ray absorption spectra. A step wedge is used to measure backlighter fluence at the film, allowing transmission through the sample to be measured with an accuracy of ±14% or better. A genetic algorithm is used to search the allowed plasma parameter space and fit synthetic spectra with 20 μm spatial resolution to the measured spectra, taking into account that the object plasma nonuniformity must be physically reasonable. The inferred plasma conditions must be allowed to vary along the absorption path in order to obtain a fit to the spectral data. The temperature is estimated to be accurate to within ±25% and the density to within a factor of two. This information is used to construct two-dimensional maps of the density and temperature of the object plasma.

  15. X-ray absorption of cadmium in the L-edge region

    SciTech Connect

    Padeznik Gomilsek, J.; Kodre, A.; Arcon, I.; Bratina, G.

    2011-11-15

    Atomic x-ray absorption of cadmium in the energy region of L edges was measured on the vapor of the element, in parallel with the absorption of Cd metal foil. Ionization thresholds of the three subshells are determined from the edge profiles, through the energies of pre-edge resonances and indium optical levels in the Z + 1 approximation. A purely experimental result, without extraneous data and with an accuracy of 0.2 eV, is the energy difference between the pre-edge resonance and the threshold energy of the metallic state. Some multielectron-excitation resonances are identified within 30 eV above the edges. The metal foil absorption is used for absolute determination of Cd absorption coefficient.

  16. Zinc ligands in the metal hyperaccumulator Thlaspi caerulescens as determined using X-ray absorption spectroscopy

    SciTech Connect

    Salt, D.E.; Prince, R.C.; Baker, A.J.M.; Raskin, I.; Pickering, I.J.

    1999-03-01

    Using the noninvasive technique of X-ray absorption spectroscopy (XAS), the authors have been able to determine the ligand environment of Zn in different tissues of the Zn-hyperaccumulator Thlaspi caerulescens. The majority of intracellular Zn in roots of T. caerulescens was found to be coordinated with histidine. In the xylem sap Zn was found to be transported mainly as the free hydrated Zn{sup 2+} cation with a smaller proportion coordinated with organic acids. In the shoots, Zn coordination occurred mainly via organic acids, with a smaller proportion present as the hydrated cation and coordinated with histidine and the cell wall. Their data suggest that histidine plays an important role in Zn homeostasis in the roots, whereas organic acids are involved in xylem transport and Zn storage in shoots.

  17. X-ray absorption studies of Ti/polymer and Cr/polymer interfaces

    SciTech Connect

    Opila, R.L.; Konstadinidis, K.; Ibidunni, A.O; Davenport, A.J.; Isaacs, H.S.

    1993-11-01

    The interface formed between metals, Ti and Cr, and polymers, epoxy, and triazine, have been studied, non-destructively, using x-ray absorption spectroscopy. The metals were sputtered onto the polymer surfaces. Titanium reacts extensively, up to Ti thickness of 100 {Angstrom} while Cr remains primarily metallic. In situ heating at 200{degree}C increases the extent of reaction for both metals. Heating has a greater effect on metal/epoxy interfaces than metal/triazine. Titanium and Cr were ion implanted into the polymer in order to determine the interactions of isolated metal atoms with the polymer. Titanium and Cr appear to form oxides as the final reaction product, and the Ti is tetrahedrally coordinated.

  18. Simulations of X-ray absorption spectra: the effect of the solvent.

    PubMed

    Penfold, Thomas J; Curchod, Basile F E; Tavernelli, Ivano; Abela, Rafael; Rothlisberger, Ursula; Chergui, Majed

    2012-07-14

    We perform quantum mechanics/molecular mechanics molecular dynamics simulations on the [Pt(2)(P(2)O(5)H(2))(4)](4-) (abbreviated PtPOP) complex; in water, dimethylformamide and ethanol. These are used to calculate the ground state X-ray absorption spectrum of the complex. The structural parameters from X-ray spectra are usually extracted using a fit of the experimental data. In such simulations the solvent is neglected meaning that any effect of the local environment will be compensated for by structural changes of the solute, leading to possible discrepancies in the extracted structural parameters. Our simulations show a significant solvent effect on the spectra, which has important implications for the structural analysis of molecules in solution.

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

    SciTech Connect

    Rai, V. N.; Rajput, Parasmani; Jha, S. N.; Bhattacharyya, D.

    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}.

  20. IN SITU STUDIES OF CORROSION USING X-RAY ABSORPTION NEAR SPECTROSCOPY (XANES)

    SciTech Connect

    ISAACS, H.S.; SCHMUKI, P.; VIRTANEN, S.

    2001-03-25

    Applications of x-ray absorption near-edge spectroscopy (XANES) and the design of cells for in situ corrosion studies are reviewed. Passive films studies require very thin metal or alloy layers be used having a thickness of the order of the films formed because of penetration of the x-ray beam into the metal substrate. The depth of penetration in water also limits the thickness of solutions that can be used because of water reduces the x-ray intensity. Solution thickness must also be limited in studies of conversion layer formation studies because the masking of the Cr in solution. Illustrative examples are taken from the anodic behavior of Al-Cr alloys, the growth of passive films on Fe and stainless steels, and the formation of chromate conversion layers on Al.

  1. Detection, identification and mapping of iron anomalies in brain tissue using X-ray absorption spectroscopy

    SciTech Connect

    Mikhaylova, A.; Davidson, M.; Toastmann, H.; Channell, J.E.T.; Guyodo, Y.; Batich, C.; Dobson, J.

    2008-06-16

    This work describes a novel method for the detection, identification and mapping of anomalous iron compounds in mammalian brain tissue using X-ray absorption spectroscopy. We have located and identified individual iron anomalies in an avian tissue model associated with ferritin, biogenic magnetite and haemoglobin with a pixel resolution of less than 5 {micro}m. This technique represents a breakthrough in the study of both intra- and extra-cellular iron compounds in brain tissue. The potential for high-resolution iron mapping using microfocused X-ray beams has direct application to investigations of the location and structural form of iron compounds associated with human neurodegenerative disorders - a problem which has vexed researchers for 50 years.

  2. ISMabs: A COMPREHENSIVE X-RAY ABSORPTION MODEL FOR THE INTERSTELLAR MEDIUM

    SciTech Connect

    Gatuzz, E.; Mendoza, C.; García, J.; Kallman, T. R.; Gorczyca, T. W. E-mail: claudio@ivic.gob.ve E-mail: timothy.r.kallman@nasa.gov

    2015-02-10

    We present an X-ray absorption model for the interstellar medium, to be referred to as ISMabs, that takes into account both neutral and ionized species of cosmically abundant elements, and includes the most accurate atomic data available. Using high-resolution spectra from eight X-ray binaries obtained with the Chandra High Energy Transmission Grating Spectrometer, we proceed to benchmark the atomic data in the model particularly in the neon K-edge region. Compared with previous photoabsorption models, which solely rely on neutral species, the inclusion of ions leads to improved spectral fits. Fit parameters comprise the column densities of abundant contributors that allow direct estimates of the ionization states. ISMabs is provided in the appropriate format to be implemented in widely used X-ray spectral fitting packages such as XSPEC, ISIS, and SHERPA.

  3. ISMabs: A Comprehensive X-Ray Absorption Model for the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Gatuzz, E.; García, J.; Kallman, T. R.; Mendoza, C.; Gorczyca, T. W.

    2015-02-01

    We present an X-ray absorption model for the interstellar medium, to be referred to as ISMabs, that takes into account both neutral and ionized species of cosmically abundant elements, and includes the most accurate atomic data available. Using high-resolution spectra from eight X-ray binaries obtained with the Chandra High Energy Transmission Grating Spectrometer, we proceed to benchmark the atomic data in the model particularly in the neon K-edge region. Compared with previous photoabsorption models, which solely rely on neutral species, the inclusion of ions leads to improved spectral fits. Fit parameters comprise the column densities of abundant contributors that allow direct estimates of the ionization states. ISMabs is provided in the appropriate format to be implemented in widely used X-ray spectral fitting packages such as XSPEC, ISIS, and SHERPA.

  4. X-ray Absorption Improvement of Single Wall Carbon Nanotube through Gadolinium Encapsulation

    NASA Astrophysics Data System (ADS)

    Alimin; Narsito, I.; Kartini; Santosa, S. J.

    2016-02-01

    X-ray absorption improvement of single-wall carbon nanotube (SWCNT) through gadolinium (Gd) encapsulation has been studied. The liquid phase adsorption using ethanol has been performed for the doping treatment. The Gd-doped SWCNT (Gd@SWCNT) was characterized by nitrogen adsorption isotherms, Raman spectroscopy, Transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA) techniques. A relatively high residual weight of Gd@SWCNT compared to non-doped SWCNT (n-SWCNT) indicated that Gd has been doped in the nanotube. Even though Gd nanoparticles could not be observed clearly by TEM image, however, a significant decrease of nitrogen uptakes at low pressure and RBM (Radial Breathing Mode) upshift of Raman spectra of Gd@SWCNT specimen suggest that the metal nanoparticles might be encapsulated in the internal tube spaces of the nanotube. It was found that Gd-doped in the SWCNT increased significantly mass attenuation coefficient of the nanotube.

  5. Multiple-scattering approach to the x-ray-absorption spectra of 3d transition metals

    NASA Astrophysics Data System (ADS)

    Kitamura, Michihide; Muramatsu, Shinji; Sugiura, Chikara

    1986-04-01

    The x-ray-absorption near-edge structure (XANES) has been calculated for the 3d transition metals Cr, Fe, Ni, and Cu from a multiple-scattering approach within the muffin-tin-potential approximation, as a first step to studying the XANES for complicated materials. The muffin-tin potential is constructed via the Mattheiss prescription using the atomic data of Herman and Skillman. It is found that the XANES is sensitive to the potential used and that the calculated XANES spectra reproduce the number of peaks and their separations observed experimentally. The final spectra, including the lifetime-broadening effect, show the general features of each material. We emphasize that the multiple-scattering theory which can be applied to the disordered systems as well as the ordered ones may be promising as a tool to analyze the XANES of complicated materials.

  6. X-ray absorption signatures of the molecular environment in water and ice.

    PubMed

    Chen, Wei; Wu, Xifan; Car, Roberto

    2010-07-02

    The x-ray absorption spectra of water and ice are calculated with a many-body approach for electron-hole excitations. The experimental features, including the effects of temperature change in the liquid, are reproduced from configurations generated by ab initio molecular dynamics. The spectral difference between the solid and the liquid is due to two major short-range order effects. One, due to breaking of hydrogen bonds, enhances the pre-edge intensity in the liquid. The other, due to a nonbonded molecular fraction in the first coordination shell, affects the main spectral edge in the conversion of ice to water. This effect may not involve hydrogen bond breaking as shown by experiment in high-density amorphous ice.

  7. X-ray absorption in pillar shaped transmission electron microscopy specimens.

    PubMed

    Bender, H; Seidel, F; Favia, P; Richard, O; Vandervorst, W

    2017-03-07

    The dependence of the X-ray absorption on the position in a pillar shaped transmission electron microscopy specimen is modeled for X-ray analysis with single and multiple detector configurations and for different pillar orientations relative to the detectors. Universal curves, applicable to any pillar diameter, are derived for the relative intensities between weak and medium or strongly absorbed X-ray emission. For the configuration as used in 360° X-ray tomography, the absorption correction for weak and medium absorbed X-rays is shown to be nearly constant along the pillar diameter. Absorption effects in pillars are about a factor 3 less important than in planar specimens with thickness equal to the pillar diameter. A practical approach for the absorption correction in pillar shaped samples is proposed and its limitations discussed. The modeled absorption dependences are verified experimentally for pillars with HfO2 and SiGe stacks.

  8. Search for correlated UV and x ray absorption of NGC 3516

    NASA Technical Reports Server (NTRS)

    Martin, Christopher; Halpern, Jules P.; Kolman, Michiel

    1991-01-01

    NGC 3516, a low-luminosity Seyfert galaxy, is one of a small fraction of Seyfert galaxies that exhibit broad absorption in a resonance line. In order to determine whether the UV and x ray absorption in NGC 3516 are related, 5 IUE observations were obtained, quasi-simultaneously with 4 Ginga observations. The results are presented and discussed. The following subject areas are covered: short-term UV variability; emission lines; galactic absorption lines; the C IV, N V, and Si IV absorption features; lower limit on the carbon column density; estimate of the distance from the absorber to the continuum source; variability in the continuum and absorption; a comparison with BAL QSO's; and the x ray-UV connection.

  9. Structural analysis of sulfur in natural rubber using X-ray absorption near-edge spectroscopy.

    PubMed

    Pattanasiriwisawa, Wanwisa; Siritapetawee, Jaruwan; Patarapaiboolchai, Orasa; Klysubun, Wantana

    2008-09-01

    X-ray absorption near-edge spectroscopy (XANES) has been applied to natural rubber in order to study the local environment of sulfur atoms in sulfur crosslinking structures introduced in the vulcanization process. Different types of chemical accelerators in conventional, semi-efficient and efficient vulcanization systems were investigated. The experimental results show the good sensitivity and reproducibility of XANES to characterize the local geometry and electronic environment of the sulfur K-shell under various conditions of vulcanization and non-vulcanization of natural rubber. Several applications of XANES in this study demonstrate an alternative way of identifying sulfur crosslinks in treated natural rubber based on differences in their spectra and oxidation states.

  10. Observing heme doming in myoglobin with femtosecond X-ray absorption spectroscopya)

    PubMed Central

    Levantino, M.; Lemke, H. T.; Schirò, G.; Glownia, M.; Cupane, A.; Cammarata, M.

    2015-01-01

    We report time-resolved X-ray absorption measurements after photolysis of carbonmonoxy myoglobin performed at the LCLS X-ray free electron laser with nearly 100 fs (FWHM) time resolution. Data at the Fe K-edge reveal that the photoinduced structural changes at the heme occur in two steps, with a faster (∼70 fs) relaxation preceding a slower (∼400 fs) one. We tentatively attribute the first relaxation to a structural rearrangement induced by photolysis involving essentially only the heme chromophore and the second relaxation to a residual Fe motion out of the heme plane that is coupled to the displacement of myoglobin F-helix. PMID:26798812

  11. Instrument for x-ray absorption spectroscopy with in situ electrical control characterizations

    SciTech Connect

    Huang, Chun-Chao; Chang, Shu-Jui; Yang, Chao-Yao; Tseng, Yuan-Chieh; Chou, Hsiung

    2013-12-15

    We report a synchrotron-based setup capable of performing x-ray absorption spectroscopy and x-ray magnetic circular dichroism with simultaneous electrical control characterizations. The setup can enable research concerning electrical transport, element- and orbital-selective magnetization with an in situ fashion. It is a unique approach to the real-time change of spin-polarized electronic state of a material/device exhibiting magneto-electric responses. The performance of the setup was tested by probing the spin-polarized states of cobalt and oxygen of Zn{sub 1-x}Co{sub x}O dilute magnetic semiconductor under applied voltages, both at low (∼20 K) and room temperatures, and signal variations upon the change of applied voltage were clearly detected.

  12. Time-resolved x-ray absorption spectroscopy with a water window high-harmonic source

    NASA Astrophysics Data System (ADS)

    Pertot, Yoann; Schmidt, Cédric; Matthews, Mary; Chauvet, Adrien; Huppert, Martin; Svoboda, Vit; von Conta, Aaron; Tehlar, Andres; Baykusheva, Denitsa; Wolf, Jean-Pierre; Wörner, Hans Jakob

    2017-01-01

    Time-resolved x-ray absorption spectroscopy (TR-XAS) has so far practically been limited to large-scale facilities, to subpicosecond temporal resolution, and to the condensed phase. We report the realization of TR-XAS with a temporal resolution in the low femtosecond range by developing a tabletop high-harmonic source reaching up to 350 electron volts, thus partially covering the spectral region of 280 to 530 electron volts, where water is transmissive. We used this source to follow previously unexamined light-induced chemical reactions in the lowest electronic states of isolated CF4+ and SF6+ molecules in the gas phase. By probing element-specific core-to-valence transitions at the carbon K-edge or the sulfur L-edges, we characterized their reaction paths and observed the effect of symmetry breaking through the splitting of absorption bands and Rydberg-valence mixing induced by the geometry changes.

  13. Melting of iron determined by X-ray absorption spectroscopy to 100 GPa

    PubMed Central

    Aquilanti, Giuliana; Trapananti, Angela; Karandikar, Amol; Kantor, Innokenty; Marini, Carlo; Mathon, Olivier; Pascarelli, Sakura; Boehler, Reinhard

    2015-01-01

    Temperature, thermal history, and dynamics of Earth rely critically on the knowledge of the melting temperature of iron at the pressure conditions of the inner core boundary (ICB) where the geotherm crosses the melting curve. The literature on this subject is overwhelming, and no consensus has been reached, with a very large disagreement of the order of 2,000 K for the ICB temperature. Here we report new data on the melting temperature of iron in a laser-heated diamond anvil cell to 103 GPa obtained by X-ray absorption spectroscopy, a technique rarely used at such conditions. The modifications of the onset of the absorption spectra are used as a reliable melting criterion regardless of the solid phase from which the solid to liquid transition takes place. Our results show a melting temperature of iron in agreement with most previous studies up to 100 GPa, namely of 3,090 K at 103 GPa. PMID:26371317

  14. Note: Sample chamber for in situ x-ray absorption spectroscopy studies of battery materials

    SciTech Connect

    Pelliccione, CJ; Timofeeva, EV; Katsoudas, JP; Segre, CU

    2014-12-01

    In situ x-ray absorption spectroscopy (XAS) provides element-specific characterization of both crystalline and amorphous phases and enables direct correlations between electrochemical performance and structural characteristics of cathode and anode materials. In situ XAS measurements are very demanding to the design of the experimental setup. We have developed a sample chamber that provides electrical connectivity and inert atmosphere for operating electrochemical cells and also accounts for x-ray interactions with the chamber and cell materials. The design of the sample chamber for in situ measurements is presented along with example XAS spectra from anode materials in operating pouch cells at the Zn and Sn K-edges measured in fluorescence and transmission modes, respectively. (C) 2014 AIP Publishing LLC.

  15. High-resolution X-ray absorption spectroscopy of iron carbonyl complexes.

    PubMed

    Atkins, Andrew J; Bauer, Matthias; Jacob, Christoph R

    2015-06-07

    We apply high-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) to study iron carbonyl complexes. Mono-, bi-, and tri-nuclear carbonyl complexes and pure carbonyl complexes as well as carbonyl complexes containing hydrocarbon ligands are considered. The HERFD-XANES spectra reveal multiple pre-edge peaks with individual signatures for each complex, which could not be detected previously with conventional XANES spectroscopy. These peaks are assigned and analysed with the help of TD-DFT calculations. We demonstrate that the pre-edge peaks can be used to distinguish the different types of iron-iron interactions in carbonyl complexes. This opens up new possibilities for applying HERFD-XANES spectroscopy to probe the electronic structure of iron catalysts.

  16. Speciation of arsenic in pyrite by micro-X-ray absorption fine- structure spectroscopy (XAFS)

    SciTech Connect

    Paktunc, D.

    2008-09-30

    Pyrite (FeS2) often contains variable levels of arsenic, regardless of the environment of formation. Arsenian pyrite has been reported in coals, sediments and ore deposits. Arsenian pyrite having As concentrations of up to 10 wt % in sedimentary rocks (Kolker et al. 1997), about 10 wt% in gold deposits (Fleet et al. 1993), 12 wt % in a refractory gold ore (Paktunc et al. 2006) and 20 wt % in a Carlin-type gold deposit in Nevada (Reich et al. 2005) have been reported. Arsenian pyrite is the carrier of gold in hydrothermal Carlin-type gold deposits, and gold concentrations of up to 0.9 wt % have been reported (Reich et al. 2005; Paktunc et al. 2006). In general, high Au concentrations correlate with As-rich zones in pyrite (Paktunc et al. 2006). Pyrite often ends up in mining and metallurgical wastes as an unwanted mineral and consititutes one of the primary sources of As in the wastes. Arsenic can be readily released to the environment due to rapid oxidative dissolution of host pyrite under atmospheric conditions. Pyrite is also the primary source of arsenic in emissions and dust resulting from combustion of bituminous coals. Despite the importance of arsenian pyrite as a primary source of anthropogenic arsenic in the environment and its economic significance as the primary carrier of gold in Carlin-type gold deposits, our understanding of the nature of arsenic in pyrite is limited. There are few papers dealing with the mode of occurrence of arsenic by bulk XAFS in a limited number of pyrite-bearing samples. The present study documents the analysis of pyrite particles displaying different morphologies and a range of arsenic and gold concentrations to determine the nature and speciation of arsenic.

  17. Sulphur speciation in bitumens and asphaltenes by X-ray absorption fine structure spectroscopy

    SciTech Connect

    Kasrai, M.; Bancroft, G.M.; Brunner, R.W. ); Jonasson, R.G. ); Tan, K.H.; Feng, X. ); Brown, J.R.

    1994-07-01

    The S L-edge and K-edge XANES spectra were collected on bitumen and asphaltene samples as well as model compounds in order to determine the feasibility of monitoring transformations of organic sulphur in bitumen during genesis, processing, and upgrading. Using the spectra of model compounds as fingerprints, it was possible to speciate the sulphur forms in bitumen and asphaltene. The reduced form of sulphur such as thiophenes are the predominant form of sulphur in the bitumen and asphaltene samples analyzed. No significant amounts of oxidized sulphur forms could be detected. Spectra collected using total electron yield and fluorescence yield were identical, confirming that there is no preferential partitioning at the bitumen/air interface, or oxidation during sample handling. Also important was the finding that bitumen could be analyzed at moderately high vacuum (10[sup [minus]8] torr). Thus XANES represents a rapid, nondestructive mean of characterizing specific classes of compounds in complex matrices, such as bitumen.

  18. An X-Ray Absorption Fine Structure Study of Ordering in Polythiophene Thin Films

    DTIC Science & Technology

    1993-09-01

    within experimental error. As a result. XAFS spectroscopy has been shown to be a useful technique for investigating the molecular structure of an...3413300 13400 13500 13600 Energy (eV) Figure 19: Br K-edge X-ray . . bsorption Near Edge Structure for 2,5 dibromothiophene collected in transmission...Structure spectroscopy as a useful technique for investigating structures of materials with potential laser- hardening applications. The near-atomic

  19. PLUTONIUM CONTAMINATION VALENCE STATE DETERMINATION USING X-RAY ABSORPTION FINE STRUCTURE PERMITS CONCRETE RECYCLE

    SciTech Connect

    Ervin, P. F.; Conradson, S. D.

    2002-02-25

    This paper describes the determination of the speciation of plutonium contamination present on concrete surfaces at the Rocky Flats Environmental Technology Site (RFETS). At RFETS, the plutonium processing facilities have been contaminated during multiple events over their 50 year operating history. Contamination has resulted from plutonium fire smoke, plutonium fire fighting water, milling and lathe operation aerosols, furnace operations vapors and plutonium ''dust'' diffusion.

  20. Near-Edge X-ray Absorption Fine Structure within Multilevel Coupled Cluster Theory.

    PubMed

    Myhre, Rolf H; Coriani, Sonia; Koch, Henrik

    2016-06-14

    Core excited states are challenging to calculate, mainly because they are embedded in a manifold of high-energy valence-excited states. However, their locality makes their determination ideal for local correlation methods. In this paper, we demonstrate the performance of multilevel coupled cluster theory in computing core spectra both within the core-valence separated and the asymmetric Lanczos implementations of coupled cluster linear response theory. We also propose a visualization tool to analyze the excitations using the difference between the ground-state and excited-state electron densities.

  1. Electronic structure of fluorinated multiwalled carbon nanotubes studied using x-ray absorption and photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Brzhezinskaya, M. M.; Muradyan, V. E.; Vinogradov, N. A.; Preobrajenski, A. B.; Gudat, W.; Vinogradov, A. S.

    2009-04-01

    This paper presents the results of combined investigation of the chemical bond formation in fluorinated multiwalled carbon nanotubes (MWCNTs) with different fluorine contents (10-55wt%) and reference compounds (highly oriented pyrolytic graphite crystals and “white” graphite fluoride) using x-ray absorption and photoelectron spectroscopy at C1s and F1s thresholds. Measurements were performed at BESSY II (Berlin, Germany) and MAX-laboratory (Lund, Sweden). The analysis of the soft x-ray absorption and photoelectron spectra points to the formation of covalent chemical bonding between fluorine and carbon atoms in the fluorinated nanotubes. It was established that within the probing depth (˜15nm) of carbon nanotubes, the process of fluorination runs uniformly and does not depend on the fluorine concentration. In this case, fluorine atoms interact with MWCNTs through the covalent attachment of fluorine atoms to graphene layers of the graphite skeleton (phase 1) and this bonding is accompanied by a change in the hybridization of the 2s and 2p valence electron states of the carbon atom from the trigonal (sp2) to tetrahedral (sp3) hybridization and by a large electron transfer between carbon an fluorine atoms. In the MWCNT near-surface region the second fluorine-carbon phase with weak electron transfer is formed; it is located mainly within two or three upper graphene monolayers, and its contribution becomes much poorer as the probing depth of fluorinated multiwalled carbon nanotubes (F-MWCNTs) increases. The defluorination process of F-MWCNTs on thermal annealing has been investigated. The conclusion has been made that F-MWCNT defluorination without destruction of graphene layers is possible.

  2. Quantitative Determination of Absolute Organohalogen Concentrations in Environmental Samples by X-ray Absorption Spectroscopy

    SciTech Connect

    Leri,A.; Hay, M.; Lanzirotti, A.; Rao, W.; Myneni, S.

    2006-01-01

    An in situ procedure for quantifying total organic and inorganic Cl concentrations in environmental samples based on X-ray absorption near-edge structure (XANES) spectroscopy has been developed. Cl 1s XANES spectra reflect contributions from all Cl species present in a sample, providing a definitive measure of total Cl concentration in chemically heterogeneous samples. Spectral features near the Cl K-absorption edge provide detailed information about the bonding state of Cl, whereas the absolute fluorescence intensity of the spectra is directly proportional to total Cl concentration, allowing for simultaneous determination of Cl speciation and concentration in plant, soil, and natural water samples. Absolute Cl concentrations are obtained from Cl 1s XANES spectra using a series of Cl standards in a matrix of uniform bulk density. With the high sensitivity of synchrotron-based X-ray absorption spectroscopy, Cl concentration can be reliably measured down to the 5-10 ppm range in solid and liquid samples. Referencing the characteristic near-edge features of Cl in various model compounds, we can distinguish between inorganic chloride (Cl{sub inorg}) and organochlorine (Cl{sub org}), as well as between aliphatic Cl{sub org} and aromatic Cl{sub org}, with uncertainties in the range of {approx}6%. In addition, total organic and inorganic Br concentrations in sediment samples are quantified using a combination of Br 1s XANES and X-ray fluorescence (XRF) spectroscopy. Br concentration is detected down to {approx}1 ppm by XRF, and Br 1s XANES spectra allow quantification of the Br{sub inorg} and Br{sub org} fractions. These procedures provide nondestructive, element-specific techniques for quantification of Cl and Br concentrations that preclude extensive sample preparation.

  3. Evolution of silver nanoparticles in the rat lung investigated by X-ray absorption spectroscopy

    DOE PAGES

    Davidson, R. Andrew; Anderson, Donald S.; Van Winkle, Laura S.; ...

    2014-12-16

    Following a 6-h inhalation exposure to aerosolized 20 and 110 nm diameter silver nanoparticles, lung tissues from rats were investigated with X-ray absorption spectroscopy, which can identify the chemical state of silver species. Lung tissues were processed immediately after sacrifice of the animals at 0, 1, 3, and 7 days post exposure and the samples were stored in an inert and low-temperature environment until measured. We found that it is critical to follow a proper processing, storage and measurement protocol; otherwise only silver oxides are detected after inhalation even for the larger nanoparticles. The results of X-ray absorption spectroscopy measurementsmore » taken in air at 85 K suggest that the dominating silver species in all the postexposure lung tissues were metallic silver, not silver oxide, or solvated silver cations. The results further indicate that the silver nanoparticles in the tissues were transformed from the original nanoparticles to other forms of metallic silver nanomaterials and the rate of this transformation depended on the size of the original nanoparticles. Furthermore, we found that 20 nm diameter silver nanoparticles were significantly modified after aerosolization and 6-h inhalation/deposition, whereas larger, 110 nm diameter nanoparticles were largely unchanged. Over the seven-day postexposure period the smaller 20 nm silver nanoparticles underwent less change in the lung tissue than the larger 110 nm silver nanoparticles. In contrast, silica-coated gold nanoparticles did not undergo any modification processes and remained as the initial nanoparticles throughout the 7-day study period.« less

  4. X-Ray Absorption, Nuclear Infrared Emission, and Dust Covering Factors of AGNs: Testing Unification Schemes

    NASA Astrophysics Data System (ADS)

    Mateos, S.; Carrera, F. J.; Alonso-Herrero, A.; Hernán-Caballero, A.; Barcons, X.; Asensio Ramos, A.; Watson, M. G.; Blain, A.; Caccianiga, A.; Ballo, L.; Braito, V.; Ramos Almeida, C.

    2016-03-01

    We present the distributions of the geometrical covering factors of the dusty tori (f2) of active galactic nuclei (AGNs) using an X-ray selected complete sample of 227 AGNs drawn from the Bright Ultra-hard XMM-Newton Survey. The AGNs have z from 0.05 to 1.7, 2-10 keV luminosities between 1042 and 1046 erg s-1, and Compton-thin X-ray absorption. Employing data from UKIDSS, 2MASS, and the Wide-field Infrared Survey Explorer in a previous work, we determined the rest-frame 1-20 μm continuum emission from the torus, which we model here with the clumpy torus models of Nenkova et al. Optically classified type 1 and type 2 AGNs are intrinsically different, with type 2 AGNs having, on average, tori with higher f2 than type 1 AGNs. Nevertheless, ˜20% of type 1 AGNs have tori with large covering factors, while ˜23%-28% of type 2 AGNs have tori with small covering factors. Low f2 are preferred at high AGN luminosities, as postulated by simple receding torus models, although for type 2 AGNs the effect is certainly small. f2 increases with the X-ray column density, which implies that dust extinction and X-ray absorption take place in material that share an overall geometry and most likely belong to the same structure, the putative torus. Based on our results, the viewing angle, AGN luminosity, and also f2 determine the optical appearance of an AGN and control the shape of the rest-frame ˜1-20 μm nuclear continuum emission. Thus, the torus geometrical covering factor is a key ingredient of unification schemes.

  5. X-RAY ABSORPTION, NUCLEAR INFRARED EMISSION, AND DUST COVERING FACTORS OF AGNs: TESTING UNIFICATION SCHEMES

    SciTech Connect

    Mateos, S.; Carrera, F. J.; Alonso-Herrero, A.; Hernán-Caballero, A.; Barcons, X.; Ramos, A. Asensio; Almeida, C. Ramos; Watson, M. G.; Blain, A.; Caccianiga, A.; Ballo, L.; Braito, V.

    2016-03-10

    We present the distributions of the geometrical covering factors of the dusty tori (f{sub 2}) of active galactic nuclei (AGNs) using an X-ray selected complete sample of 227 AGNs drawn from the Bright Ultra-hard XMM-Newton Survey. The AGNs have z from 0.05 to 1.7, 2–10 keV luminosities between 10{sup 42} and 10{sup 46} erg s{sup −1}, and Compton-thin X-ray absorption. Employing data from UKIDSS, 2MASS, and the Wide-field Infrared Survey Explorer in a previous work, we determined the rest-frame 1–20 μm continuum emission from the torus, which we model here with the clumpy torus models of Nenkova et al. Optically classified type 1 and type 2 AGNs are intrinsically different, with type 2 AGNs having, on average, tori with higher f{sub 2} than type 1 AGNs. Nevertheless, ∼20% of type 1 AGNs have tori with large covering factors, while ∼23%–28% of type 2 AGNs have tori with small covering factors. Low f{sub 2} are preferred at high AGN luminosities, as postulated by simple receding torus models, although for type 2 AGNs the effect is certainly small. f{sub 2} increases with the X-ray column density, which implies that dust extinction and X-ray absorption take place in material that share an overall geometry and most likely belong to the same structure, the putative torus. Based on our results, the viewing angle, AGN luminosity, and also f{sub 2} determine the optical appearance of an AGN and control the shape of the rest-frame ∼1–20 μm nuclear continuum emission. Thus, the torus geometrical covering factor is a key ingredient of unification schemes.

  6. Density Measurement for MORB Melts by X-ray Absorption Method

    NASA Astrophysics Data System (ADS)

    Sakamaki, T.; Urakawa, S.; Ohtani, E.; Suzuki, A.; Katayama, Y.

    2005-12-01

    Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the edge-length of 6 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 4 GPa, from 300 to 2200 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

  7. Density Measurement for MORB Melts by X-ray Absorption Method

    NASA Astrophysics Data System (ADS)

    Sakamaki, T.; Urakawa, S.; Suzuki, A.; Ohtani, E.; Katayama, Y.

    2006-12-01

    Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the top anvil sizes of 6 mm and 4 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 5 GPa, from 300 to 2000 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

  8. Soft X-ray absorption spectra in the 0 K region of microporous carbon and some reference aromatic compounds

    SciTech Connect

    Muramatsu, Yasuji; Kuramoto, Kentaro; Gullikson, Eric M.; Perera, Rupert C.C.

    2003-06-01

    To analyze the oxidation states of the graphitic surface of microporous carbon, soft X-ray absorption spectra in the 0 K region have been obtained for microporous carbon and various aromatic compounds. The aromatic molecules studied are substituted with one or more of the following oxygenated functional groups: hydroxy (-OH), carboxy (-COOH), carbonyl (>C=O), formyl (-CH=O), and ether (-O-). From comparison of the soft X-ray absorption spectra of microporous carbon and of reference aromatic compounds, the most probable chemical bonding states of oxygen in microporous carbon are found to be -COOH and >C(H)=O. Spectral features in the soft X-ray absorption spectra of microporous carbon are well explained by the O2p density of states in these oxygenated functional groups from discrete variational (DV)-X{alpha} molecular orbital calculations.

  9. Low-Dimensional Water on Ru(0001)Model System for X-ray Absorption Spectroscopy Studies of Liquid Water

    SciTech Connect

    Nordlund, D

    2012-02-14

    We present an x-ray absorption spectroscopy results for fully broken to a complete H-bond network of water molecules on Ru(0001) by varying the morphology from isolated water molecules via two-dimensional clusters to a fully covered monolayer as probed by scanning tunneling microscopy. The sensitivity of x-ray absorption to the symmetry of H-bonding is further elucidated for the amino (-NH{sub 2}) group in glycine adsorbed on Cu(110) where the E-vector is parallel either to the NH donating an H-bond or to the non-H-bonded NH. The results give further evidence for the interpretation of the various spectral features of liquid water and for the general applicability of x-ray absorption spectroscopy to analyze H-bonded systems.

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

    PubMed

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

    2013-08-07

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

  11. General Method for Determination of the Surface Composition in Bimetallic Nanoparticle Catalysts from the L Edge X-ray Absorption Near-Edge Spectra

    SciTech Connect

    Wu, Tiapin; Childers, David; Gomez, Carolina; Karim, Ayman M.; Schweitzer, Neil; Kropf, Arthur; Wang, Hui; Bolin, Trudy B.; Hu, Yongfeng; Kovarik, Libor; Meyer, Randall; Miller, Jeffrey T.

    2012-10-08

    Bimetallic PtPd on silica nano-particle catalysts have been synthesized and their average structure determined by Pt L3 and Pd K-edge extended X-ray absorption finestructure (EXAFS) spectroscopy. The bimetallic structure is confirmed from elemental line scans by STEM for the individual 1-2 nm sized particles. A general method is described to determine the surface composition in bimetallic nanoparticles even when both metals adsorb, for example, CO. By measuring the change in the L3 X-ray absorption near-edge structure (XANES) spectra with and without CO in bimetallic particles and comparing these changes to those in monometallic particles of known size the fraction of surface atoms can be determined. The turnover rates (TOR) and neopentane hydrogenolysis and isomerization selectivities based on the surface composition suggest that the catalytic and spectroscopic properties are different from those in monometallic nano-particle catalysts. At the same neo-pentane conversion, the isomerization selectivity is higher for the PtPd catalyst while the TOR is lower than that of both Pt and Pd. As with the catalytic performance, the infrared spectra of adsorbed CO are not a linear combination of the spectra on monometallic catalysts. Density functional theory calculations indicate that the Pt-CO adsorption enthalpy increases while the Pd-CO bond energy decreases. The ability to determine the surface composition allows for a better understanding of the spectroscopic and catalytic properties of bimetallic nanoparticle catalysts.

  12. Comparison of x-ray absorption spectra between water and ice: New ice data with low pre-edge absorption cross-section

    SciTech Connect

    Sellberg, Jonas A.; Nilsson, Anders; Kaya, Sarp; Segtnan, Vegard H.; Chen, Chen; Tyliszczak, Tolek; Ogasawara, Hirohito; Nordlund, Dennis; Pettersson, Lars G. M.

    2014-07-21

    The effect of crystal growth conditions on the O K-edge x-ray absorption spectra of ice is investigated through detailed analysis of the spectral features. The amount of ice defects is found to be minimized on hydrophobic surfaces, such as BaF{sub 2}(111), with low concentration of nucleation centers. This is manifested through a reduction of the absorption cross-section at 535 eV, which is associated with distorted hydrogen bonds. Furthermore, a connection is made between the observed increase in spectral intensity between 544 and 548 eV and high-symmetry points in the electronic band structure, suggesting a more extended hydrogen-bond network as compared to ices prepared differently. The spectral differences for various ice preparations are compared to the temperature dependence of spectra of liquid water upon supercooling. A double-peak feature in the absorption cross-section between 540 and 543 eV is identified as a characteristic of the crystalline phase. The connection to the interpretation of the liquid phase O K-edge x-ray absorption spectrum is extensively discussed.

  13. Cytochrome c in a Dry Trehalose Matrix: Structural and Dynamical Effects Probed by X-Ray Absorption Spectroscopy

    PubMed Central

    Giachini, Lisa; Francia, Francesco; Cordone, Lorenzo; Boscherini, Federico; Venturoli, Giovanni

    2007-01-01

    We report on the structure and dynamics of the Fe ligand cluster of reduced horse heart cytochrome c in solution, in a dried polyvinyl alcohol (PVA) film, and in two trehalose matrices characterized by different contents of residual water. The effect of the solvent/matrix environment was studied at room temperature using Fe K-edge x-ray absorption fine structure (XAFS) spectroscopy. XAFS data were analyzed by combining ab initio simulations and multi-parameter fitting in an attempt to disentangle structural from disorder parameters. Essentially the same structural and disorder parameters account adequately for the XAFS spectra measured in solution, both in the absence and in the presence of glycerol, and in the PVA film, showing that this polymer interacts weakly with the embedded protein. Instead, incorporation in trehalose leads to severe structural changes, more prominent in the more dried matrix, consisting of 1), an increase up to 0.2 Å of the distance between Fe and the imidazole N atom of the coordinating histidine residue and 2), an elongation up to 0.16 Å of the distance between Fe and the fourth-shell C atoms of the heme pyrrolic units. These structural distortions are accompanied by a substantial decrease of the relative mean-square displacements of the first ligands. In the extensively dried trehalose matrix, extremely low values of the Debye Waller factors are obtained for the pyrrolic and for the imidazole N atoms. This finding is interpreted as reflecting a drastic hindering in the relative motions of the Fe ligand cluster atoms and an impressive decrease in the static disorder of the local Fe structure. It appears, therefore, that the dried trehalose matrix dramatically perturbs the energy landscape of cyrochrome c, giving rise, at the level of local structure, to well-resolved structural distortions and restricting the ensemble of accessible conformational substates. PMID:17142287

  14. Dissimilar behavior of technetium and rhenium in borosilicatewaste glass as determined by X-ray absorption spectroscopy

    SciTech Connect

    Lukens, Wayne W.; McKeown, David A.; Buechele, Andrew C.; Muller,Isabelle S.; Shuh, David K.; Pegg, Ian L.

    2006-11-09

    Technetium-99 is an abundant, long-lived (t1/2 = 213,000 yr)fission product that creates challenges for the safe, long-term disposalof nuclear waste. While 99Tc receives attention largely due to its highenvironmental mobility, it also causes problems during its incorporationinto nuclear waste glass due to the volatility of Tc(VII) compounds. Thisvolatility decreases the amount of 99Tc stabilized in the waste glass andcauses contamination of the waste glass melter and off-gas system. Theapproach to decrease the volatility of 99Tc that has received the mostattention is reduction of the volatile Tc(VII) species to less volatileTc(IV) species in the glass melt. On engineering scale experiments,rhenium is often used as a non-radioactive surrogate for 99Tc to avoidthe radioactive contamination problems caused by volatile 99Tc compounds.However, Re(VII) is more stable towards reduction than Tc(VII), so morereducing conditions would be required in the glass melt to produceRe(IV). To better understand the redox behavior of Tc and Re in nuclearwaste glass, a series of glasses were prepared under different redoxconditions. The speciation of Tc and Re in the resulting glasses wasdetermined by X-ray absorption fine structure spectroscopy. Surprisingly,Re and Tc do not behave similarly in the glass melt. Although Tc(0),Tc(IV), and Tc(VII) were observed in these samples, only Re(0) andRe(VII) were found. In no case was Re(IV) (or Re(VI))observed.

  15. Characteristics of Organobentonite and Study of Iodide Adsorption on Organobentonite using X-ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yoon, J.; Ha, J.; Hwang, B.; Hwang, J.; Brown, G. E.

    2008-12-01

    The adsorption of iodide on untreated bentonite and bentonites modified with organic cation (i.e., hexadecylpyridinium chloride monohydrate (HDP+)) was investigated, and the organobentonites were characterized using uptake measurements, micro X-ray diffraction (micro-XRD), and electrophoretic mobility measurements prior to reaction with KI solutions. Uptake measurements indicate that bentonite has a high affinity for HDP+. Increasing [HDP+](aq) results in an increase in HDP+ uptake on bentonite by up to 280% of the CEC equivalents of bentonite, and causes a concomitant increase in Na released as a result of the replacement of exchangeable inorganic cations in bentonite interlayers. Based micro-XRD, the d001 spacing of untreated bentonite was 1.22 nm whereas organobentonites modified with HDP+ at different equivalent amounts, corresponding to 100%, 200%, and 400% of the cation exchange capacity (CEC) of bentonite, showed d001 spacings of 1.96 nm, 3.77 nm, and 3.77 nm, respectively. Our micro-XRD study indicates that organobentonites significantly expanded in basal spacing and organic cations were substantially intercalated into the interlayer spaces of montmorillonite. The electrophoretic mobility indicates that the untreated bentonite had a negative surface charge over the entire pH range examined (pH 2-12) whereas the organobentonite at an equivalent amount corresponding to 200% of the CEC had a positive surface charge over this pH range. We found significant differences in adsorption capacities of iodide depending on the bentonite properties as follows: iodide adsorption capacities were 439 mmol/kg for the bentonite modified with HDP+ at an equivalent amount corresponding to 200% of the CEC of bentonite whereas no adsorption of iodide was observed for the untreated bentonite. The molecular environments of iodine adsorbed on organobentonites were further studied using I K-edge and LIII-edge x-ray absorption spectroscopy (XAS). The X-ray absorption near

  16. X-ray absorption spectroscopy systematics at the tungsten L-edge.

    PubMed

    Jayarathne, Upul; Chandrasekaran, Perumalreddy; Greene, Angelique F; Mague, Joel T; DeBeer, Serena; Lancaster, Kyle M; Sproules, Stephen; Donahue, James P

    2014-08-18

    A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W(0)(PMe3)6], [W(II)Cl2(PMePh2)4], [W(III)Cl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [W(IV)Cl4(PMePh2)2], [W(V)(NPh)Cl3(PMe3)2], and [W(VI)Cl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W(IV)(mdt)2(CO)2] and [W(IV)(mdt)2(CN)2](2-) (mdt(2-) = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W(IV) species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate

  17. X-ray Absorption Spectroscopy Systematics at the Tungsten L-Edge

    PubMed Central

    2015-01-01

    A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W0(PMe3)6], [WIICl2(PMePh2)4], [WIIICl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [WIVCl4(PMePh2)2], [WV(NPh)Cl3(PMe3)2], and [WVICl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [WIV(mdt)2(CO)2] and [WIV(mdt)2(CN)2]2– (mdt2– = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively WIV species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal–ligand distances, exaggerate the difference

  18. Time-resolved x-ray absorption spectroscopy of photoinduced insulator-metal transition in a colossal magnetoresistive manganite

    SciTech Connect

    Rini, M.; Tobey, R.; Wall, S.; Zhu, Y.; Tomioka, Y.; Tokura, Y.; Cavalleri, A.; Schoenlein, R.W.

    2008-08-01

    We studied the ultrafast insulator-metal transition in a manganite by means of picosecond X-ray absorption at the O K- and Mn L-edges, probing photoinduced changes in O-2p and Mn-3d electronic states near the Fermi level.

  19. Influence of substituents on the N K X-ray absorption near-edge structure of pyrrole derivatives

    NASA Astrophysics Data System (ADS)

    Hennig, C.; Hallmeier, K. H.; Bach, A.; Bender, S.; Franke, R.; Hormes, J.; Szargan, R.

    1996-08-01

    The X-ray absorption and electron yield spectra of monomeric pyrrole including derivatives with different substituents, thiazole and oxazole have been investigated. Inductive and mesomeric effects on the spectral features are discussed. Inductive effects create energy shifts of the π ∗ resonances: mesomeric effects cause a splitting and energy shifts of the π ∗ resonances.

  20. Revealing electronic structure changes in Chevrel phase cathodes upon Mg insertion using X-ray absorption spectroscopy

    SciTech Connect

    Wan, Liwen F.; Wright, Joshua; Perdue, Brian R.; Fister, Timothy T.; Kim, Soojeong; Apblett, Christopher A.; Prendergast, David

    2016-06-10

    Following previous work predicting the electronic response of the Chevrel phase Mo6S8 upon Mg insertion (Thole et al., Phys. Chem. Chem. Phys., 2015, 17, 22548), we provide the experimental proof, evident in X-ray absorption spectroscopy, to illustrate the charge compensation mechanism of the Chevrel phase compound during Mg insertion and de-insertion processes.

  1. Beyond structure: ultrafast X-ray absorption spectroscopy as a probe of non-adiabatic wavepacket dynamics.

    PubMed

    Neville, Simon P; Averbukh, Vitali; Patchkovskii, Serguei; Ruberti, Marco; Yun, Renjie; Chergui, Majed; Stolow, Albert; Schuurman, Michael S

    2016-12-16

    The excited state non-adiabatic dynamics of polyatomic molecules, leading to the coupling of structural and electronic dynamics, is a fundamentally important yet challenging problem for both experiment and theory. Ongoing developments in ultrafast extreme vacuum ultraviolet (XUV) and soft X-ray sources present new probes of coupled electronic-structural dynamics because of their novel and desirable characteristics. As one example, inner-shell spectroscopy offers localized, atom-specific probes of evolving electronic structure and bonding (via chemical shifts). In this work, we present the first on-the-fly ultrafast X-ray time-resolved absorption spectrum simulations of excited state wavepacket dynamics: photo-excited ethylene. This was achieved by coupling the ab initio multiple spawning (AIMS) method, employing on-the-fly dynamics simulations, with high-level algebraic diagrammatic construction (ADC) X-ray absorption cross-section calculations. Using the excited state dynamics of ethylene as a test case, we assessed the ability of X-ray absorption spectroscopy to project out the electronic character of complex wavepacket dynamics, and evaluated the sensitivity of the calculated spectra to large amplitude nuclear motion. In particular, we demonstrate the pronounced sensitivity of the pre-edge region of the X-ray absorption spectrum to the electronic and structural evolution of the excited-state wavepacket. We conclude that ultrafast time-resolved X-ray absorption spectroscopy may become a powerful tool in the interrogation of excited state non-adiabatic molecular dynamics.

  2. Probing CuI in Homogeneous Catalysis using High-Energy-Resolution Fluorescence-Detected X-ray Absorption Spectroscopy

    PubMed Central

    Walroth, Richard C.; Uebler, Jacob W. H.

    2015-01-01

    Metal-to-ligand charge transfer excitations in CuI X-ray absorption spectra are introduced as spectroscopic handles for the characterization of species in homogeneous catalytic reaction mixtures. Analysis is supported by correlation of a spectral library to calculations and to complementary spectroscopic parameters. PMID:25994112

  3. Solvent Dependence of the Molecular Order in Ion-Exchanged Self-Assembled dialkylammonium Monolayers on Mica Studied with Soft X-ray Absorption

    SciTech Connect

    Hahner,G.; Zwahlen, M.; Caseri, W.

    2005-01-01

    Dialkyldimethylammonium films on mica prepared via ion exchange from solution have been reported to be of high quality in terms of their density and molecular orientation. Different preparation procedures are described in the literature. The molecular order and the inclination of the alkyl chains, however, are often deduced from indirect experimental evidence such as the wettability and the film thickness. In the present study we employed near edge X-ray absorption fine structure spectroscopy (NEXAFS) to determine directly the order of the molecules adsorbed from different solvents (water, methanol, water/methanol 1:1, cyclohexanol, and chloroform). It was found that films prepared from different solvents are displaying large differences in the established surface coverage and orientation. In particular, NEXAFS disclosed that the orientation of the alkyl chains can differ significantly even when similar water contact angle values are observed.

  4. Carbon X-ray absorption spectra of fluoroethenes and acetone: a study at the coupled cluster, density functional, and static-exchange levels of theory.

    PubMed

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

    2013-03-28

    Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as the state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger π-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to π∗-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate π∗-peak separations due to spectral compressions, a characteristic which is inherent to this

  5. Carbon X-ray absorption spectra of fluoroethenes and acetone: A study at the coupled cluster, density functional, and static-exchange levels of theory

    SciTech Connect

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

    2013-03-28

    Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as the state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger {pi}-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to {pi}*-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate {pi}*-peak separations due to spectral compressions, a characteristic which is inherent to this

  6. Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Qinghao; Qiao, Ruimin; Wray, L. Andrew; Chen, Jun; Zhuo, Zengqing; Chen, Yanxue; Yan, Shishen; Pan, Feng; Hussain, Zahid; Yang, Wanli

    2016-10-01

    Most battery positive electrodes operate with a 3d transition-metal (TM) reaction centre. A direct and quantitative probe of the TM states upon electrochemical cycling is valuable for understanding the detailed cycling mechanism and charge diffusion in the electrodes, which is related with many practical parameters of a battery. This review includes a comprehensive summary of our recent demonstrations of five different types of quantitative analysis of the TM states in battery electrodes based on soft x-ray absorption spectroscopy and multiplet calculations. In LiFePO4, a system of a well-known two-phase transformation type, the TM redox could be strictly determined through a simple linear combination of the two end-members. In Mn-based compounds, the Mn states could also be quantitatively evaluated, but a set of reference spectra with all the three possible Mn valences needs to be deliberately selected and considered in the fitting. Although the fluorescence signals suffer the self-absorption distortion, the multiplet calculations could consider the distortion effect, which allows a quantitative determination of the overall Ni oxidation state in the bulk. With the aid of multiplet calculations, one could also achieve a quasi-quantitative analysis of the Co redox evolution in LiCoO2 based on the energy position of the spectroscopic peak. The benefit of multiplet calculations is more important for studying electrode materials with TMs of mixed spin states, as exemplified by the quantitative analysis of the mixed spin Na2-x Fe2(CN)6 system. At the end, we showcase that such quantitative analysis could provide valuable information for optimizing the electrochemical performance of Na0.44MnO2 electrodes for Na-ion batteries. The methodology summarized in this review could be extended to other energy application systems with TM redox centre for detailed analysis, for example, fuel cell and catalytic materials.

  7. X-ray Absorption Spectroscopy Characterization of a Li/S Cell

    DOE PAGES

    Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; ...

    2016-01-11

    The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br₋) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface duringmore » the charge/discharge processes make the capacity decay. Lastly, a modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.« less

  8. First in-flight synchrotron X-ray absorption and photoemission study of carbon soot nanoparticles

    NASA Astrophysics Data System (ADS)

    Ouf, F.-X.; Parent, P.; Laffon, C.; Marhaba, I.; Ferry, D.; Marcillaud, B.; Antonsson, E.; Benkoula, S.; Liu, X.-J.; Nicolas, C.; Robert, E.; Patanen, M.; Barreda, F.-A.; Sublemontier, O.; Coppalle, A.; Yon, J.; Miserque, F.; Mostefaoui, T.; Regier, T. Z.; Mitchell, J.-B. A.; Miron, C.

    2016-11-01

    Many studies have been conducted on the environmental impacts of combustion generated aerosols. Due to their complex composition and morphology, their chemical reactivity is not well understood and new developments of analysis methods are needed. We report the first demonstration of in-flight X-ray based characterizations of freshly emitted soot particles, which is of paramount importance for understanding the role of one of the main anthropogenic particulate contributors to global climate change. Soot particles, produced by a burner for several air-to-fuel ratios, were injected through an aerodynamic lens, focusing them to a region where they interacted with synchrotron radiation. X-ray photoelectron spectroscopy and carbon K-edge near-edge X-ray absorption spectroscopy were performed and compared to those obtained for supported samples. A good agreement is found between these samples, although slight oxidation is observed for supported samples. Our experiments demonstrate that NEXAFS characterization of supported samples provides relevant information on soot composition, with limited effects of contamination or ageing under ambient storage conditions. The highly surface sensitive XPS experiments of airborne soot indicate that the oxidation is different at the surface as compared to the bulk probed by NEXAFS. We also report changes in soot’s work function obtained at different combustion conditions.

  9. X-ray absorption spectroscopy studies of reactions of technetium, uranium and neptunium with mackinawite.

    PubMed

    Livens, Francis R; Jones, Mark J; Hynes, Amanda J; Charnock, John M; Mosselmans, J Fred W; Hennig, Christoph; Steele, Helen; Collison, David; Vaughan, David J; Pattrick, Richard A D; Reed, Wendy A; Moyes, Lesley N

    2004-01-01

    Technetium, uranium and neptunium may all occur in the environment in more than one oxidation state (IV or VII, IV or VI and IV or V respectively). The surface of mackinawite, the first-formed iron sulfide phase in anoxic conditions, can promote redox changes so a series of laboratory experiments were carried out to explore the interactions of Tc, U and Np with this mineral. The products of reaction were characterised using X-ray absorption spectroscopy. Technetium, added as TcO4(-), is reduced to oxidation state IV and forms a TcS(2)-like species. On oxidation of the mackinawite in air to form goethite, Tc remains in oxidation state IV but in an oxide, rather than a sulfide environment. At low concentrations, uranium forms uranyl surface complexes on oxidised regions of the mackinawite surface but at higher concentrations, the uranium promotes surface oxidation and forms a mixed oxidation state oxide phase. Neptunium is reduced to oxidation IV and forms a surface complex with surface sulfide ions. The remainder of the Np coordination sphere is filled with water molecules or hydroxide ions.

  10. Atomic-scale roughness of Li metal surface evident in soft X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Prendergast, David; Wan, Liwen; Liang, Yufeng; Chuang, Yi-De; Qiao, Ruimin; Yan, Shishen; Yang, Wanli

    2015-03-01

    Realizing Li metal electrodes depends on fundamental understanding and efficient control of surface properties, which requires reliable characterization of the Li metal surface. Controlled experiments of Li K-edge soft X-ray absorption spectroscopy (XAS) reveal evidence of steady oxidation of the Li metal surface even under ultrahigh vacuum (UHV) conditions. The XAS of the short-lived Li metal surface, prepared by in-situ scratching, exhibits a prominent peak at 55.6 eV, more intense and at a slightly higher energy than the first peak expected for bulk Li metal at 55 eV. First-principles XAS calculations explain the origin of both the increased intensity and energy shift. This required the use of surface structural models with under-coordinated Li atoms and an estimated 4 Åinelastic mean-free-path for Auger electrons, implying extreme surface sensitivity of the measurements to the first 2-3 atomic layers. This work provides a benchmark on both experiment and theory for further studies of Li and other reactive metal surfaces, which are currently under scrutiny for next-generation energy storage devices. DP, LW, and YL acknowledge support from the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Dept. of Energy, Office of Science, Basic Energy Sciences.

  11. Finite temperature effects on the X-ray absorption spectra of energy related materials

    NASA Astrophysics Data System (ADS)

    Pascal, Tod; Prendergast, David

    2014-03-01

    We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole (XCH) approach. Based on thermodynamic sampling via ab-initio molecular dynamics (MD) simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1 s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. This work was conducted within the Batteries for Advanced Transportation Technologies (BATT) Program, supported by the U.S. Department of Energy Vehicle Technologies Program under Contract No. DE-AC02-05CH11231.

  12. Predicting X-ray absorption spectra of semiconducting polymers for electronic structure and morphology characterization

    NASA Astrophysics Data System (ADS)

    Su, Gregory; Patel, Shrayesh; Pemmaraju, C. Das; Kramer, Edward; Prendergast, David; Chabinyc, Michael

    2015-03-01

    Core-level X-ray absorption spectroscopy (XAS) reveals important information on the electronic structure of materials and plays a key role in morphology characterization. Semiconducting polymers are the active component in many organic electronics. Their electronic properties are critically linked to device performance, and a proper understanding of semiconducting polymer XAS is crucial. Techniques such as resonant X-ray scattering rely on core-level transitions to gain materials contrast and probe orientational order. However, it is difficult to identify these transitions based on experiments alone, and complementary simulations are required. We show that first-principles calculations can capture the essential features of experimental XAS of semiconducting polymers, and provide insight into which molecular model, such as oligomers or periodic boundary conditions, are best suited for XAS calculations. Simulated XAS can reveal contributions from individual atoms and be used to visualize molecular orbitals. This allows for improved characterization of molecular orientation and scattering analysis. These predictions lay the groundwork for understanding how chemical makeup is linked to electronic structure, and to properly utilize experiments to characterize semiconducting polymers.

  13. Iodine valence and local environments in borosilicate waste glasses using X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    McKeown, David A.; Muller, Isabelle S.; Pegg, Ian L.

    2015-01-01

    The radioisotope 129I, a fission product in spent nuclear fuel, has a long half-life, and can be highly mobile in the environment. Iodine K-edge X-ray absorption spectra were collected to characterize the iodine valence and coordination environment in simulated Hanford low activity waste glasses. Both iodine XANES and EXAFS data for eleven borosilicate glasses indicate iodide-like environments within the glass structure, where I- has Na or Li nearest-neighbors, and where the nearest-neighbor cation-type correlates to the most common network-modifying cation in the glass. This is further supported by the systematic increase of iodine incorporation with the combined Na2O + Li2O content in the glass. EXAFS analyses determined I-Na distances near 3.04 Å with coordination numbers near 4.0 and I-Li distances near 2.80 Å with coordination numbers near 3.0. I-Na environments determined for the glasses are similar to the tetrahedral INa4 coordination found in NaI-sodalite. These weakly bound iodine-alkali configurations may be the only pathways for iodine to be retained in the glass. These environments may be precursors to NaI-sodalite crystallization in Na-rich glass. Iodine also shows distinct differences from chlorine in terms of the preferred sites in the glass structure.

  14. Identification of lead chemical form in mine waste materials by X-ray absorption spectroscopy

    SciTech Connect

    Taga, Raijeli L.; Ng, Jack; Zheng Jiajia; Huynh, Trang; Noller, Barry; Harris, Hugh H.

    2010-06-23

    X-ray absorption spectroscopy (XAS) provides a direct means for measuring lead chemical forms in complex samples. In this study, XAS was used to identify the presence of plumbojarosite (PbFe{sub 6}(SO{sub 4}){sub 4}(OH){sub 12}) by lead L{sub 3}-edge XANES spectra in mine waste from a small gold mining operation in Fiji. The presence of plumbojarosite in tailings was confirmed by XRD but XANES gave better resolution. The potential for human uptake of Pb from tailings was measured using a physiologically based extract test (PBET), an in-vitro bioaccessibility (BAc) method. The BAc of Pb was 55%. Particle size distribution of tailings indicated that 40% of PM{sub 10} particulates exist which could be a potential risk for respiratory effects via the inhalation route. Food items collected in the proximity of the mine site had lead concentrations which exceed food standard guidelines. Lead within the mining lease exceeded sediment guidelines. The results from this study are used to investigate exposure pathways via ingestion and inhalation for potential risk exposure pathways of Pb in that locality. The highest Pb concentration in soil and tailings was 25,839 mg/kg, exceeding the Australian National Environment Protection Measure (NEPM) soil health investigation levels.

  15. Identification of lead chemical form in mine waste materials by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Taga, Raijeli L.; Zheng, Jiajia; Huynh, Trang; Ng, Jack; Harris, Hugh H.; Noller, Barry

    2010-06-01

    X-ray absorption spectroscopy (XAS) provides a direct means for measuring lead chemical forms in complex samples. In this study, XAS was used to identify the presence of plumbojarosite (PbFe6(SO4)4(OH)12) by lead L3-edge XANES spectra in mine waste from a small gold mining operation in Fiji. The presence of plumbojarosite in tailings was confirmed by XRD but XANES gave better resolution. The potential for human uptake of Pb from tailings was measured using a physiologically based extract test (PBET), an in-vitro bioaccessibility (BAc) method. The BAc of Pb was 55%. Particle size distribution of tailings indicated that 40% of PM10 particulates exist which could be a potential risk for respiratory effects via the inhalation route. Food items collected in the proximity of the mine site had lead concentrations which exceed food standard guidelines. Lead within the mining lease exceeded sediment guidelines. The results from this study are used to investigate exposure pathways via ingestion and inhalation for potential risk exposure pathways of Pb in that locality. The highest Pb concentration in soil and tailings was 25,839 mg/kg, exceeding the Australian National Environment Protection Measure (NEPM) soil health investigation levels.

  16. Sulfur speciation in heavy petroleums: Information from X-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Waldo, Geoffrey S.; Carlson, Robert M. K.; Moldowan, J. Michael; Peters, Kenneth E.; Penner-hahn, James E.

    1991-03-01

    The chemical speciation of sulfur in heavy petroleums, petroleum source rock extracts, and source rock pyrolysis products was studied using X-ray absorption near-edge structure (XANES) spectroscopy. The good energy resolution (ca. 0.5 eV) at the sulfur K edge and the strong dependence of XANES on the sulfur environment combine to give excellent sensitivity to changes in the electronic and structural environment of the sulfur. This has permitted identification and approximate quantitation of different classes of sulfur-containing compounds (e.g., sulfur, sulfides (including disulfides and polysulfides as a group), thiophenes, sulfoxides, sulfones, sulfinic acids, sulfonic acids, and sulfate) in a series of petroleums and petroleum source rocks. Our results indicate that the sulfur speciation of geological samples can be correlated with differences in source depositional environment, thermal maturity, and aromaticity. We report organosulfur compositions for the asphaltene, maltene, and liquid Chromatographie fractions of two sulfur-rich oils. In addition, we find that the organosulfur species in some, but not all, oils are subject to oxidation upon storage and thus may also be susceptible to oxidation in shallow reservoirs exposed to oxic waters. This work illustrates the utility of XANES as a direct spectroscopic probe for the quantitative determination of sulfur species in geological samples.

  17. An X-ray diffraction and X-ray absorption spectroscopy joint study of neuroglobin.

    PubMed

    Arcovito, Alessandro; Moschetti, Tommaso; D'Angelo, Paola; Mancini, Giordano; Vallone, Beatrice; Brunori, Maurizio; Della Longa, Stefano

    2008-07-01

    Neuroglobin (Ngb) is a member of the globin family expressed in the vertebrate brain, involved in neuroprotection. A combined approach of X-ray diffraction (XRD) on single crystal and X-ray absorption spectroscopy (XAS) in solution, allows to determine the oxidation state and the structure of the Fe-heme both in the bis-histidine and the CO-bound (NgbCO) states. The overall data demonstrate that under X-ray the iron is photoreduced fairly rapidly, and that the previously reported X-ray structure of ferric Ngb [B. Vallone, K. Nienhaus, M. Brunori, G.U. Nienhaus, Proteins 56 (2004) 85-92] very likely refers to a photoreduced species indistinguishable from the dithionite reduced protein. Results from the XAS analysis of NgbCO in solution are in good agreement with XRD data on the crystal. However prolonged X-ray exposure at 15K determines CO release. This preliminary result paves the way to experiments aimed at the characterization of pentacoordinate ferrous Ngb, the only species competent in binding external ligands such as O2, CO or NO.

  18. Tables of X-ray absorption corrections and dispersion corrections: the new versus the old

    NASA Astrophysics Data System (ADS)

    Creagh, Dudley

    1990-11-01

    This paper compares the data on X-ray absorption coefficients calculated by Creagh and Hubbell and tabulated in International Tables for Crystallography, vol. C, ed. A.J.C. Wilson (1990) section 4.2.4 [1] with empirical (Saloman, Hubbell and Scofield, At. Data and Nucl. Data Tables 38 (1988) 1, [6]) and semi-empirical (Hubbell, McMaster, Kerr Del Grande and Mallett, in: International Tables for Crystallography, vol. IV, eds. Ibers and Hamilton (Kynoch, Birmingham, 1974) [2]) tabulations as well as the renormalized relativistic Dirac-Hartree-Fock calculations of Scofield [6]. It also makes comparisons of the real part of the dispersion correction ƒ‧(ω, 0) and tabulated in ref. [1], with theoretical data sets (Cromer and Liberman, J. Chem. Phys. 53 (1970) 1891, and Acta Crystallogr. A37 (1981) 267 [4,5]; Wang, Phys. Rev. A34 (1986) 636 [85]; Kissel, in: Workshop Report on New Dimensions in X-ray Scattering, CONF-870459 (Livermore, 1987) p. 9 [86]) and data collected using a variety of experimental techniques. In both cases the data tabulated in ref. [1] is shown to give improved self-consistency and agreement with experiment.

  19. X-ray absorption spectroscopy of iron at multimegabar pressures in laser shock experiments

    NASA Astrophysics Data System (ADS)

    Harmand, M.; Ravasio, A.; Mazevet, S.; Bouchet, J.; Denoeud, A.; Dorchies, F.; Feng, Y.; Fourment, C.; Galtier, E.; Gaudin, J.; Guyot, F.; Kodama, R.; Koenig, M.; Lee, H. J.; Miyanishi, K.; Morard, G.; Musella, R.; Nagler, B.; Nakatsutsumi, M.; Ozaki, N.; Recoules, V.; Toleikis, S.; Vinci, T.; Zastrau, U.; Zhu, D.; Benuzzi-Mounaix, A.

    2015-07-01

    Taking advantage of the new opportunities provided by x-ray free electron laser (FEL) sources when coupled to a long laser pulse as available at the Linear Coherent Light Source (LCLS), we have performed x-ray absorption near-edge spectroscopy (XANES) of laser shock compressed iron up to 420 GPa (±50 ) and 10 800 K (±1390 ). Visible diagnostics coupled with hydrodynamic simulations were used to infer the thermodynamical conditions along the Hugoniot and the release adiabat. A modification of the pre-edge feature at 7.12 keV in the XANES spectra is observed above pressures of 260 GPa along the Hugoniot. Comparing with ab initio calculations and with previous laser-heated diamond cell data, we propose that such changes in the XANES pre-edge could be a signature of molten iron. This interpretation then suggests that iron is molten at pressures and temperatures higher than 260 GPa (±29 ) and 5680 K (±700 ) along the principal Fe Hugoniot.

  20. Characterising legacy spent nuclear fuel pond materials using microfocus X-ray absorption spectroscopy.

    PubMed

    Bower, W R; Morris, K; Mosselmans, J F W; Thompson, O R; Banford, A W; Law, K; Pattrick, R A D

    2016-11-05

    Analysis of a radioactive, coated concrete core from the decommissioned, spent nuclear fuel cooling pond at the Hunterston-A nuclear site (UK) has provided a unique opportunity to study radionuclides within a real-world system. The core, obtained from a dividing wall and sampled at the fill level of the pond, exhibited radioactivity (dominantly (137)Cs and (90)Sr) heterogeneously distributed across both painted faces. Chemical analysis of the core was undertaken using microfocus spectroscopy at Diamond Light Source, UK. Mapping of Sr across the surface coatings using microfocus X-ray fluorescence (μXRF) combined with X-ray absorption spectroscopy showed that Sr was bound to TiO2 particles in the paint layers, suggesting an association between TiO2 and radiostrontium. Stable Sr and Cs sorption experiments using concrete coupons were also undertaken to assess their interactions with the bulk concrete in case of a breach in the coating layers. μXRF and scanning electron microscopy showed that Sr was immobilized by the cement phases, whilst at the elevated experimental concentrations, Cs was associated with clay minerals in the aggregates. This study provides a crucial insight into poorly understood infrastructural contamination in complex systems and is directly applicable to the UK's nuclear decommissioning efforts.

  1. X-ray Absorption Spectroscopy Characterization of a Li/S Cell

    PubMed Central

    Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; Feng, Bingmei; Liu, Yi-Sheng; Marcus, Matthew A.; Feng, Jun; Cairns, Elton J.; Guo, Jinghua; Zhu, Junfa

    2016-01-01

    The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We have investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br−) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface during the charge/discharge processes make the capacity decay. A modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies. PMID:28344271

  2. Understanding Sulfur Poisoning and Regeneration of Nickel Biomass Conditioning Catalysts using X-Ray Absorption Spectroscopy

    SciTech Connect

    Yung, M. M.; Cheah, S.; Kuhn, J. N.

    2013-01-01

    The production of biofuels can proceed via a biomass gasification to produce syngas, which can then undergo catalytic conditioning and reforming reactions prior to being sent to a fuel synthesis reactor. Catalysts used for biomass conditioning are plagued by short lifetimes which are a result of, among other things, poisoning. Syngas produced from biomass gasification may contain between 30-300 ppm H2S, depending on the feedstock and gasification conditions, and H2S is a key catalyst poison. In order to overcome catalyst poisoning, either an H2S-tolerant catalyst or an efficient regeneration protocol should be employed. In this study, sulfur K-edge X-ray absorption near edge spectroscopy (XANES) was used to monitor sulfur species on spent catalyst samples and the transformation of these species from sulfides to sulfates during steam and air regeneration on a Ni/Mg/K/Al2O3 catalyst used to condition biomass-derived syngas. Additionally, nickel K-edge EXAFS and XANES are used to examine the state of nickel species on the catalysts. Post-reaction samples showed the presence of sulfides on the H2S-poisoned nickel catalyst and although some gaseous sulfur species were observed to leave the catalyst bed during regeneration, sulfur remained on the catalyst and a transformation from sulfides to sulfates was observed. The subsequent H2 reduction led to a partial reduction of sulfates back to sulfides. A proposed reaction sequence is presented and recommended regeneration strategies are discussed.

  3. First in-flight synchrotron X-ray absorption and photoemission study of carbon soot nanoparticles

    PubMed Central

    Ouf, F.-X.; Parent, P.; Laffon, C.; Marhaba, I.; Ferry, D.; Marcillaud, B.; Antonsson, E.; Benkoula, S.; Liu, X.-J.; Nicolas, C.; Robert, E.; Patanen, M.; Barreda, F.-A.; Sublemontier, O.; Coppalle, A.; Yon, J.; Miserque, F.; Mostefaoui, T.; Regier, T. Z.; Mitchell, J.-B. A.; Miron, C.

    2016-01-01

    Many studies have been conducted on the environmental impacts of combustion generated aerosols. Due to their complex composition and morphology, their chemical reactivity is not well understood and new developments of analysis methods are needed. We report the first demonstration of in-flight X-ray based characterizations of freshly emitted soot particles, which is of paramount importance for understanding the role of one of the main anthropogenic particulate contributors to global climate change. Soot particles, produced by a burner for several air-to-fuel ratios, were injected through an aerodynamic lens, focusing them to a region where they interacted with synchrotron radiation. X-ray photoelectron spectroscopy and carbon K-edge near-edge X-ray absorption spectroscopy were performed and compared to those obtained for supported samples. A good agreement is found between these samples, although slight oxidation is observed for supported samples. Our experiments demonstrate that NEXAFS characterization of supported samples provides relevant information on soot composition, with limited effects of contamination or ageing under ambient storage conditions. The highly surface sensitive XPS experiments of airborne soot indicate that the oxidation is different at the surface as compared to the bulk probed by NEXAFS. We also report changes in soot’s work function obtained at different combustion conditions. PMID:27883014

  4. Soft x-ray absorption spectroscopy studies of doped Pr-containing cuprates

    NASA Astrophysics Data System (ADS)

    Chen, J. M.; Liu, S. J.; Chang, C. F.; Lin, J.-Y.; Gou, Y. S.; Yang, H. D.

    2003-01-01

    Using high-resolution O K-edge x-ray absorption near-edge-structure (XANES) spectroscopy, unoccupied states of the YxPr1-xBa2Cu3O7 (x=0 1) thin films and polycrystalline Pr1-xCaxBa2Cu3O7 (x=0 0.3) as well as R0.8Pr0.2Ba2Cu3O7 samples (R=Tm, Dy, Gd, and Sm) are investigated. In YxPr1-xBa2Cu3O7, hole numbers in the CuO2 planes decrease significantly with increasing Pr doping level. Hole carriers generated via Ca doping in Pr1-xCaxBa2Cu3O7 are directed predominantly into both the Zhang-Rice and Fehrenbacher-Rice (FR) states, while those in the CuO3 ribbons remain almost unchanged with Ca substitution. In R0.8Pr0.2Ba2Cu3O7, the hole content in the CuO2 planes decreases monotonically with increasing ionic size of the R3+ ions, confirming the hole depletion effect based on the Pr 4f O 2p hybridization. We demonstrate the spectroscopic evidence of the existence of the FR states. The present XANES results provide a deeper understanding of the nature of hybridization and the origin of the ionic size effect.

  5. Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides.

    PubMed

    Butorin, Sergei M; Modin, Anders; Vegelius, Johan R; Suzuki, Michi-To; Oppeneer, Peter M; Andersson, David A; Shuh, David K

    2016-04-19

    A systematic X-ray absorption study at actinide N6,7 (4f → 6d transitions) edges was performed for light-actinide oxides including data obtained for the first time for NpO2, PuO2, and UO3. The measurements were supported by ab initio calculations based on local-density-approximation with added 5f-5f Coulomb interaction (LDA+U). Improved energy resolution compared to common experiments at actinide L(2,3) (2p → 6d transitions) edges allowed us to resolve the major structures of the unoccupied 6d density of states (DOS) and estimate the crystal-field splittings in the 6d shell directly from the spectra of light-actinide dioxides. The measurements demonstrated an enhanced sensitivity of the N(6,7) spectral shape to changes in the compound crystal structure. For nonstoichiometric NpO(2-x), the filling of the entire band gap with Np 6d states was observed thus supporting a phase coexistence of Np metal and stoichiometric NpO2 which is in agreement with the tentative Np-O phase diagram.

  6. Properties of aqueous nitrate and nitrite from x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Smith, Jacob W.; Lam, Royce K.; Shih, Orion; Rizzuto, Anthony M.; Prendergast, David; Saykally, Richard J.

    2015-08-01

    Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study. In this work, we describe the study of aqueous solutions of sodium nitrate and nitrite via X-ray absorption spectroscopy (XAS), interpreted in light of first-principles density functional theory electronic structure calculations. Experimental and calculated spectra of the nitrogen K-edge XA spectra of bulk solutions exhibit a large 3.7 eV shift between the XA spectra of nitrate and nitrite resulting from greater stabilization of the nitrogen 1s energy level in nitrate. A similar shift is not observed in the oxygen K-edge XA spectra of NO3- and NO2-. The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.

  7. Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

    PubMed Central

    Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; Sharma, Surbhi; Ganguly, Abhijit; Papakonstantinou, Pagona; Chiou, Jau-Wern; Tsai, Huang-Ming; Shiu, Hung-Wei; Chen, Chia-Hao; Lin, Hong-Ji; Guo, Jinghua; Pong, Way-Faung

    2017-01-01

    Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements. PMID:28186190

  8. Resonant photoemission and X-ray absorption spectroscopies of lithiated magnetite thin film

    NASA Astrophysics Data System (ADS)

    Tsuchiya, Takashi; Kawamura, Kinya; Namiki, Wataru; Furuichi, Shoto; Takayanagi, Makoto; Minohara, Makoto; Kobayashi, Masaki; Horiba, Koji; Kumigashira, Hiroshi; Terabe, Kazuya; Higuchi, Tohru

    2017-04-01

    Resonant photoemission spectroscopy (RPES) and X-ray absorption spectroscopy (XAS) were used to investigate the effect of lithiation on the electronic structure of Fe3O4 thin film relevant to the operation mechanism of nanoionic devices to enable magnetic property tuning. Comparison of the Fe 2p XAS spectrum for lithiated Fe3O4 (Li-Fe3O4) with that for pristine Fe3O4 clearly demonstrated that the number of Fe2+ ions at octahedral B sites is increased by lithiation. The valence band RPES spectra of Li-Fe3O4 further showed that lithiation increases the density of states near the Fermi level originating Fe2+ ions at octahedral B sites. These findings agree well with the observed decrease in the saturation magnetization in the magnetization-magnetic field (M-H) loop of Li-Fe3O4 thin film, indicating that minority spins (down spins) increase (i.e., total spins decrease) due to lithiation. The variation in the number of Fe2+ ions at B sites is suggested to be an underlying operating mechanism of a nanoionics-based magnetic property tuning device.

  9. X-ray absorption and soft x-ray fluorescence analysis of KDP optics

    SciTech Connect

    Nelson, A J; van Buuren, T; Miller, E; Land, T A; Bostedt, C; Franco, N; Whitman, P K; Baisden, P A; Terminello, L J; Callcott, T A

    2000-08-09

    Potassium Dihydrogen Phosphate (KDP) is a non-linear optical material used for laser frequency conversion and optical switches. Unfortunately, when KDP crystals are coated with a porous silica anti-reflection coating [1] and then exposed to ambient humidity, they develop dissolution pits [2,3]. Previous investigations [2] have shown that thermal annealing renders KDP optics less susceptible to pitting suggesting that a modification of surface chemistry has occurred. X-ray absorption and fluorescence were used to characterize changes in the composition and structure of KDP optics as a function of process parameters. KDP native crystals were also analyzed to provide a standard basis for interpretation. Surface sensitive total electron yield and bulk sensitive fluorescence yield from the K 2p, P 2p (L{sub 2,3}-edge) and O 1s (K-edge) absorption edges were measured at each process step. Soft X-ray fluorescence was also used to observe changes associated with spectral differences noted in the absorption measurements. Results indicate that annealing at 160 C dehydrates the surface of KDP resulting in a metaphosphate surface composition with K:P:O = 1:1:3.

  10. Examination of arsenic speciation in sulfidic solutions using X-ray absorption spectroscopy.

    PubMed

    Beak, Douglas G; Wilkin, Richard T; Ford, Robert G; Kelly, Shelly D

    2008-03-01

    Both thioarsenites and thioarsenates have been demonstrated to exist in sulfidic waters, yet there is uncertainty regarding the geochemical conditions that govern the formation of these arsenic species. The purpose of this research was to use advanced spectroscopy techniques, speciation modeling, and chromatography to elucidate the chemical speciation of arsenic in sulfidic solutions initially containing arsenite and sulfide. Results of X-ray absorption spectroscopy (XAS) show that experimental solutions contained mixtures of arsenite and thioarsenites with increasing substitution of sulfur for oxygen on arsenic as the sulfide concentration increased. Experimental samples showed no evidence of polymeric arsenic species, or transformation of thioarsenites to thioarsenates. The arsenic speciation measured using XAS was similar to predictions obtained from a thermodynamic model for arsenic speciation, excluding thioarsenate species in sulfidic systems. Our data cast some doubt on the application of chromatographic methods for determining thioarsenates and thioarsenites (or mixtures) in natural waters in cases where the arsenic oxidation state cannot be independently verified. The same chromatographic peak positions proposed for thioarsenates can be explained bythioarsenite species. Furthermore, sample dilution was shown to change the species distribution and care should be taken to avoid sample dilution prior to chromatographic analysis.

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

    NASA Technical Reports Server (NTRS)

    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.

  12. Fabrication of 200 nanometer period centimeter area hard x-ray absorption gratings by multilayer deposition

    PubMed Central

    Lynch, S K; Liu, C; Morgan, N Y; Xiao, X; Gomella, A A; Mazilu, D; Bennett, E E; Assoufid, L; de Carlo, F; Wen, H

    2012-01-01

    We describe the design and fabrication trials of x-ray absorption gratings of 200 nm period and up to 100:1 depth-to-period ratios for full-field hard x-ray imaging applications. Hard x-ray phase-contrast imaging relies on gratings of ultra-small periods and sufficient depth to achieve high sensitivity. Current grating designs utilize lithographic processes to produce periodic vertical structures, where grating periods below 2.0 μm are difficult due to the extreme aspect ratios of the structures. In our design, multiple bilayers of x-ray transparent and opaque materials are deposited on a staircase substrate, and mostly on the floor surfaces of the steps only. When illuminated by an x-ray beam horizontally, the multilayer stack on each step functions as a micro-grating whose grating period is the thickness of a bilayer. The array of micro-gratings over the length of the staircase works as a single grating over a large area when continuity conditions are met. Since the layers can be nanometers thick and many microns wide, this design allows sub-micron grating periods and sufficient grating depth to modulate hard x-rays. We present the details of the fabrication process and diffraction profiles and contact radiography images showing successful intensity modulation of a 25 keV x-ray beam. PMID:23066175

  13. Examination of arsenic speciation in sulfidic solutions using x-ray absorption spectroscopy.

    SciTech Connect

    Beak, D. G.; Wilkin, R. T.; Ford, R. G.; Kelly, S. D.; Biosciences Division; EPA

    2008-03-01

    Both thioarsenites and thioarsenates have been demonstrated to exist in sulfidic waters, yet there is uncertainty regarding the geochemical conditions that govern the formation of these arsenic species. The purpose of this research was to use advanced spectroscopy techniques, speciation modeling, and chromatography to elucidate the chemical speciation of arsenic in sulfidic solutions initially containing arsenite and sulfide. Results of X-ray absorption spectroscopy (XAS) show that experimental solutions contained mixtures of arsenite and thioarsenites with increasing substitution of sulfur for oxygen on arsenic as the sulfide concentration increased. Experimental samples showed no evidence of polymeric arsenic species, or transformation of thioarsenites to thioarsenates. The arsenic speciation measured using XAS was similar to predictions obtained from a thermodynamic model for arsenic speciation, excluding thioarsenate species in sulfidic systems. Our data cast some doubt on the application of chromatographic methods for determining thioarsenates and thioarsenites (or mixtures) in natural waters in cases where the arsenic oxidation state cannot be independently verified. The same chromatographic peak positions proposed for thioarsenates can be explained by thioarsenite species. Furthermore, sample dilution was shown to change the species distribution and care should be taken to avoid sample dilution prior to chromatographic analysis.

  14. X-ray absorption spectroscopy study of a copper-containing material after thermal treatment.

    PubMed

    Wei, Y-L; Huang, M-Y; Wang, H-C; Huang, H-C; Lee, J-F

    2006-04-17

    Thermal immobilization of copper contaminant in a copper-containing solid material collected from local copper smelting and foundry area is investigated in the present work. X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) are employed for copper speciation. XAS results indicate that cupric hydroxide is the major copper species in the solid material dried at 105 degrees C. After being subjected to a 500 degrees C thermal process, cupric hydroxide still remains as the main copper species, but some Cu(II) is chemically reduced to Cu(I). More cupric hydroxide is progressively converted to Cu(I) as the sample was heated at 1100 degrees C than that heated at 500 degrees C. The sample heated at 500 degrees C is in its original powder form. However, thermal treatment at 1100 degrees C transforms the powder into a hardened granule-like form that is much bigger in size and difficult to be ground into powders. The sample is sintered with the sparingly soluble cuprous oxide and elemental copper being encapsulated inside. Toxicity characteristic leaching procedure (TCLP) results depict that amount of copper leached from the sample (containing 133,000 mg copper kg-1) heated at 1100 degrees C for 2 h is considerably minor, being 367 mg copper kg-1.

  15. X-ray absorption spectroscopy of lithium sulfur battery reaction intermediates

    NASA Astrophysics Data System (ADS)

    Wujcik, Kevin; Pascal, Tod; Prendergast, David; Balsara, Nitash

    2015-03-01

    Lithium sulfur batteries have a theoretical energy density nearly five times greater than current lithium ion battery standards, but questions still remain regarding the reaction pathways through which soluble lithium polysulfide (Li2Sx, ``x'' ranging from 2 to 8) reaction intermediates are formed. Complicating spectroelectrochemical approaches to elucidate redox pathways is the challenge of obtaining spectral standards for individual Li2Sx species. Lithium polysulfides cannot be isolated as individual component and exist only in solution as a distribution of different Li2Sx molecules formed via disproportionation reactions (e.g. 2Li2S4 goes to Li2S3 + Li2S5). X-ray absorption spectroscopy (XAS) at the sulfur K-edge has recently been employed as a technique to study Li-S chemistry. We have recently obtained XAS standards for individual Li2Sx species via first principles DFT simulations and the excited electron and core hole approach. Here, experimental sulfur K-edge XAS of Li2Sx species dissolved in poly(ethylene oxide) are compared to spectra obtained from analogous theoretical calculations. The impact that polysulfide solution concentration and the presence of other lithium salts (e.g. LiNO3) have on X-ray spectra of Li2Sx species is explored via experiment and theory.

  16. X-ray absorption spectroscopy as a probe of dissolved polysulfides in lithium sulfur batteries

    NASA Astrophysics Data System (ADS)

    Pascal, Tod; Prendergast, David

    2015-03-01

    There has been enormous interest lately in lithium sulfur batteries, since they have 5 times the theoretical capacity of lithium ion batteries. Large-scale adoption of this technology has been hampered by numerous shortcomings, chiefly the poor utilization of the active cathode material and rapid capacity fading during cycling. Overcoming these limitations requires methods capable of identifying and quantifying the products of the poorly understood electrochemical reactions. One recent advance has been the use of X-ray absorption spectroscopy (XAS), an element-specific probe of the unoccupied energy levels around an excited atom upon absorption of an X-ray photon, to identify the reaction products and intermediates. In this talk, we'll present first principles molecular dynamics and spectral simulations of dissolved lithium polysulfide species, showing how finite temperature dynamics, molecular geometry, molecular charge state and solvent environment conspire to determine the peak positions and intensity of the XAS. We'll present a spectral analysis of the radical (-1e charge) species, and reveal a unique low energy feature that can be used to identify these species from their more common dianion (-2e charge) counterparts.

  17. Effects of Spatially Heterogeneous Porosity on Matrix-Diffusion as Investigated by X ray Absorption Imaging

    SciTech Connect

    Boney, C.; Christian-Frear, T.; Meigs, L.C.; Tidwell, V.C.

    1998-10-20

    Laboratory experiments were performed to investigate the effects of spatial variation in porosity on matrix-diffusion processes. Four centimeter-scale slabs of Culebra dolomite taken from the Waste Isolation Pilot Plant site were used in the tests. Experiments involved the simple diffusion of iodine into a single edge of each rock slab while X ray absorption imaging was used to measure the resulting two-dmensional solute concentration field as a function of time. X ray imaging was also used to quantify the two-dimensional porosity field of each rock slab. Image analysis provided a unique opportunity to both visuake and quantifj the effects of the spatially variable porosi~ on matrixdMusion. Four key results were obtained. First, significant variation in rates of diffusion were realized over the relatively small length (centimeter) and time scales (months) investigated. Second, clear evidence of diffusion preferentially following zones of relatively higher porosity was noted. Third, rate of difhion was found to vary as tracer diffused into the rock slabs encountering changing porosity conditions. Fourth, strong correlation between porosi~ and the calculated diffusion coefficients was found. In fact, the nature of the correlation can be related to the geometry, position, and orientation of the heterogeneous porosity features populating each rock slab.

  18. Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study.

    PubMed

    Chuang, Cheng-Hao; Ray, Sekhar C; Mazumder, Debarati; Sharma, Surbhi; Ganguly, Abhijit; Papakonstantinou, Pagona; Chiou, Jau-Wern; Tsai, Huang-Ming; Shiu, Hung-Wei; Chen, Chia-Hao; Lin, Hong-Ji; Guo, Jinghua; Pong, Way-Faung

    2017-02-10

    Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp(2)-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

  19. X-ray Absorption Spectroscopy Characterization of a Li/S Cell

    SciTech Connect

    Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; Feng, Bingmei; Liu, Yi-Sheng; Marcus, Matthew A.; Feng, Jun; Cairns, Elton J.; Guo, Jinghua; Zhu, Junfa

    2016-01-11

    The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br₋) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface during the charge/discharge processes make the capacity decay. Lastly, a modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.

  20. Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lam, Royce K.; Smith, Jacob W.; Saykally, Richard J.

    2016-05-01

    While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.

  1. High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue

    NASA Astrophysics Data System (ADS)

    Collingwood, J. F.; Mikhaylova, A.; Davidson, M. R.; Batich, C.; Streit, W. J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R. S.; Dobson, J.

    2005-01-01

    Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (<5 microns). Recent progress in developing the technique is reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterise anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution ~5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

  2. High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue

    SciTech Connect

    Collingwood, J.F.; Mikhaylova, A.; Davidson, M.R.; Batich, C.; Streit, W.J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R.S.; Dobson, J.

    2008-06-16

    Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (< 5 microns). Recent progress in developing the technique is reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterize anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution {approx} 5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

  3. X-Ray Absorption Spectroscopy and Computer Modelling Study of Nanocrystalline Binary Alkaline Earth Fluorides

    NASA Astrophysics Data System (ADS)

    Chadwick, A. V.; Düvel, A.; Heitjans, P.; Pickup, D. M.; Ramos, S.; Sayle, D. C.; Sayle, T. X. T.

    2015-04-01

    Nanocrystalline samples of Ba1-xCaxF2 prepared by high-energy milling show an unusually high F- ion conductivity, which exhibit a maximum in the magnitude and a minimum in the activation energy at x = 0.5. Here, we report an X-ray absorption spectroscopy (XAS) at the Ca and Sr K edges and the Ba L3 edge and a molecular dynamics (MD) simulation study of the pure and mixed fluorides. The XAS measurements on the pure binary fluorides, CaF2, SrF2 and BaF2 show that high-energy ball-milling produces very little amorphous material, in contrast to the results for ball milled oxides. XAS measurements of Ba1-xCaxF2 reveal that for 0 < x <1 there is considerable disorder in the local environments of the cations which is highest for x = 0.5. Hence the maximum in the conductivity corresponds to the composition with the maximum level of local disorder. The MD calculations also show a highly disordered structure consistent with the XAS results and similarly showing maximum disorder at x = 0.5.

  4. On the relation between X-ray absorption and optical extinction in AGN

    NASA Astrophysics Data System (ADS)

    Ordovás-Pascual, I.; Mateos, S.; Carrera, F. J.; Wiersema, K.; Caccianiga, A.; Della Ceca, R.; Severgnini, P.; Moretti, A.; Ballo, L.

    2017-03-01

    According to the Unified Model of Active Galactic Nuclei (AGN), an X-ray unabsorbed AGN should appear as unobscured in the optical band (the so called type-1 AGN). However, there is an important fraction (10–30%) of AGN whose optical and X-ray classifications do not match. To provide insight into the origin of such apparent discrepancies, we have conducted two types of analysis: 1) a detailed study of the UV-to-near-IR emission of two X-ray low absorbed AGN with high optical extinction drawn from the Bright Ultra-Hard XMM-Newton Survey (BUXS); 2) a statistical analysis of the optical obscuration and X-ray absorption properties of 159 type-1 AGN drawn from BUXS to determine the distribution of dust-to-gas ratios in AGN over a broad range of luminosities and redshifts. We have determined the impact of contamination from the AGN hosts in their optical classification (detection or lack of detection of rest-frame UV-optical broad emission lines). This is an on-going project, but our preliminary results, reported below, are very promising.

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

    SciTech Connect

    Vaverka, April Susan Montoya

    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.

  6. Millisecond Kinetics of Nanocrystal Cation Exchange UsingMicrofluidic X-ray Absorption Spectroscopy

    SciTech Connect

    Chan, Emory M.; Marcus, Matthew A.; Fakra, Sirine; Elnaggar,Mariam S.; Mathies, Richard A.; Alivisatos, A. Paul

    2007-05-07

    We describe the use of a flow-focusing microfluidic reactorto measure the kinetics of theCdSe-to-Ag2Se nanocrystal cation exchangereaction using micro-X-ray absorption spectroscopy (mu XAS). The smallmicroreactor dimensions facilitate the millisecond mixing of CdSenanocrystal and Ag+ reactant solutions, and the transposition of thereaction time onto spatial coordinates enables the in situ observation ofthe millisecond reaction with mu XAS. XAS spectra show the progression ofCdSe nanocrystals to Ag2Se over the course of 100 ms without the presenceof long-lived intermediates. These results, along with supporting stoppedflow absorption experiments, suggest that this nanocrystal cationexchange reaction is highly efficient and provide insight into how thereaction progresses in individual particles. This experiment illustratesthe value and potential of in situ microfluidic X-ray synchrotrontechniques for detailed studies of the millisecond structuraltransformations of nanoparticles and other solution-phase reactions inwhich diffusive mixing initiates changes in local bond structures oroxidation states.

  7. First in-flight synchrotron X-ray absorption and photoemission study of carbon soot nanoparticles.

    PubMed

    Ouf, F-X; Parent, P; Laffon, C; Marhaba, I; Ferry, D; Marcillaud, B; Antonsson, E; Benkoula, S; Liu, X-J; Nicolas, C; Robert, E; Patanen, M; Barreda, F-A; Sublemontier, O; Coppalle, A; Yon, J; Miserque, F; Mostefaoui, T; Regier, T Z; Mitchell, J-B A; Miron, C

    2016-11-24

    Many studies have been conducted on the environmental impacts of combustion generated aerosols. Due to their complex composition and morphology, their chemical reactivity is not well understood and new developments of analysis methods are needed. We report the first demonstration of in-flight X-ray based characterizations of freshly emitted soot particles, which is of paramount importance for understanding the role of one of the main anthropogenic particulate contributors to global climate change. Soot particles, produced by a burner for several air-to-fuel ratios, were injected through an aerodynamic lens, focusing them to a region where they interacted with synchrotron radiation. X-ray photoelectron spectroscopy and carbon K-edge near-edge X-ray absorption spectroscopy were performed and compared to those obtained for supported samples. A good agreement is found between these samples, although slight oxidation is observed for supported samples. Our experiments demonstrate that NEXAFS characterization of supported samples provides relevant information on soot composition, with limited effects of contamination or ageing under ambient storage conditions. The highly surface sensitive XPS experiments of airborne soot indicate that the oxidation is different at the surface as compared to the bulk probed by NEXAFS. We also report changes in soot's work function obtained at different combustion conditions.

  8. X-ray absorption spectroscopy of biomimetic dye molecules for solar cells

    SciTech Connect

    Cook, Peter L.; Liu Xiaosong; Himpsel, F. J.; Yang Wanli

    2009-11-21

    Dye-sensitized solar cells are potentially inexpensive alternatives to traditional semiconductor solar cells. In order to optimize dyes for solar cells we systematically investigate the electronic structure of a variety of porphyrins and phthalocyanines. As a biological model system we use the heme group in cytochrome c which plays a role in biological charge transfer processes. X-ray absorption spectroscopy of the N 1s and C 1s edges reveals the unoccupied molecular orbitals and the orientation of the molecules in thin films. The transition metal 2p edges reflect the oxidation state of the central metal atom, its spin state, and the ligand field of the surrounding N atoms. The latter allows tuning of the energy position of the lowest unoccupied orbital by several tenths of an eV by tailoring the molecules and their deposition. Fe and Mn containing phthalocyanines oxidize easily from +2 to +3 in air and require vacuum deposition for obtaining a reproducible oxidation state. Chlorinated porphyrins, on the other hand, are reduced from +3 to +2 during vacuum deposition at elevated temperatures. These findings stress the importance of controlled thin film deposition for obtaining photovoltaic devices with an optimum match between the energy levels of the dye and those of the donor and acceptor electrodes, together with a molecular orientation for optimal overlap between the {pi} orbitals in the direction of the carrier transport.

  9. Toward picosecond time-resolved X-ray absorption studies of interfacial photochemistry

    NASA Astrophysics Data System (ADS)

    Gessner, Oliver; Mahl, Johannes; Neppl, Stefan

    2016-05-01

    We report on the progress toward developing a novel picosecond time-resolved transient X-ray absorption spectroscopy (TRXAS) capability for time-domain studies of interfacial photochemistry. The technique is based on the combination of a high repetition rate picosecond laser system with a time-resolved X-ray fluorescent yield setup that may be used for the study of radiation sensitive materials and X-ray spectroscopy compatible photoelectrochemical (PEC) cells. The mobile system is currently deployed at the Advanced Light Source (ALS) and may be used in all operating modes (two-bunch and multi-bunch) of the synchrotron. The use of a time-stamping technique enables the simultaneous recording of TRXAS spectra with delays between the exciting laser pulses and the probing X-ray pulses spanning picosecond to nanosecond temporal scales. First results are discussed that demonstrate the viability of the method to study photoinduced dynamics in transition metal-oxide semiconductor (SC) samples under high vacuum conditions and at SC-liquid electrolyte interfaces during photoelectrochemical water splitting. Opportunities and challenges are outlined to capture crucial short-lived intermediates of photochemical processes with the technique. This work was supported by the Department of Energy Office of Science Early Career Research Program.

  10. Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

    NASA Astrophysics Data System (ADS)

    Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; Sharma, Surbhi; Ganguly, Abhijit; Papakonstantinou, Pagona; Chiou, Jau-Wern; Tsai, Huang-Ming; Shiu, Hung-Wei; Chen, Chia-Hao; Lin, Hong-Ji; Guo, Jinghua; Pong, Way-Faung

    2017-02-01

    Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

  11. Atomic Structure of Pt3Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy.

    PubMed

    Becknell, Nigel; Kang, Yijin; Chen, Chen; Resasco, Joaquin; Kornienko, Nikolay; Guo, Jinghua; Markovic, Nenad M; Somorjai, Gabor A; Stamenkovic, Vojislav R; Yang, Peidong

    2015-12-23

    Understanding the atomic structure of a catalyst is crucial to exposing the source of its performance characteristics. It is highly unlikely that a catalyst remains the same under reaction conditions when compared to as-synthesized. Hence, the ideal experiment to study the catalyst structure should be performed in situ. Here, we use X-ray absorption spectroscopy (XAS) as an in situ technique to study Pt3Ni nanoframe particles which have been proven to be an excellent electrocatalyst for the oxygen reduction reaction (ORR). The surface characteristics of the nanoframes were probed through electrochemical hydrogen underpotential deposition and carbon monoxide electrooxidation, which showed that nanoframe surfaces with different structure exhibit varying levels of binding strength to adsorbate molecules. It is well-known that Pt-skin formation on Pt-Ni catalysts will enhance ORR activity by weakening the binding energy between the surface and adsorbates. Ex situ and in situ XAS results reveal that nanoframes which bind adsorbates more strongly have a rougher Pt surface caused by insufficient segregation of Pt to the surface and consequent Ni dissolution. In contrast, nanoframes which exhibit extremely high ORR activity simultaneously demonstrate more significant segregation of Pt over Ni-rich subsurface layers, allowing better formation of the critical Pt-skin. This work demonstrates that the high ORR activity of the Pt3Ni hollow nanoframes depends on successful formation of the Pt-skin surface structure.

  12. X-Ray Absorption Spectroscopic Characterization of the Molybdenum Site of 'Escherichia Coli' Dimethyl Sulfoxide Reductase

    SciTech Connect

    George, G.N.; Doonan, C.J.; Rothery, R.A.; Boroumand, N.; Weiner, J.H.; /Saskatchewan U. /Alberta U.

    2007-07-09

    Structural studies of dimethyl sulfoxide (DMSO) reductases were hampered by modification of the active site during purification. We report an X-ray absorption spectroscopic analysis of the molybdenum active site of Escherichia coli DMSO reductase contained within its native membranes. The enzyme in these preparations is expected to be very close to the form found in vivo. The oxidized active site was found to have four Mo-S ligands at 2.43 angstroms, one Mo=O at 1.71 angstroms, and a longer Mo-O at 1.90 angstroms. We conclude that the oxidized enzyme is a monooxomolybdenum(VI) species coordinated by two molybdopterin dithiolenes and a serine. The bond lengths determined for E. coli DMSO reductase are very similar to those determined for the well-characterized Rhodobacter sphaeroides DMSO reductase, suggesting similar active site structures for the two enzymes. Furthermore, our results suggest that the form found in vivo is the monooxobis(molybdopterin) species.

  13. Speciation of Selenium in Stream Insects Using X-Ray Absorption Spectroscopy

    SciTech Connect

    Andrahennadi, R.; Wayland, M.; Pickering, I.J.

    2009-05-28

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

  14. Speciation of selenium in stream insects using X-ray absorption spectroscopy

    SciTech Connect

    Ruwandi Andrahennadi; Mark Wayland; Ingrid J. Pickering

    2007-11-15

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

  15. Coupling MD Simulations and X-ray Absorption Spectroscopy to Study Ions in Solution

    SciTech Connect

    Marcos, E. Sanchez; Beret, E. C.; Martinez, J. M.; Pappalardo, R. R.; Ayala, R.; Munoz-Paez, A.

    2007-11-29

    The structure of ionic solutions is a key-point in understanding physicochemical properties of electrolyte solutions. Among the reduced number of experimental techniques which can supply direct information on the ion environment, X-ray Absorption techniques (XAS) have gained importance during the last decades although they are not free of difficulties associated to the data analysis leading to provide reliable structures. Computer simulations of ions in solution is a theoretical alternative to provide information on the solvation structure. Thus, the use of computational chemistry can increase the understanding of these systems although an accurate description of ionic solvation phenomena represents nowadays a significant challenge to theoretical chemistry. We present: (a) the assignment of features in the XANES spectrum to well defined structural motif in the ion environment, (b) MD-based evaluation of EXAFS parameters used in the fitting procedure to make easier the structural resolution, and (c) the use of the agreement between experimental and simulated XANES spectra to help in the choice of a given intermolecular potential for Computer Simulations. Chemical problems examined are: (a) the identification of the second hydration shell in dilute aqueous solutions of highly-charged cations, such as Cr{sup 3+}, Rh{sup 3+}, Ir{sup 3+}, (b) the invisibility by XAS of certain structures characterized by Computer Simulations but exhibiting high dynamical behavior and (c) the solvation of Br{sup -} in acetonitrile.

  16. Properties of aqueous nitrate and nitrite from x-ray absorption spectroscopy

    SciTech Connect

    Smith, Jacob W.; Lam, Royce K.; Saykally, Richard J.; Shih, Orion; Rizzuto, Anthony M.; Prendergast, David

    2015-08-28

    Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study. In this work, we describe the study of aqueous solutions of sodium nitrate and nitrite via X-ray absorption spectroscopy (XAS), interpreted in light of first-principles density functional theory electronic structure calculations. Experimental and calculated spectra of the nitrogen K-edge XA spectra of bulk solutions exhibit a large 3.7 eV shift between the XA spectra of nitrate and nitrite resulting from greater stabilization of the nitrogen 1s energy level in nitrate. A similar shift is not observed in the oxygen K-edge XA spectra of NO{sub 3}{sup −} and NO{sub 2}{sup −}. The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.

  17. Characterization of the Aqueous Uranyl-Silicate Complex Using X-Ray Absorption Spectroscopy and Ab Initio Modeling

    NASA Astrophysics Data System (ADS)

    Vu, M.; Massey, M.; Huang, P.

    2015-12-01

    The speciation of aqueous uranium ions is an important factor in predicting its mobility and fate in the environment. Two major controls on speciation are pH and the presence of complexing ligands. For the case of aqueous uranyl, UO22+(aq), some common complexes include uranyl-hydroxy, uranyl-carbonato, and uranyl-calcium-carbonato complexes, all of which differ in chemical reactivity and mobility. Uranyl-silicate complexes are also known but remain poorly characterized. In this work, we studied uranyl speciation in a series of aqueous solutions of 0.1 mM uranyl and 2 mM silicate with pH ranging from 4 to 7. Extended X-Ray Absorption Fine Structure (EXAFS) spectra of these samples were recorded at the Stanford Synchrotron Radiation Lightsource (SLAC National Accelerator Laboratory). Of particular note are the uranyl and silicate concentrations employed in our experiments, which are lower than conditions in previously reported EXAFS studies and approach conditions in natural groundwater systems. Preliminary analyses of EXAFS data indicate that uranyl speciation changes across the pH range, consistent with published thermodynamic data that suggest uranyl-silicate complexes may be important for pH ~ 5 and below, while uranyl-carbonato complexes become dominant at circumneutral pH. To guide the interpretation of the EXAFS data, molecular-scale simulations were carried out using density functional theory. We considered two classes of models: (i) hydrated clusters, and (ii) ab initio molecular dynamics simulations of 3D-periodic models involving uranyl and silicate in water. These calculations reveal that at pH ~ 5, the uranyl speciation is the [UO2(H2O)4H3SiO4]+ complex formed by the substitution of an equatorial uranyl water with a monodentate silicate ligand. The evidence from experiments and simulations provide a consistent picture for the uranyl-silicate complex, which may be important in the transport of uranyl in acidic, silicate-rich waters.

  18. Structural consequences of ammonia binding to the manganese center of the photosynthetic oxygen-evolving complex: an X-ray absorption spectroscopy study of isotropic and oriented photosystem II particles.

    PubMed

    Dau, H; Andrews, J C; Roelofs, T A; Latimer, M J; Liang, W; Yachandra, V K; Sauer, K; Klein, M P

    1995-04-18

    The structure and orientation of the manganese complex in NH3-treated photosystem II (PS II) membrane particles of spinach are being studied by X-ray absorption spectroscopy. On the basis of earlier work by our group, a structure for the tetranuclear manganese complex of PS II, which consists of two di-mu-oxo-bridged binuclear Mn units linked by a mono-mu-oxo group, has been proposed [Yachandra, V. K., et al. (1993) Science 260, 675-679]. The extended X-ray absorption fine structure (EXAFS) of the complex modified by NH3 binding in the S2-state is suggestive of an increase in the Mn-Mn distance of one of these units from 2.72 +/- 0.02 to 2.87 +/- 0.02 A, whereas the Mn-Mn distance of the second unit seems to be unaffected by NH3 treatment. The elongation of one binuclear center could result from the replacement of one bridging mu-oxo by an amido group. The lengthening of one Mn-Mn distance means that, by NH3 treatment, the distance degeneracy of the 2.7 A Mn-Mn EXAFS interaction is removed. Consequently, the orientation of individual binuclear units with respect to the membrane normal becomes resolvable by EXAFS spectroscopy of partially oriented PS II membrane particles. The angle between the normal of the PS II-containing membrane and the Mn-Mn vector is determined to be 67 degrees +/- 3 degrees for the 2.87 A distance and 55 degrees +/- 4 degrees for the 2.72 A distance. Only small effects on position, shape, and orientation dependence of Mn K-edge spectra result from NH3 treatment, indicating that the Mn oxidation state, the symmetry of the Mn ligand environment, and the orientation of the complex remain essentially unaffected in the annealed NH3 S2-state. Therefore, it seems likely that the angles determined for the ammonia-modified manganese complex are similar to the respective angles of the untreated complex. The structure of the manganese complex and its orientation in the membrane are discussed.

  19. The S3 state of photosystem II: differences between the structure of the manganese complex in the S2 and S3 states determined by X-ray absorption spectroscopy.

    PubMed

    Guiles, R D; Zimmermann, J L; McDermott, A E; Yachandra, V K; Cole, J L; Dexheimer, S L; Britt, R D; Wieghardt, K; Bossek, U; Sauer, K

    1990-01-16

    O2-evolving photosystem II (PSII) membranes from spinach have been cryogenically stabilized in the S3 state of the oxygen-evolving complex. The cryogenic trapping of the S3 state was achieved using a double-turnover illumination of dark-adapted PSII preparations maintained at 240 K. A double turnover of PSII was accomplished using the high-potential acceptor, Q400, which is the high-spin iron of the iron-quinone acceptor complex. EPR spectroscopy was the principal tool establishing the S-state composition and defining the electron-transfer events associated with a double turnover of PSII. The inflection point energy of the Mn X-ray absorption K-edge of PSII preparations poised in the S3 state is the same as for those poised in the S2 state. This is surprising in light of the loss of the multiline EPR signal upon advancing to the S3 state. This indicates that the oxidative equivalent stored within the oxygen-evolving complex (OEC) during this transition resides on another intermediate donor which must be very close to the manganese complex. An analysis of the Mn extended X-ray absorption fine structure (EXAFS) of PSII preparations poised in the S2 and S3 states indicates that a small structural rearrangement occurs during this photoinduced transition. A detailed comparison of the Mn EXAFS of these two S states with the EXAFS of four multinuclear mu-oxo-bridged manganese compounds indicates that the photosynthetic manganese site most probably consists of a pair of binuclear di-mu-oxo-bridged manganese structures. However, we cannot rule out, on the basis of the EXAFS analysis alone, a complex containing a mononuclear center and a linear trinuclear complex. The subtle differences observed between the S states are best explained by an increase in the spread of Mn-Mn distances occurring during the S2----S3 state transition. This increased disorder in the manganese distances suggests the presence of two inequivalent di-mu-oxo-bridged binuclear structures in the S3 state.

  20. Characterization of the manganese O2-evolving complex and the iron-quinone acceptor complex in photosystem II from a thermophilic cyanobacterium by electron paramagnetic resonance and X-ray absorption spectroscopy.

    PubMed

    McDermott, A E; Yachandra, V K; Guiles, R D; Cole, J L; Dexheimer, S L; Britt, R D; Sauer, K; Klein, M P

    1988-05-31

    The Mn donor complex in the S1 and S2 states and the iron-quinone acceptor complex (Fe2+-Q) in O2-evolving photosystem II (PS II) preparations from a thermophilic cyanobacterium, Synechococcus sp., have been studied with X-ray absorption spectroscopy and electron paramagnetic resonance (EPR). Illumination of these preparations at 220-240 K results in formation of a multiline EPR signal very similar to that assigned to a Mn S2 species observed in spinach PS II, together with g = 1.8 and 1.9 EPR signals similar to the Fe2+-QA- acceptor signals seen in spinach PS II. Illumination at 110-160 K does not produce the g = 1.8 or 1.9 EPR signals, nor the multiline or g = 4.1 EPR signals associated with the S2 state of PS II in spinach; however, a signal which peaks at g = 1.6 appears. The most probable assignment of this signal is an altered configuration of the Fe2+-QA- complex. In addition, no donor signal was seen upon warming the 140 K illuminated sample to 215 K. Following continuous illumination at temperatures between 140 and 215 K, the average X-ray absorption Mn K-edge inflection energy changes from 6550 eV for a dark-adapted (S1) sample to 6551 eV for the illuminated (S2) sample. The shift in edge inflection energy indicates an oxidation of Mn, and the absolute edge inflection energies indicate an average Mn oxidation state higher than Mn(II). Upon illumination a significant change was observed in the shape of the features associated with 1s to 3d transitions. The S1 spectrum resembles those of Mn(III) complexes, and the S2 spectrum resembles those of Mn(IV) complexes. The extended X-ray absorption fine structure (EXAFS) spectrum of the Mn complex is similar in the S1 and S2 states. Simulations indicate O or N ligands at 1.75 +/- 0.05 A, transition metal neighbor(s) at 2.73 +/- 0.05 A, which are assumed to be Mn, and terminal ligands which are probably N and O at a range of distances around 2.2 A. The Mn-O bond length of 1.75 A and the transition metal at 2.7 A

  1. A X-Ray Absorption Study on Melting, Double Electron Excitation and Hemerythrin.

    NASA Astrophysics Data System (ADS)

    Zhang, Ke.

    In this study, X-ray absorption spectroscopy is applied to three systems: xenon atoms; an oxygen transport protein--hemerythrin; and mercury impurities in lead metal. An X-ray absorption experiment on xenon gas shows a clear evidence of the electron shaking up (off) from the valence shells when an L-shell electron is excited. A (DELTA)SCF (self consistent field) calculation in the dipole approximation was performed, which used a local exchange potential and the sudden approximation. The calculation shows that the (DELTA)SCF model is qualitatively and semi -quantitatively correct. The lowest lying shake up channel was found to be more than 70 percent of the total double excitation strength. The model was also used to investigate the many-body effect in the EXAFS. Various forms of hemerythrin (Hr) and their model compounds have been measured by EXAFS. The data analysis shows that the oxy-form of Hr is similar to the met-forms. On release of O(,2) in oxy-Hr, the (mu)-oxo bridge with Fe -O distance of 1.8 (ANGSTROM) is converted to a (mu)-OH bridge of 2.0 (ANGSTROM) and the iron-iron distance is changed from 3.24 (ANGSTROM) to 3.50 (ANGSTROM). Accompanying this change is a large increase in vibrational amplitude around the active site. The entropy increase associated with this vibrational change contributes most of the entropy change driving the transition. A new error analysis procedure is introduced to estimate the fitting errors introduced by modeling the unknown with the standards. It is found that the dominant part of the errors was introduced by the modeling itself, namely, the standards used are not quite transferable with the unknowns. The EXAFS on the samples of Hg impurities in Pb and pure Pb have been measured in the temperature range from 10 K to right below the melting temperatures. The measurement focuses on the local structure of both lead and mercury atoms, which is an advantage provided by the technique. The Debye-Waller factor (DWF) change exhibits

  2. Complex X-ray Absorption and the Fe K(alpha) Profile in NGC 3516

    NASA Technical Reports Server (NTRS)

    Turner, T. J.; Kraemer, S. B.; George, I. M.; Reeves, J. N.; Botorff, M. C.

    2004-01-01

    We present data from simultaneous Chandra, XMM-Newton and BeppoSAX observations of the Seyfert 1 galaxy NGC 3516, taken during 2001 April and November. We have investigated the nature of the very flat observed X-ray spectrum. Chandra grating data show the presence of X-ray absorption lines, revealing two distinct components of the absorbing gas, one which is consistent with our previous model of the UV/X-ray absorber while the other, which is outflowing at a velocity of approximately 1100 kilometers per second, has a larger column density and is much more highly ionized. The broad-band spectral characteristics of the X-ray continuum observed with XMM during 2001 April, reveal the presence of a third layer of absorption consisting of a very large column (approximately 2.5 x 10(exp 23) per square centimeter) of highly ionized gas with a covering fraction approximately 50%. This low covering fraction suggests that the absorber lies within a few 1t-days of the X-ray source and/or is filamentary in structure. Interestingly, these absorbers are not in thermal equilibrium with one another. The two new components are too highly ionized to be radiatively accelerated, which we suggest is evidence for a hydromagnetic origin for the outflow. Applying our model to the November dataset, we can account for the spectral variability primarily by a drop in the ionization states of the absorbers, as expected by the change in the continuum flux. When this complex absorption is accounted for we find the underlying continuum to be typical of Seyfert 1 galaxies. The spectral curvature attributed to the high column absorber, in turn, reduces estimates of the flux and extent of any broad Fe emission line from the accretion disk.

  3. High Resolution X-Ray Absorption Spectroscopy: Distribution of Matter in and around Galaxies

    NASA Astrophysics Data System (ADS)

    Schulz, Norbert; MIT/CAT Team

    2015-10-01

    The chemical evolution of the Universe embraces aspects that reachdeep into modern astrophysics and cosmology. We want to know how present and past matter is affected by various levels and types of nucleo-synthesis and stellar evolution. Three major categories were be identified: 1. The study of pre-mordial star formation including periods of super-massive black hole formation, 2. The embedded evolution of the intergalactic medium IGM, 3. The status and evolution of stars and the interstellar medium ISM in galaxies. Today a fourth category relates to our understanding of dark matter in relationwith these three categories. The X-ray band is particularly sensitive to K- and L-shell absorption and scattering from high abundant elements like C, N, O, Ne, Mg, Si, S,Ar, Ca, Fe, and Ni. Like the Lyman alpha forest in the optical band, absorbers in the IGM produce an X-ray line forest along the line of sight in the X-rayspectrum of a background quasar. Similary bright X-ray sources within galaxies and the Milky Way produce a continuum, which is being absorbed by elements invarious phases of the ISM. High resolution X-ray absorption surveys are possible with technologies ready for flight within decade. == high efficiency X-ray optics with optical performance 3== high resolution X-ray gratings with R 3000 for E 1.5 keV== X-ray micro-calorimeters with R 2000 for E 1.5 keV. The vision for the next decade needs to lead to means and strategies which allows us to perform such absorption surveys as effectively as surveys are now or in very near future quite common in astronomy pursued in other wave length bands such as optical, IR, and sub-mm.

  4. Discovery of Broad Soft X-ray Absorption Lines from the Quasar Wind in PDS 456

    NASA Astrophysics Data System (ADS)

    Reeves, J. N.; Braito, V.; Nardini, E.; Behar, E.; O'Brien, P. T.; Tombesi, F.; Turner, T. J.; Costa, M. T.

    2016-06-01

    High-resolution soft X-ray spectroscopy of the prototype accretion disk wind quasar, PDS 456, is presented. Here, the XMM-Newton reflection grating spectrometer spectra are analyzed from the large 2013-2014 XMM-Newton campaign, consisting of five observations of approximately 100 ks in length. During the last observation (OBS. E), the quasar is at a minimum flux level, and broad absorption line (BAL) profiles are revealed in the soft X-ray band, with typical velocity widths of {σ }{{v}}˜ {{10,000}} km s-1. During a period of higher flux in the third and fourth observations (OBS. C and D, respectively), a very broad absorption trough is also present above 1 keV. From fitting the absorption lines with models of photoionized absorption spectra, the inferred outflow velocities lie in the range ˜ 0.1{--}0.2c. The absorption lines likely originate from He and H-like neon and L-shell iron at these energies. A comparison with earlier archival data of PDS 456 also reveals a similar absorption structure near 1 keV in a 40 ks observation in 2001, and generally the absorption lines appear most apparent when the spectrum is more absorbed overall. The presence of the soft X-ray BALs is also independently confirmed by an analysis of the XMM-Newton EPIC spectra below 2 keV. We suggest that the soft X-ray absorption profiles could be associated with a lower ionization and possibly clumpy phase of the accretion disk wind, where the latter is known to be present in this quasar from its well-studied iron K absorption profile and where the wind velocity reaches a typical value of 0.3c.

  5. X-ray absorption and electrochemical studies of direct methanol fuel cell catalysts

    SciTech Connect

    Zurawski, D.J.; Aldykiewicz, A.J. Jr.; Baxter, S.F.; Krumpelt, M.

    1996-12-31

    In order for polymer electrolyte fuel cells to operate directly on methanol instead of hydrogen, a distinct advantage for portable applications, methanol oxidation must be catalyzed effectively in the acidic environment of the cell. Platinum-ruthenium and platinum-ruthenium oxide are generally considered to be the most active catalysts for this purpose. The presence of ruthenium significantly enhances the activity of platinum in these catalysts, for reasons not yet fully understood. We are using X-ray absorption spectroscopy (XAS) and electrochemical techniques to evaluate the mechanisms proposed to account for this enhancement in order to further improve the catalyst`s activity. We are considering three enhancement mechanisms. An intermediate in the oxidation of methanol on platinum is carbon monoxide and its oxidation is the rate-determining step in the overall oxidation mechanism. It has been proposed that ruthenium facilitates the removal of carbon monoxide from the platinum surface. First, it has been proposed that ruthenium decreases the strength of the platinum-carbon monoxide bond. Carbon monoxide bonds to the catalyst by interacting with the d-band of platinum, therefore a change in the d-band occupancy of platinum as a result of alloying may influence the bond strength of carbon monoxide. Another proposed enhancement mechanism involves lowering of the potential for the formation of the CO-oxidizing species. Finally, the binary catalysts may have a structure which is more conducive to the methanol dehydrogenation and carbon monoxide reactions. Based on these three proposed enhancement mechanisms, a goal of this study is to correlate catalyst electronic properties, structure, and oxidation state with the performance of proton-exchange membrane (Nafion) direct methanol fuel cells.

  6. The use of (micro)-X-ray absorption spectroscopy in cement research.

    PubMed

    Scheidegger, A M; Vespa, M; Grolimund, D; Wieland, E; Harfouche, M; Bonhoure, I; Dähn, R

    2006-01-01

    Long-term predictions on the mobility and the fate of radionuclides and contaminants in cementitious waste repositories require a molecular-level understanding of the geochemical immobilization processes involved. In this study, the use of X-ray absorption spectroscopy (XAS) for chemical speciation of trace elements in cementitious materials will be outlined presenting two examples relevant for nuclear waste management. The first example addresses the use of XAS on powdered cementitious materials to determine the local coordination environment of Sn(IV) bound to calcium silicate hydrates (C-S-H). Sn K-edge XAS data of Sn(IV) doped C-S-H can be rationalized by corner sharing binding of Sn octahedra to Si tetrahedra of the C-S-H structure. XAS was further applied to determine the binding mechanism of Sn(IV) in the complex cement matrix. The second example illustrates the potential of emerging synchrotron-based X-ray micro-probe techniques for elucidating the spatial distribution and the speciation of contaminants in highly heterogeneous cementitious materials at the micro-scale. Micro X-ray fluorescence (XRF) and micro-XAS investigations were carried out on Co(II) doped hardened cement paste. These preliminary investigations reveal a highly heterogeneous spatial Co distribution. The presence of a Co(II)-hydroxide-like phase Co(OH)2 and/or Co-Al layered double hydroxide (Co-Al LDH) or Co-phyllosilicate was observed. Surprisingly, some of the initial Co(II) was partially oxidized and incorporated into a Co(III)O(OH)-like phase or a Co-phyllomanganate.

  7. On the relation of optical obscuration and X-ray absorption in Seyfert galaxies

    NASA Astrophysics Data System (ADS)

    Burtscher, L.; Davies, R. I.; Graciá-Carpio, J.; Koss, M. J.; Lin, M.-Y.; Lutz, D.; Nandra, P.; Netzer, H.; Orban de Xivry, G.; Ricci, C.; Rosario, D. J.; Veilleux, S.; Contursi, A.; Genzel, R.; Schnorr-Müller, A.; Sternberg, A.; Sturm, E.; Tacconi, L. J.

    2016-02-01

    The optical classification of a Seyfert galaxy and whether it is considered X-ray absorbed are often used interchangeably. There are many borderline cases, however, and also numerous examples where the optical and X-ray classifications appear to be in disagreement. In this article we revisit the relation between optical obscuration and X-ray absorption in active galactic nuclei (AGNs). We make use of our "dust colour" method to derive the optical obscuration AV, and consistently estimated X-ray absorbing columns using 0.3-150 keV spectral energy distributions. We also take into account the variable nature of the neutral gas column NH and derive the Seyfert subclasses of all our objects in a consistent way. We show in a sample of 25 local, hard-X-ray detected Seyfert galaxies (log LX/ (erg / s) ≈ 41.5-43.5) that there can actually be a good agreement between optical and X-ray classification. If Seyfert types 1.8 and 1.9 are considered unobscured, the threshold between X-ray unabsorbed and absorbed should be chosen at a column NH = 1022.3 cm-2 to be consistent with the optical classification. We find that NH is related to AV and that the NH/AV ratio is approximately Galactic or higher in all sources, as indicated previously. However, in several objects we also see that deviations from the Galactic ratio are only due to a variable X-ray column, showing that (1) deviations from the Galactic NH/AV can be simply explained by dust-free neutral gas within the broad-line region in some sources; that (2) the dust properties in AGNs can be similar to Galactic dust and that (3) the dust colour method is a robust way to estimate the optical extinction towards the sublimation radius in all but the most obscured AGNs.

  8. Intermediate coupling for core-level excited states: Consequences for X-Ray absorption spectroscopy

    SciTech Connect

    Bagus, Paul S.; Sassi, Michel J.; Rosso, Kevin M.

    2015-04-01

    The origin of the complex NEXAFS features of X-Ray Absorption, XAS, spectra in transition metal complexes is analyzed and interpreted in terms of the angular momentum coupling of the open shell electrons. Especially for excited configurations where a core-electron is promoted to an open valence shell, the angular momentum coupling is intermediate between the two limits of Russell- Saunders, RS, coupling where spin-orbit splitting of the electron shells is neglected and j-j coupling where this splitting is taken as dominant. The XAS intensities can be understood in terms of two factors: (1) The dipole selection rules that give the allowed excited RS multiplets and (2) The contributions of these allowed multiplets to the wavefunctions of the intermediate coupled levels. It is shown that the origin of the complex XAS spectra is due to the distribution of the RS allowed multiplets over several different intermediate coupled excited levels. The specific case that is analyzed is the L2,3 edge XAS of an Fe3+ cation, because this cation allows a focus on the angular momentum coupling to the exclusion of other effects; e.g., chemical bonding. Arguments are made that the properties identified for this atomic case are relevant for more complex materials. The analysis is based on the properties of fully relativistic, ab initio, many-body wavefunctions for the initial and final states of the XAS process. The wavefunction properties considered include the composition of the wavefunctions in terms of RS multiplets and the occupations of the spin-orbit split open shells; the latter vividly show whether the coupling is j-j or not.

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

    PubMed

    Lozano, Janeth M; Clark, David L; Conradson, Steven D; Den Auwer, Christophe; Fillaux, Clara; Guilaumont, Dominique; Keogh, D Webster; Mustre de Leon, Jose; Palmer, Phillip D; Simoni, Eric

    2009-11-28

    Experimental L(III) X-ray absorption near edge structure (XANES) spectra of the distorted octahedral neptunium oxo ions NpO(2)(OH)(4)(2-), NpO(4)(OH)(2)(3-), and NpO(6)(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.

  10. Probing the structure of iron at extreme conditions by X-ray absorption near-edge structure calculations

    NASA Astrophysics Data System (ADS)

    Raji, A. T.; Scandolo, S.; Härting, M.; Britton, D. T.

    2013-03-01

    We present the K-edge X-ray absorption near edge spectra of hexagonal-closed packed iron at pressure and temperature conditions relevant to Earth's mantle conditions. The calculated spectra have been obtained using the first-principles scheme based on the continued-fraction approach and norm-conserving pseudopotentials. The atomic configurations used for the X-ray absorption near edge spectroscopy calculations were obtained from classical molecular dynamics simulations, using an optimized embedded-atom potential. We compare our calculated spectra to recently available experiment results (R. Boehler, H.G. Musshoff, R. Ditz, G. Aquilanti, and A. Trapananti, Rev. Sci. Instrum. 80 (2009), pp. 045103-045108) and identify the main features of the spectra that may indicate onset of melting in iron.

  11. X-ray absorption and diffraction studies of the metal binding sites in amyloid beta-peptide.

    PubMed

    Streltsov, Victor

    2008-03-01

    A major source of neurodegeneration observed in Alzheimer's disease is believed to be caused by the toxicity from reactive oxygen species produced in the brain mediated by the A beta protein and mainly copper species. An atomic model of an amyloid beta-peptide (A beta) Cu2+ complex or at least the structure of the metal binding site is of great interest. Accurate information about the Cu-binding site of A beta protein can facilitate simulation of redox chemistry using high level quantum mechanics. Complementary X-ray diffraction and X-ray absorption techniques can be employed to obtain such accurate information. This review provides a blend of X-ray diffraction results on amyloid structures and selected works on A beta Cu2+ binding based on spectroscopic measurements with emphasis on the X-ray absorption technique.

  12. Mn L3,2 X-ray absorption and magnetic circular dichroism inferromagnetic Ga1-xMnxP

    SciTech Connect

    Stone, P.R.; Scarpulla, M.A.; Farshchi, R.; Sharp, I.D.; Haller,E.E.; Dubon, O.D.; Yu, K.M.; Beeman, J.W.; Arenholz, E.; Denlinger, J.D.; Ohldag, H.

    2006-03-25

    We have measured the X-ray absorption and X-ray magnetic circular dichroism (XMCD) at the Mn L{sub 3,2} edges in ferromagnetic Ga{sub 1-x}Mn{sub x}P for 0.018 {le} x {le} 0.042. Large XMCD asymmetries at the L{sub 3} edge indicate significant spin-polarization of the density of states at the Fermi energy. The temperature dependence of the XMCD and moment per Mn of 2.67 {+-} 0.45 {mu}{sub B} calculated using sum rules are consistent with magnetometry values. The spectral shapes of the X-ray absorption and XMCD are nearly identical with those for Ga{sub 1-x}Mn{sub x}As indicating that the hybridization of Mn d and anion p states is similar in the two materials.

  13. Glitch-free X-ray absorption spectrum under high pressure obtained using nano-polycrystalline diamond anvils.

    PubMed

    Ishimatsu, Naoki; Matsumoto, Ken; Maruyama, Hiroshi; Kawamura, Naomi; Mizumaki, Masaichiro; Sumiya, Hitoshi; Irifune, Tetsuo

    2012-09-01

    Nano-polycrystalline diamond (NPD) [Irifune et al. (2003), Nature (London), 421, 599] has been used to obtain a glitch-free X-ray absorption spectrum under high pressure. In the case of conventional single-crystal diamond (SCD) anvils, glitches owing to Bragg diffraction from the anvils are superimposed on X-ray absorption spectra. The glitch has long been a serious problem for high-pressure research activities using X-ray spectroscopy because of the difficulties of its complete removal. It is demonstrated that NPD is one of the best candidate materials to overcome this problem. Here a glitch-free absorption spectrum using the NPD anvils over a wide energy range is shown. The advantage and capability of NPD anvils is discussed by a comparison of the glitch map with that of SCD anvils.

  14. Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis

    SciTech Connect

    Lu, Qingquan; Zhang, Jian; Peng, Pan; Zhang, Guanghui; Huang, Zhiliang; Yi, Hong; Miller, Jeffrey T.; Lei, Aiwen

    2015-05-26

    An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(II) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(I) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(II) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions.

  15. First-principles calculation of principal Hugoniot and K-shell X-ray absorption spectra for warm dense KCl

    SciTech Connect

    Zhao, Shijun; Zhang, Shen; Kang, Wei; Li, Zi; Zhang, Ping; He, Xian-Tu

    2015-06-15

    Principal Hugoniot and K-shell