Science.gov

Sample records for absorption fine-structure exafs

  1. 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.

  2. Thermal Expansion Behaviour of Silver Examined by Extended X-Ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Dubiel, M.; Chasse, A.; Haug, J.; Schneider, R.; Kruth, H.

    2007-02-02

    EXAFS (extended X-ray absorption fine structure) investigations are reported concerning the thermal expansion behaviour of silver in an extended range of temperature from 10 K to about 950 K measured in transmission mode. Both the ratio method and an EXAFS fitting procedure were applied to reveal the temperature dependence of EXAFS parameters. Models based on quantum and classical thermodynamic perturbation theory have been used to interpret experimental data and compared to XRD (X-ray diffraction) results of bulk silver material. The description of thermodynamic data of thermal expansion of silver in the complete range of temperature by EXAFS Spectroscopy was successful by first calculations using third order quantum perturbation theory.

  3. Local vibrational properties of GaAs studied by extended X-ray absorption fine structure.

    PubMed

    Ahmed, S I; Aquilanti, G; Novello, N; Olivi, L; Grisenti, R; Fornasini, P

    2013-10-28

    Extended X-ray absorption fine structure (EXAFS) has been measured at both the K edges of gallium and arsenic in GaAs, from 14 to 300 K, to investigate the local vibrational and thermodynamic behaviour in terms of bond expansion, parallel, and perpendicular mean square relative displacements and third cumulant. The separate analysis of the two edges allows a self-consistent check of the results and suggests that a residual influence of Ga EXAFS at the As edge cannot be excluded. The relation between bond expansion, lattice expansion, and expansion due to anharmonicity of the effective potential is quantitatively clarified. The comparison with previous EXAFS results on other crystals with the diamond or zincblende structure shows that the values of a number of parameters determined from EXAFS are clearly correlated with the fractional ionicity and with the strength and temperature interval of the lattice negative expansion. PMID:24182054

  4. Fine-structure Constancy Measurements in QSO Absorption Lines

    NASA Astrophysics Data System (ADS)

    Whitmore, Jonathan B.

    2013-01-01

    The ESO Large Programme 185.A-0745 has awarded 10 nights on the VLT-UVES spectrograph for the study of the possible variation in the fine structure constant. We will present the fine-structure measurements from two lines of sight and several absorption systems. We will also present updated systematic error analyses.

  5. A platform for x-ray absorption fine structure study of dynamically compressed materials above 1 Mbar

    NASA Astrophysics Data System (ADS)

    Ping, Y.; Hicks, D. G.; Yaakobi, B.; Coppari, F.; Eggert, J.; Collins, G. W.

    2013-12-01

    A platform consisting of a multi-shock drive and an implosion backlighter has been developed for x-ray absorption fine structure (XAFS) measurements on materials compressed to multi-Mbar pressures. The experimental setup, target design, and backlighter characteristics are presented. Extended XAFS (EXAFS) measurements for various materials have been demonstrated. A quintuple-crystal design is described to enhance the efficiency of the x-ray spectrometer, enabling observation of very weak EXAFS signals in a single shot.

  6. Extended x-ray absorption fine structure of NaBr and Ge at high pressure

    SciTech Connect

    Ingalls, R.; Crozier, E.D.; Whitmore, J.E.; Seary, A.J.; Tranquada, J.M.

    1980-06-01

    The x-ray absorption spectra of Ge and of Br in NaBr have been measured to pressures of 52 and 21 kbars, respectively, in a boron carbide and diamond anvil cell in which pressure was measured via the ruby-fluorescence technique. Although Bragg peaks from the diamond anvil reduced the accuracy, atomic spacings in both materials could be determined by extended x-ray absorption fine-structure (EXAFS) analysis. Changes in the nearest-neighbor separations in NaBr, and Ge to at least 40 kbars, agreed with literature values, indicating that the EXAFS phase shifts are quite insensitive to such pressures. In addition the near-edge peak positions in the NaBr spectra appeared to readily shift with pressure, which suggests that NaBr may be quite suitable as a pressure standard in future work of this type.

  7. Polarized X-ray absorption fine structure of La 2CuO 4-y single crystal

    NASA Astrophysics Data System (ADS)

    Oyanagi, Hiroyuki; Oka, Kunihiko; Unoki, Hiromi; Nishihara, Yoshikazu; Murata, Keizo; Matsushita, Tadashi; Tokumoto, Madoka; Kimura, Yoichi

    1989-06-01

    Polarized X-ray absorption fine structure (XAFS) has been measured on the Cu K-edge for undoped La2CuO4-y bulk single crystal (15 × 20 × 3 mm) grown by the top-seeded solution growth method. Strong polarization dependence observed in the near-edge and EXAFS regions demonstrates the quasi-2D character of the CuO2 plane in terms of both electron states and local structure.

  8. Anharmonicity of the Bending and Stretching Vibrations Observed in Extended X-Ray Absorption Fine Structure of Tetrahedral Molecules

    NASA Astrophysics Data System (ADS)

    Yokoyama, Toshihiko; Yonamoto, Yoshiki; Ohta, Toshiaki

    1996-12-01

    We have measured and analyzed the temperature dependence of extended X-ray absorption fine structure (EXAFS) spectra of tetrahedral systems MBr4 ( M=C, Si, Ge). The EXAFS analysis by means of the cumulant expansion technique enables one to obtain information about force constants including the third-order anharmonicity. The second-order cumulants obtained experimentally are in excellent agreement with the values expected by the vibrational data and the third-order cumulants have been determined successfully. For the first nearest neighbor (NN) Br M shells the stretching motions are apparently dominant to describe EXAFS, while for the second NN Br Br shell the bending modes are found to contribute significantly to the cumulants especially for the third-order anharmonicity. The obtained force constants are compared to each other and the origin of observed bending anharmonicity is discussed.

  9. 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. PMID:22833100

  10. 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

  11. Support Effects on Electronic Behaviors of Gold Nanoparticles Studied by X-Ray Absorption Fine Structure

    SciTech Connect

    Li Zhongrui; Yan Wensheng; Wei Shiqiang

    2007-02-02

    The electronic properties of gold nanoparticles supported on different supports were studied with X-ray absorption fine structure (XAFS). It was found that the tunability of the d-electron distribution in the nano-sized Au clusters can be realized by selective supporting. The Au atoms in the clusters gain 5d electrons when supported on SiO2, and lose 5d electrons when loaded over MgO, Al2O3, and TiO2. Contractions in bond lengths of between 0.5 and 1.6% from bulk metal values were observed from EXAFS data. This work demonstrates that the important role of the different supports in the 5d-charge distribution of Au nanoparticles and usefulness of XAFS in probing the electronic behavior of noble metal nanoparticles.

  12. Titanium local structure in tektite probed by X-ray absorption fine structure spectroscopy.

    PubMed

    Wang, Ling; Yoshiasa, Akira; Okube, Maki; Takeda, Takashi

    2011-11-01

    The local structure of titanium in tektites from six strewn fields was studied by Ti K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) in order to provide quantitative data on Ti-O distance and Ti coordination number. The titanium in tektites possessed different coordination environment types. XANES spectra patterns revealed resemblance to high-temperature TiO(2)-SiO(2) glass and TiO(2) anatase. All samples showed that the valence of Ti is 4+. Based on the Ti-O distances, coordination numbers and radial distribution function determined by EXAFS analyses, the tektites were classified into three types: type I, Ti occupies a four-coordinated tetrahedral site with Ti-O distances of 1.84-1.79 Å; type II, Ti occupies a five-coordinated trigonal bipyramidal or tetragonal pyramidal site with Ti-O distances of 1.92-1.89 Å; type III, Ti occupies a six-coordinated octahedral site with Ti-O distances of 2.00-1.96 Å. Although Ti occupies the TiO(6) octahedral site in most titanium minerals under ambient conditions, some tektites have four- and five-coordinated Ti. This study indicated that the local structure of Ti might change in impact events and the following stages. PMID:21997913

  13. Extended X-ray absorption fine structure study of mixed-ligand copper(II) complexes having analogous structures

    NASA Astrophysics Data System (ADS)

    Gaur, Abhijeet; Shrivastava, B. D.; Srivastava, Krishna; Prasad, J.

    2013-02-01

    X-ray absorption fine structure spectra have been studied at the Cu K-edge in five mixed-ligand copper(II) complexes, viz., [Cu(L-glu)(bipy)] 1, [Cu(L-glu)(phen) (H2O)].3H2O 2, [Cu(L-tyro)(bipy)(ClO4)].2H2O 3, [Cu(L-phen)(bipy)(H2O)] (ClO4) 4, and [Cu(L-tyro)(phen)(H2O)] (ClO4).1.5H2O 5 (where L-glu = L-glutamate dianion, L-tyro = L-tyrosinate anion, bipy = 2,2'-bipyridine, and phen =1,10-phenanthroline), having essentially the same structure. The crystallographic data are available for all the complexes using which five theoretical models have been generated. Firstly, extended X-ray absorption fine structure (EXAFS) data of each complex has been analyzed using its own theoretical model and the results obtained are found to be comparable with the crystallographic results. Then, the EXAFS data of each complex has been analyzed using the theoretical models of the remaining four of these complexes. For each complex, the structural parameters obtained by fitting EXAFS data with theoretical models of the four remaining complexes have been found to be comparable with those obtained by fitting its own theoretical model. Thus, it has been found that if the crystal structure is not available for a complex, then the crystal structure of similar or analogous complex can be used satisfactorily for generating the theoretical model for the EXAFS data analysis of that complex, even if different ligands are attached to the central metal atom. On the basis of EXAFS data analysis, the coordination geometries around the central metal ions in these complexes have been depicted.

  14. Extended-X-ray-absorption-fine-structure investigations of zinc in 5-aminolaevulinate dehydratase.

    PubMed Central

    Hasnain, S S; Wardell, E M; Garner, C D; Schlösser, M; Beyersmann, D

    1985-01-01

    The zinc co-ordination in 5-aminolaevulinate dehydratase (5-aminolaevulinate hydro-lyase, EC 4.2.1.24) was investigated by recording and interpreting the extended X-ray-absorption fine structure (e.x.a.f.s.) associated with the zinc K-edge. The enzyme has a molecular mass of 280 000 Da and consists of eight subunits of 35 000 Da each; the samples studied contained approx. 1 g-atom of zinc/mol of subunit. Four forms of the enzyme were investigated and details of the zinc environment were elucidated, as follows. In the native enzyme, zinc is considered to be co-ordinated to three sulphur atoms at 0.228(2)nm [2.28(2)A] and a lower-Z atom at 0.192(5)nm [1.92(5)A] (if nitrogen) or 0.189(5)nm [1.89(5)A] (if oxygen). Reaction of the enzyme with the inhibitor 2-bromo-3-(imidazol-5-yl)propionic acid produced significant changes in the e.x.a.f.s., the nature of which are consistent with co-ordination by about three sulphur atoms at 0.222(2)nm [2.22(2)A], a nitrogen atom at 0.193(5)nm [1.93(5)A] and a nitrogen atom from the inhibitor at 0.214(5)nm [2.14(5)A]. Inactivation of the enzyme by air-oxidation of essential thiol groups and binding of the substrate produce slight changes in the e.x.a.f.s. consistent with slight re-arrangement of ligands with additional lighter ligands (nitrogen or oxygen). These results, when combined with previous findings, are taken to indicate that zinc has a structural rather than a direct catalytic role in 5-aminolaevulinate dehydratase. PMID:4062868

  15. Probing the Limits of Conventional Extended X-ray Absorption Fine Structure Analysis Using Thiolated Gold Nanoparticles.

    PubMed

    Chill, Samuel T; Anderson, Rachel M; Yancey, David F; Frenkel, Anatoly I; Crooks, Richard M; Henkelman, Graeme

    2015-04-28

    We present a method for quantifying the accuracy of extended X-ray absorption fine structure (EXAFS) fitting models. As a test system, we consider the structure of bare Au147 nanoparticles as well as particles bound with thiol ligands, which are used to systematically vary disorder in the atomic structure of the nanoparticles. The accuracy of the fitting model is determined by comparing two distributions of bond lengths: (1) a direct average over a molecular dynamics (MD) trajectory using forces and energies from density functional theory (DFT) and (2) a fit to the theoretical EXAFS spectra generated from that same trajectory. Both harmonic and quasi-harmonic EXAFS fitting models are used to characterize the first-shell Au-Au bond length distribution. The harmonic model is found to significantly underestimate the coordination number, disorder, and bond length. The quasi-harmonic model, which includes the third cumulant of the first-shell bond length distribution, yields accurate bond lengths, but incorrectly predicts a decrease in particle size and little change in the disorder with increasing thiol ligands. A direct analysis of the MD data shows that the particle surfaces become much more disordered with ligand binding, and the high disorder is incorrectly interpreted by the EXAFS fitting models. Our DFT calculations compare well with experimental EXAFS measurements of Au nanoparticles, synthesized using a dendrimer encapsulation technique, showing that systematic errors in EXAFS fitting models apply to nanoparticles 1-2 nm in size. Finally we show that a combination of experimental EXAFS analysis with candidate models from DFT is a promising strategy for a more accurate determination of nanoparticle structures. PMID:25853740

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

    NASA Astrophysics Data System (ADS)

    Sanson, Andrea

    2016-08-01

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

  17. Local structure of NiAl compounds investigated by extended X-ray absorption fine-structure spectroscopy.

    PubMed

    Tian, J S; Han, G M; Wei, H; Jin, T; Dargusch, M S

    2012-07-01

    The local structures of pure NiAl and Ti-, Co-doped NiAl compounds have been obtained utilizing extended X-ray absorption fine-structure (EXAFS) spectroscopy. The results provide experimental evidence that Ni antisite defects exist in the Ni-rich NiAl compounds. The site preference of Ti and Co has been confirmed. Ti occupies the Al sublattice, while Co occupies the Ni sublattice. The structure parameters obtained by EXAFS were consistent with the X-ray diffraction results. Owing to the precipitation of α-Cr, the local structure of NiAl-Cr has not been obtained, making the site preference of Cr unclear. PMID:22713881

  18. A History of X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Stumm von Bordwehr, R.

    This historical account of X-ray absorption fine structure (XAFS) spectroscopy from the origin to 1975 begins with the first observations of X-ray absorption edges and the experimental setups used at the turn of the century. Then, the discovery of XAFS and Kossel's early interpretation are discussed. A close look is taken at the three outstanding papers written by Kronig to explain XAFS in solids and molecules. Petersen's development of XAFS in molecules and Smoluchowski's investigation of XAFS in crystals during the thirties are reviewed. Then, the Japanese and Soviet contributions to X-ray absorption spectroscopy up to the sixties are described. We conclude with the advent of the present understanding of XAFS developed in the early seventies. Although many experiments are presented, we emphasize the conceptual evolution of the interpretation of XAFS, including false steps and overlooked works. Cette histoire de la spectroscopie de structure fine des seuils d'absorption X (XAFS) des origines à 1975 commence par présenter les premières observations de seuils d'absorption X ainsi que les dispositifs expérimentaux utilisés au début du siècle. Puis on décrit la découverte des structures fines et l'interprétation qu'en donne Kossel. On discute en details les trois remarquables articles écrits par Kronig pour expliquer les XAFS dans les solides et les molécules. On montre comment Petersen a développé la théorie des XAFS des molécules et Smoluchowski celle des cristaux. Puis on passe en revue les contributions japonaises et soviétiques à cette spectroscopie jusqu'aux années soixante. On conclut par la description de la théorie actuelle des XAFS qui s'est développée au début des années soixante-dix. Bien que décrivant des nombreuses expériences, ce travail met l'accent sur l'évolution conceptuelle de l'interprétation des XAFS, en tenant compte des faux pas et des contributions négligées.

  19. 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

  20. X-ray absorption fine structure of aged, Pu-doped glass and ceramic waste forms

    NASA Astrophysics Data System (ADS)

    Hess, N. J.; Weber, W. J.; Conradson, S. D.

    1998-04-01

    X-ray absorption spectroscopic (XAS) studies were performed on three compositionally identical, Pu-doped, borosilicate glasses prepared 15 years ago at different α-activities by varying the 239Pu/ 238Pu isotopic ratio. The resulting α-activities ranged from 1.9×10 7 to 4.2×10 9 Bq/g and have current, accumulated doses between 8.8×10 15 to 1.9×10 18 α-decays/g. Two ceramic, polycrystalline zircon (ZrSiO 4) samples prepared 16 years ago with 10.0 wt% Pu was also investigated. Varying the 239Pu/ 238Pu isotopic ratio in these samples resulted in α-activities of 2.5×10 8 and 5.6×10 10 Bq/g and current, accumulated doses of 1.2×10 17 and 2.8×10 19 α-decays/g. The multicomponent composition of the waste forms permitted XAS investigations at six absorption edges for the borosilicate glass and at three absorption edges for the polycrystalline zircons. For both waste forms, analysis of extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectra indicates that the local environment around the cations exhibits different degrees of disorder as a result of the accumulated α-decay dose. In general, cations with short cation-oxygen bonds show little effect from self-radiation whereas cations with long cation-oxygen bonds show a greater degree of disorder with accumulated α-decay dose.

  1. X-ray absorption fine structure study of amorphous metal oxide thin films prepared by photochemical metalorganic deposition

    NASA Astrophysics Data System (ADS)

    Trudel, Simon; Daryl Crozier, E.; Gordon, Robert A.; Budnik, Peter S.; Hill, Ross H.

    2011-05-01

    The oxidation state and local geometry of the metal centers in amorphous thin films of Fe 2O 3 (Fe 3+ oxidation state), CoFe 2O 4 (Co 2+/Fe 3+ oxidation states), and Cr 2O 3 (Cr 3+ oxidation state) are determined using K edge X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. The metal oxide thin films were prepared by the solid-state photochemical decomposition of the relevant metal 2-ethylhexanoates, spin cast as thin films. No peaks are observed in the X-ray diffraction patterns, indicating the metal oxides are X-ray amorphous. The oxidation state of the metals is determined from the edge position of the K absorption edges, and in the case of iron-containing samples, an analysis of the pre-edge peaks. In all cases, the EXAFS analysis indicates the first coordination shell consists of oxygen atoms in an octahedral geometry, with a second shell consisting of metals. No higher shells are observed beyond 3.5 Å for all samples, indicating the metal oxides are truly amorphous, consistent with X-ray diffraction results.

  2. 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.

  3. 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

    2016-09-01

    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. PMID:27385480

  4. 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. PMID:19921074

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  6. Extended x-ray absorption fine structure spectroscopy in Co{sub 0.013}NbSe{sub 2}.

    SciTech Connect

    Weber, F.; Castellan, J.-P.; Rosenkranz, S.; Osborn, R.; Rosenmann, D.; Iavarone, M.; Materials Science Division

    2010-01-01

    We present a study of the local environment of the Co atom in single crystalline Co{sub x}NbSe{sub 2}, x = 0.013, via Extended X-ray Absorption Fine Structure (EXAFS) measurements at the Co K-edge (7.7 keV) at various temperatures. Co intercalation quickly suppresses superconductivity and the charge-density wave (CDW) present in pure NbSe{sub 2}. In order to study the effect of impurities on superconducting and CDW states one has to verify the random distribution of the intercalated atoms in contrast to possible clustering which could lead to additional, e.g. magnetic, interactions in the case of Co intercalation. Our measurements show that the Co atoms are indeed randomly distributed in Co{sub 0.013}NbSe{sub 2}.

  7. 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.

  8. Structural Analysis of Freshwater-Cultured Pearls with Different Lusters Using the Extended X-Ray Absorption Fine Structure Technique

    NASA Astrophysics Data System (ADS)

    Monarumit, N.; Noirawee, N.; Phlayrahan, A.; Promdee, K.; Won-in, K.; Satitkune, S.

    2016-05-01

    The quality of freshwater-cultured pearls (Chamberlainia hainesiana) is determined by their luster, which is related to the content of the two CaCO3 mineral phases: aragonite and vaterite. The atomic structures of pearl samples were analyzed by the extended X-ray absorption fine structure (EXAFS) technique using synchrotron radiation to compare the atomic environment and atomic bonding around Ca atoms of high- and low-luster pearls. The Ca K-edge EXAFS spectra of the pearl samples were determined and interpreted in terms of the photoelectron wave number and the distance between Ca atoms and neighboring atoms. From the results, the wave oscillation of high-luster pearls is less than that of low-luster pearls. This indicates the presence of the aragonite phase in high-luster pearls and a combination of aragonite and vaterite phases in low-luster pearls, especially in the fi rst and second shells of Ca atoms. It can be concluded that the different lusters of freshwater-cultured pearls are related to the different CaCO3 phases in their structures.

  9. Studies of vibrational properties in Ga stabilized delta-Pu by extended X-ray absorption fine structure

    SciTech Connect

    Allen, P.G.; Henderson, A.L.; Sylwester, E.R.; Turchi, P.E.A.; Shen, T.H.; Gallegos, G.F.; Booth, C.H.

    2002-02-14

    Temperature dependent extended x-ray absorption fine structure (EXAFS) spectra were measured for a 3.3 at. % Ga stabilized Pu alloy over the range T= 20 - 300 K. EXAFS data were acquired at both the Ga K-edge and the Pu L{sub III} edge. Curve-fits were performed to the first shell interactions to obtain pair-distance distribution widths, {sigma}, as a function of temperature. The temperature dependence of {sigma}(T) was accurately modeled using a correlated-Debye model for the lattice vibrational properties, suggesting Debye-like behavior in this material. Using this formalism, we obtain pair-specific correlated-Debye temperatures, {Theta}{sub cD}, of 110.7 {+-} 1.7 K and 202.6 {+-} 3.7 K, for the Pu-Pu and Ga-Pu pairs, respectively. The result for the Pu-{Theta}{sub cD} value compares well with previous vibrational studies on {delta}-Pu. In addition, our results represent the first unambiguous determination of Ga-specific vibrational properties in Pu-Ga alloys, i.e, {Theta}{sub cD} for the Ga-Pu pair. Because the Debye temperature can be related to a measure of the lattice stiffness, these results indicate the Ga-Pu bonds are significantly stronger than the Pu-Pu bonds. This effect has important implications for lattice stabilization mechanisms in these alloys.

  10. Extended x-ray absorption fine structure measurements on radio frequency magnetron sputtered HfO2 thin films deposited with different oxygen partial pressures.

    PubMed

    Maidul Haque, S; Nayak, C; Bhattacharyya, Dibyendu; Jha, S N; Sahoo, N K

    2016-03-20

    Two sets of HfO2 thin film have been deposited by the radio frequency magnetron sputtering technique at various oxygen partial pressures, one set without any substrate bias and another set with a 50 W pulsed dc substrate bias. The films have been characterized by extended x-ray absorption fine structure (EXAFS) measurements at the Hf L3 edge, and the structural information obtained from analysis of the EXAFS data has been used to explain the macroscopic behavior of the refractive index obtained from spectroscopic ellipsometry measurements. It has been observed that the variation of refractive index with oxygen partial pressure depends on the Hf-Hf bond length for the set of films deposited without substrate bias, while for the other set of films deposited with pulsed dc substrate bias, it depends on the oxygen coordination of the nearest neighbor shell surrounding Hf sites. PMID:27140550

  11. 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.

  12. 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.

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

    NASA Astrophysics Data System (ADS)

    Aoyagi, Kiyoshi; Kajiura, Masako; Sugano, Satoru

    1981-11-01

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

  14. Structural characterization of (H sub x Re sub 3 (CO) sub 12 ) sup x-3 (x = 2, 3) by extended x-ray absorption fine structure spectroscopy

    SciTech Connect

    Van Zon, F.B.M.; Koningsberger, D.C. ); Kirlin, P.S.; Gates, B.C. )

    1989-03-23

    Extended x-ray absorption fine structure (EXAFS) measurements on the ReL{sub III} edge have been used to elucidate the structures of H{sub 3}ReP{sub 3}(CO){sub 12} and (H{sub 2}Re{sub 3}(CO){sub 12}){sup {minus}}. The data analysis is based on empirically determined EXAFS functions, including that of Os{sub 3}(CO){sub 12}, to account for the multiple scattering effects characteristic of metal carbonyls. The results confirm the presence of a triangular Re{sub 3} skeleton in each cluster, with the Re-Re bonds in the neutral cluster being of equal length (3.285 {angstrom}). The disorder in the Re-Re shell characterizing the anionic cluster indicates that not all the Re-Re bonds are of equal length, which implies the presence of bridging hydride ligands associated with the longer Re-Re bonds. Comparison of the EXAFS data with published x-ray diffraction data characterizing (HRe{sub 3}(CO){sub 12}){sup 2{minus}} shows a trend of decreasing Re-C distances and increasing C-O distances with increasing negative charge on the cluster, which is explained by {pi}-back-bonding.

  15. Extended x-ray absorption fine structure measurements on asymmetric bipolar pulse direct current magnetron sputtered Ta(2)O(5) thin films.

    PubMed

    Maidul Haque, S; Sagdeo, Pankaj R; Shinde, D D; Misal, J S; Jha, S N; Bhattacharyya, D; Sahoo, N K

    2015-08-01

    Tantalum pentoxide (Ta2O5) thin films have been deposited on fused silica substrates using a novel asymmetric bipolar DC magnetron sputtering technique under a mixed ambient of oxygen and argon. Films have been prepared at different oxygen-to-argon ratios, and the sputtering ambient and optical properties of the films have been investigated by spectroscopic ellipsometry, while the structural analysis of the films has been carried out by grazing incidence x-ray diffraction and extended x-ray absorption fine structure (EXAFS) measurements. The concentration of oxygen and tantalum in the Ta2O5 films has been estimated by Rutherford backscattering spectrometry (RBS). The variation of the optical constants of the films with changes in deposition parameters has been explained in the light of the change in average Ta-O bond lengths and oxygen coordination around Ta sites as obtained from EXAFS measurements. The trend in variation of the oxygen-to-tantalum ratio in the films obtained from RBS measurement, as a function of oxygen partial pressure used during sputtering, is found to follow the trend in variation of the oxygen coordination number around Ta sites obtained from EXAFS measurement. PMID:26368089

  16. Lead Is Not Off Center in PbTe: The Importance of r-Space Phase Information in Extended X-Ray Absorption Fine Structure Spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

    PbTe is a well-known thermoelectric material. Recent x-ray total scattering studies suggest that Pb moves off center along 100 in PbTe, by ˜0.2Å 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.

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

    NASA Astrophysics Data System (ADS)

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

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

  18. Surface extended x-ray absorption fine structure of low-Z absorbates using fluorescence detection

    SciTech Connect

    Stoehr, J.; Kollin, E.B.; Fischer, D.A.; Hastings, J.B.; Zaera, F.; Sette, F.

    1985-05-01

    Comparison of x-ray fluorescence yield (FY) and electron yield surface extended x-ray absorption fine structure spectra above the S K-edge for c(2 x 2) S on Ni(100) reveals an order of magnitude higher sensitivity of the FY technique. Using FY detection, thiophene (C/sub 4/H/sub 4/S) chemisorption on Ni(100) is studied with S coverages down to 0.08 monolayer. The molecule dissociates at temperatures as low as 100K by interaction with fourfold hollow Ni sites. Blocking of these sites by oxygen leaves the molecule intact.

  19. Near-Edge X-Ray Absorption Fine Structures Revealed in Core Ionization Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Nakano, M.; Selles, P.; Lablanquie, P.; Hikosaka, Y.; Penent, F.; Shigemasa, E.; Ito, K.; Carniato, S.

    2013-09-01

    Simultaneous core ionization and core excitation have been observed in the C2H2n (n=1, 2, 3) molecular series using synchrotron radiation and a magnetic bottle time-of-flight electron spectrometer. Rich satellite patterns corresponding to (K-2V) core excited states of the K-1 molecular ions have been identified by detecting in coincidence the photoelectron with the two Auger electrons resulting from the double core hole relaxation. A theoretical model is proposed providing absolute photoionization cross sections and revealing clear signatures of direct (monopolar) and conjugate (dipolar near-edge x-ray absorption fine structure) shakeup lines of comparable magnitude.

  20. Near-edge x-ray absorption fine structures revealed in core ionization photoelectron spectroscopy.

    PubMed

    Nakano, M; Selles, P; Lablanquie, P; Hikosaka, Y; Penent, F; Shigemasa, E; Ito, K; Carniato, S

    2013-09-20

    Simultaneous core ionization and core excitation have been observed in the C(2)H(2n) (n=1, 2, 3) molecular series using synchrotron radiation and a magnetic bottle time-of-flight electron spectrometer. Rich satellite patterns corresponding to (K(-2)V) core excited states of the K(-1) molecular ions have been identified by detecting in coincidence the photoelectron with the two Auger electrons resulting from the double core hole relaxation. A theoretical model is proposed providing absolute photoionization cross sections and revealing clear signatures of direct (monopolar) and conjugate (dipolar near-edge x-ray absorption fine structure) shakeup lines of comparable magnitude. PMID:24093255

  1. 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.

  2. 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})

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    SciTech Connect

    Antonio, M.R.; Soderholm, L.; Song, I.

    1995-06-12

    A purpose-built spectroelectrochemical cell for in situ fluorescence XAFS (X-ray Absorption Fine Structure) measurements of bulk solution species during constant-potential electrolysis is described. The cell performance was demonstrated by the collection of europium L{sub 3}-edge XANES (X-ray Absorption Near Edge Structure) throughout the course of electrolysis of an aqueous solution of EuCl{sub 3}{center_dot}6H{sub 2}O in 1 M H{sub 2}SO{sub 4}. The europium L{sub 3}-edge resonances reported here for the Eu{sup III} and Eu{sup II} ions demonstrate that their 2p{sub 3/2} {yields} 5d electronic transition probabilities are not the same.

  5. An extended-X-ray-absorption-fine-structure study of freeze-dried and solution ovotransferrin. Evidence for water co-ordination at the metal-binding sites.

    PubMed Central

    Hasnain, S S; Evans, R W; Garratt, R C; Lindley, P F

    1987-01-01

    Our previous extended-X-ray-absorption-fine-structure (e.x.a.f.s.) study has shown that the probable iron environment in chicken ovotransferrin involves two low-Z ligands (consistent with phenolate linkages) at 0.185(1) nm and four low-Z ligands at 0.204(1) nm [Garratt, Evans, Hasnain & Lindley (1986) Biochem. J. 233, 479-484]. Herein we provide additional information from the e.x.a.f.s. and near-edge structure suggestive of a decrease in the co-ordination number of ovotransferrin-bound iron upon freeze-drying. These effects are reversible, and exposure of the freeze-dried material to a humid atmosphere results in reversion to the solution spectra. Progressive rehydration was monitored by using e.p.r. spectroscopy and was confirmed by recording the high-resolution X-ray-absorption near-edge structure (x.a.n.e.s.). The results suggest the presence of a labile water molecule at the iron-binding sites of ovotransferrin in solution. PMID:2827627

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  7. Xe nanocrystals in Si studied by x-ray absorption fine structure spectroscopy

    SciTech Connect

    Faraci, Giuseppe; Pennisi, Agata R.; Zontone, Federico

    2007-07-15

    The structural configuration of Xe clusters, obtained by ion implantation in a Si matrix, has been investigated as a function of the temperature by x-ray absorption fine structure spectroscopy. In contrast with previous results, we demonstrate that an accurate analysis of the data, using high order cumulants, gives evidence of Xe fcc nanocrystals at low temperature, even in the as-implanted Si; expansion of the Xe lattice is always found as a function of the temperature, with no appreciable overpressure. We point out that a dramatic modification of these conclusions can be induced by an incorrect analysis using standard symmetrical pair distribution function G(r); for this reason, all the results were checked by x-ray diffraction measurements.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-11-01

    In mammalian cells, DNA-bound Fe(II) reacts with H 2O 2 producing the highly reactive hydroxyl radical ( rad OH) in situ. Since rad 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.

  10. 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.

  11. 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.

  12. Structural analysis of polymer-protected Pd/Pt bimetallic clusters as dispersed catalysts by using extended x-ray absorption fine structure spectroscopy

    SciTech Connect

    Toshima, Naoki; Harada, Masafumi; Yonezawa, Tetsu; Kushihashi, Kakuta; Asakura, Kiyotaka )

    1991-09-19

    Extended X-ray absorption fine structure (EXAFS) was applied to the determination of the structure of colloidal dispersions of the poly (N-vinyl-2-pyrrolidone)-protected palladium/platinum bimetallic clusters, which work as the catalysts for selective partial hydrogenation of 1,3-cyclooctadiene to cyclooctene. The catalytic activity was found to depend on the structure of the bimetallic clusters. The EXAFS data on the Pd/Pt (4/1) bimetallic clusters, which are the most active catalysts, indicate a Pt core structure, in which the 42 Pd atoms are on the surface of the cluster particle and 13 Pt atoms are at the center of the particle, forming a core. In contrast, the Pd/Pt (1/1) bimetallic clusters are suggested to have a modified Pt core structure, in which 28 Pt atoms connect directly with each other, being located both in the core and on the surface, and 27 Pd atoms form three islands on the surface of the cluster particle. These bimetallic clusters work as active catalysts for selective hydrogenation of olefins, selective partial hydrogenation of diene to monoene, and visible light-induced hydrogen generation from water.

  13. Incomplete transformations of Pb to pyromorphite by phosphate-induced immobilization investigated by X-ray absorption fine structure (XAFS) spectroscopy.

    PubMed

    Hashimoto, Yohey; Takaoka, Masaki; Oshita, Kazuyuki; Tanida, Hajime

    2009-07-01

    For an accurate assessment of immobilization technologies, it is necessary to illustrate the transformation of target metal species into their final products. The present study employed extended X-ray absorption fine structure (EXAFS) spectroscopy combined with linear combination fitting (LCF) to determine Pb species and their proportions in contaminated soils treated with phosphate amendments. Lead contaminated soils collected from a shooting range were separately treated with calcium phosphate (CP), hydroxyapatite synthesized from ceramic waste (CHA), and incinerated poultry litter (PW). Soils were incubated at 32% water content for 7 and 380 d. The EXAFS-LCF analysis illustrated that Pb speciation in the control soil included organically-complexed phases (Pb(org), 32%), PbO (22%), PbCO(3) (28%), and Pb(3)(CO(3))(2)(OH)(2) (8%). As the incubation period increased, the proportion of chloropyromorphite [Pb(5)(PO(4))(3)Cl] increased from 20% to 27% in CHA and from 19% to 31% in CP soils. The spectra of PW-amended soils were reproduced adequately with a combination of Pb(org), PbO, and chloropyromorphite in the proportion of about 20%, 45%, and 23%, respectively. The effectiveness of amendments on Pb immobilization as indicated by the chloropyromorphite proportion was in the order of CP (31%)>CHA (27%)>PW (23%) after 380 d of incubation. Our study indicates that about 70% of Pb species was not immobilized as a form of chloropyromorphite, and the additional supply of phosphate amendment scarcely promoted chloropyromorphite formation. The EXAFS-LCF approach illustrated that organically-complexed Pb was persistent in all amended soils, suggesting that an enriched soil organic carbon may be an inhibitory factor for pyromorphite transformations. PMID:19467557

  14. Molecular structures and solvation of free monomeric and dimeric ferriheme in aqueous solution: insights from molecular dynamics simulations and extended X-ray absorption fine structure spectroscopy.

    PubMed

    Kuter, David; Streltsov, Victor; Davydova, Natalia; Venter, Gerhard A; Naidoo, Kevin J; Egan, Timothy J

    2014-10-20

    CHARMM force field parameters have been developed to model nonprotein bound five-coordinate ferriheme (ferriprotoporphyrin IX) species in aqueous solution. Structures and solvation were determined from molecular dynamics (MD) simulations at 298 K of monomeric [HO-ferriheme](2-), [H2O-ferriheme](-), and [H2O-ferriheme](0); π-π dimeric [(HO-ferriheme)2](4-), [(H2O-ferriheme)(HO-ferriheme)](3-), [(H2O-ferriheme)2](2-), and [(H2O-ferriheme)2](0); and μ-oxo dimeric [μ-(ferriheme)2O](4-). Solvation of monomeric species predominated around the axial ligand, meso-hydrogen atoms of the porphyrin ring (Hmeso), and the unligated face. Existence of π-π ferriheme dimers in aqueous solution was supported by MD calculations where such dimers remained associated over the course of the simulation. Porphyrin rings were essentially coplanar. In these dimers major and minor solvation was observed around the axial ligand and Hmeso positions, respectively. In μ-oxo ferriheme, strong solvation of the unligated face and bridging oxide ligand was observed. The solution structure of the μ-oxo dimer was investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy. The EXAFS spectrum obtained from frozen solution was markedly different from that recorded on dried μ-oxo ferriheme solid. Inclusion of five solvent molecules obtained from spatial distribution functions in the structure generated from MD simulation was required to produce acceptable fits to the EXAFS spectra of the dimer in solution, while the solid was suitably fitted using the crystal structure of μ-oxo ferriheme dimethyl ester which included no solvent molecules. PMID:25275882

  15. X-ray absorption fine structure of artificial antigens for cadmium

    NASA Astrophysics Data System (ADS)

    Lu, Liang; Liu, Aiping; Chen, Fusheng; Wang, Xiaohong

    2011-11-01

    Immunoassay technology as a quick and large-scale screening method to detect metal ions in foods and environmental samples has rapidly been developed due to several advantages over conventional instrument-intensive methods. Unlike biomacromolecule, metal ions are haptens without immunogenicity, so successful preparation of artificial antigens is the first critical step for establishing immunoassay methods for them. In the current paper, cadmium ions were conjugated to BSA and OVA, respectively, using bifunctional chelator, p-SCN-Bn-DTPA. The ultraviolet analysis indicated that the maximum absorption peak of Cd-p-SCN-DTPA-BSA and Cd-p-SCN-DTPA-OVA had a small peak shift and an apparent absorbance increase compared to that of BSA and OVA, and the extents of substitution of ɛ-amino in both conjugates were 51.2% and 58.6%, respectively. In addition, the EXAFS of conjugates implied that Cd 2+ coordinated with N and O atoms of DTPA in artificial antigens, the coordination type and number of Cd-DTPA, Cd-p-SCN-Bn-DTPA-BSA, Cd-p-SCN-Bn-DTPA-OVA were the same. XANES region and geometries of the three compounds were also same. These results implied that the three antigens had the similar local structure and atomic geometry. This was the first time that the XAFS was attempted for the identification of artificial heavy metal ion antigens.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

    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.

  18. EXAFS study of copper thiosemicarbazide complexes

    NASA Astrophysics Data System (ADS)

    Mishra, Ashutosh; Mishra, S.; Ninama, S.; Pritam, A.

    2014-09-01

    The present paper deals with the synthesis of transition metal Schiff base complexes of copper by chemical root method. The synthesized metal complexes have been studied by extended X-ray absorption fine structure (EXAFS) technique. The metal ligand bond length have been determined using LSS, Levy's and Lytle's methods. Bond-lengths have also been determined from the Fourier transform of the EXAFS data. Bond lengths determined from these methods are comparable to each other.

  19. Near-Edge X-Ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

    SciTech Connect

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

    2009-05-26

    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 and 0.16 {+-} 0.04 eV, respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different degrees 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 nanoparticles.

  20. 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.

  1. Dynamics of Femtosecond Laser Ablation Plume Studied With Ultrafast X-ray Absorption Fine Structure Imaging

    SciTech Connect

    Oguri, Katsuya; Okano, Yasuaki; Nishikawa, Tadashi; Nakano, Hidetoshi

    2010-10-08

    We investigated the dynamic process of an expanding femtosecond laser ablation plume of aluminum generated in an irradiation intensity range of 10{sup 13}-10{sup 15} W/cm{sup 2} with the ultrafast x-ray absorption fine structure (XAFS) imaging technique. The XAFS spectra of the aluminum L{sub II,III} edge of the plume revealed that the plume consists of doubly and singly charged ions, neutral atoms, liquid particles, and possible atomic clusters. Scanning electron microscopy of deposited ablation particles confirmed that the liquid particles corresponds to the spherical nanoparticles with a size ranging from several tens nanometers to approximately 200 nm. The spatiotemporal evolution of the XAFS image of the plume shows the sequential appearance of each ablation particle from aluminum surface according to its ejection velocity. The result suggests that the photomechanical fragmentation process, which was theoretically proposed, is dominant mechanism for the nanoparticle ejection under the irradiation intensity far from the ablation threshold of aluminum. This study clearly demonstrates the potential of our technique for measuring the ultrafast dynamics of femtosecond laser ablation process.

  2. X-ray absorption fine structure spectroscopic study of uranium nitrides

    SciTech Connect

    Poineau, Frederic; Yeamans, Charles B.; Cerefice, Gary S.; Sattelberger, Alfred P; Czerwinski, Ken R.

    2012-01-01

    Uranium mononitride (UN), sesquinitride (U2N3) and dinitride (UN2) were characterized by extended X-Ray absorption fine structure spectroscopy. Analysis on UN indicate the presence of three uranium shells at distances of 3.46(3), 4.89(5) and 6.01(6) A and a nitrogen shell at a distance of 2.46(2) A . For U2N3, two absorbing uranium atoms at different crystallographic positions are present in the structure. One of the uranium atoms is surrounded by nitrogen atoms at 2.28(2) A and by uranium atoms at 3.66(4) and 3.95(4) A . The second type of uranium atom is surrounded by nitrogen atoms at 2.33(2) and 2.64(3) A and by uranium atoms at 3.66(4), 3.95(4) and 5.31(5) A . Results on UN2 indicate two uranium shells at 3.71(4) and 5.32(5) A and two nitrogen shells at 2.28(2).

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

    PubMed

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

    2012-09-01

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

  4. X-ray absorption fine structure study of the effect of protonation on disorder and multiple scattering in phosphate solutions and solids.

    PubMed

    Rouff, Ashaki A; Rabe, Stefan; Nachtegaal, Maarten; Vogel, Frédéric

    2009-06-25

    Phosphorus K-edge X-ray absorption fine structure (XAFS) was explored as a means to distinguish between aqueous and solid phosphates and to detect changes in phosphate protonation state. Data were collected for H(3)PO(4), KH(2)PO(4), K(2)HPO(4) and K(3)PO(4) solids and solutions and for the more complex phosphates, hydroxylapatite (HAP) and struvite (MAP). The X-ray absorption near-edge structure (XANES) spectra for solid samples are distinguishable from those of solutions by a shoulder at approximately 4.5 eV above the edge, caused by scattering from cation sites. For phosphate species, the intensity of the white line peak increased for solid and decreased for aqueous samples, respectively, with phosphate deprotonation. This was assigned to increasing charge delocalization in solid samples, and the effect of solvating water molecules on charge for aqueous samples. In the extended X-ray absorption fine structure (EXAFS), backscattering from first-shell O atoms dominated the chi(k) spectra. Multiple scattering (MS) via a four-legged P-O(1)-P-O(1)-P collinear path was localized in the lower k region at approximately 3.5 A(-1) and contributed significantly to the beat pattern of the first oscillation. For EXAFS analysis, increasing Debye-Waller factors suggest more disorder in the P-O shell with addition of protons to the crystal structure due to the lengthening effects of P-OH bonds. This disorder produces splitting in the hybridized P 3p-O 2p band in the density of states. For aqueous samples, however, increased protonation reduced the structural disorder within this shell. This was linked to a change from kosmotropic to chaotropic behavior of the phosphate species, with reduced effects of H bonding on structural distortion. The intensity of MS is correlated to the degree of disorder in the P-O shell, with more ordered structures exhibiting enhanced MS. The observed trends in the XAFS data can be used to distinguish between phosphate species in both solid and

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

    SciTech Connect

    Songaila, A.; Cowie, L. L.

    2014-10-01

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

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

    NASA Astrophysics Data System (ADS)

    Songaila, A.; Cowie, L. L.

    2014-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1996-09-01

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

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

    SciTech Connect

    Pease, D. M.; Daniel, M.; Budnick, J. I.; Rhodes, T.; Hammes, M.; Potrepka, D. M.; Sills, K.; Nelson, C.; Heald, S. M.; Brewe, D. I.

    2000-09-01

    We have constructed an x-ray monochromator based on a log spiral of revolution covered with highly oriented pyrolytic graphite. Such a monochromator is used for obtaining x-ray absorption edge fine structure by the fluorescence method, and is particularly useful for measuring the fine structure of dilute element A in a concentrated matrix of element B, where B is to the left of A in the Periodic Table. Using the log spiral monochromator, we measure good Cr x-ray fine structure in an alloy of 1% Cr in a V matrix, whereas the corresponding spectrum is severely distorted by the V background if nonmonochromatized fluorescence is used. We also obtain excellent rejection of Mn fluorescence relative to Cr fluorescence in a Cr{sub 80}Mn{sub 20} alloy, and can tune the monochromator such that the entire Mn step height is significantly smaller than the Cr x-ray absorption edge fine structure oscillations for this system. (c) 2000 American Institute of Physics.

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

    NASA Astrophysics Data System (ADS)

    Salomone-Stagni, Marco; Vogt, Sonja; Shima, Seigo; Meyer-Klaucke, Wolfram

    2009-11-01

    Hydrogenases are enzymes that catalyze the reversible oxidation of molecular hydrogen. Although their structure and catalytic mechanism are of considerable applied interest as models for the development of efficient catalysts for hydrogen fueled processes, the understanding of how hydrogenases react with H2 is only in its infancy. Two of the three known types of hydrogenases are iron-sulfur proteins that contain a dinuclear metal center, either [NiFe] or [FeFe]. In contrast, [Fe]-hydrogenase is the only mononuclear hydrogenase and thus a perfect system for studying the structural and electronic determinants of these enzymes. Here we summarize recent improvements in modeling based on the EXAFS signal and the geometric structure of this metalloenzyme in its as isolated or reconstituted form. The individual contributions to the EXAFS resulting in two different structural models are presented and discussed. Inspired by the new crystal structure, we show an advanced EXAFS model for the enzyme from Methanothermobacter marburgensis.

  10. Characterizing phosphorus speciation of Chesapeake Bay sediments using chemical extraction, 31P NMR, and X-ray absorption fine structure spectroscopy.

    PubMed

    Li, Wei; Joshi, Sunendra R; Hou, Guangjin; Burdige, David J; Sparks, Donald L; Jaisi, Deb P

    2015-01-01

    Nutrient contamination has been one of the lingering issues in the Chesapeake Bay because the bay restoration is complicated by temporally and seasonally variable nutrient sources and complex interaction between imported and regenerated nutrients. Differential reactivity of sedimentary phosphorus (P) pools in response to imposed biogeochemical conditions can record past sediment history and therefore a detailed sediment P speciation may provide information on P cycling particularly the stability of a P pool and the formation of one pool at the expense of another. This study examined sediment P speciation from three sites in the Chesapeake Bay: (i) a North site in the upstream bay, (ii) a middle site in the central bay dominated by seasonally hypoxic bottom water, and (iii) a South site at the bay-ocean boundary using a combination of sequential P extraction (SEDEX) and spectroscopic techniques, including (31)P NMR, P X-ray absorption near edge structure spectroscopy (XANES), and Fe extended X-ray absorption fine structure (EXAFS). Results from sequential P extraction reveal that sediment P is composed predominantly of ferric Fe-bound P and authigenic P, which was further confirmed by solid-state (31)P NMR, XANES, and EXAFS analyses. Additionally, solution (31)P NMR results show that the sediments from the middle site contain high amounts of organic P such as monoesters and diesters, compared to the other two sites, but that these compounds rapidly decrease with sediment depth indicating remineralized P could have precipitated as authigenic P. Fe EXAFS enabled to identify the changes in Fe mineral composition and P sinks in response to imposed redox condition in the middle site sediments. The presence of lepidocrocite, vermiculite, and Fe smectite in the middle site sediments indicates that some ferric Fe minerals can still be present along with pyrite and vivianite, and that ferric Fe-bound P pool can be a major P sink in anoxic sediments. These results provide

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

    NASA Astrophysics Data System (ADS)

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

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

  12. X-ray-Excited Optical Luminescence (XEOL) and X-ray Absorption Fine Structures (XAFS) Studies of Gold(I) Complexes with Diphosphine and Bipyridine Ligands

    SciTech Connect

    Kim, Pil-Sook G.; Hu, Yongfeng; Brandys, Marie-C.; Burchell, Tara J.; Puddephatt, Richard J.; Sham, Tsun K.

    2008-10-14

    Synchrotron techniques, X-ray-excited optical luminescence (XEOL) combined with X-ray absorption fine structures (XAFS), have been used to study the electronic structure and optical properties of a series of luminescent gold(I) complexes with diphosphine and bipyridine ligands using tunable X-rays (in the regions of the C and P K-edges and the Au L{sub 3}-edge) and UV from synchrotron light sources. The effects of gold-ligand and aurophilic interactions on the luminescence from these gold(I) complexes have been investigated. It is found that the luminescence from these complexes is phosphorescence, primarily due to the decay of the Au (5d) {yields} PR{sub 3} ({pi}*), metal to ligand charge transfer (MLCT) excitation as well as contributions from the conjugated {pi}-system in the bipyridine ligands via the gold-nitrogen bond. The large Au 5d spin-orbit coupling enhances the intersystem crossing. The elongation of the hydrocarbon chain of the diphosphine ligand does not greatly affect the spectral features of the luminescence from the gold(I) complexes. However, the intensity of the luminescence was reduced significantly when the bipyridine ligand was replaced with 1,2-bis(4-pyridylamido)benzene. The aurophilic interaction, as investigated by EXAFS at the Au L{sub 3}-edge, is shown to be only one of the factors that contribute to the luminescence of the complexes.

  13. 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.

  14. 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

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

    PubMed

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

    2005-07-22

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

  16. 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.

  17. 100-picosecond time-resolved X-ray absorption fine structure of FeII(1,10-phenanthroline)3

    NASA Astrophysics Data System (ADS)

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

    2009-02-01

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

  18. X-ray absorption study of octafluorodirhenate(III): EXAFS structures and resonance raman spectroscopy of octahalodirhenates

    SciTech Connect

    Conradson, S.D.; Sattelberger, A.P.; Woodruff, W.H.

    1988-02-17

    The structure, bonding, spectroscopy, and photophysics of transition-metal complexes containing quadruple metal-metal bonds are subjects of intense and general interest. For both historic and fundamental reasons, the octahalodirhenate(III) ions have become the paradigms of this field. Extensive spectroscopic and photophysical studies exist for the entire Re/sub 2/X/sub 8//sup 2 -/ series (X = F, Cl, Br, and I). However, while excellent structural data exist for X = Cl and Br, the structures of Re/sub 2/Fe/sub 8//sup 2 -/ and Re/sub 2/I/sub 8//sup 2 -/ have not been determined. These structures are essential for complete understanding of the bonding and physical and chemical behavior in these systems. Toward this end, the authors report structural features of Re/sub 2/F/sub 8//sup 2 -/ determined by extended X-ray absorption fine structure (EXAFS) spectroscopy. They also report X-ray absorption near-edge spectra (XANES); resonance Raman (RR) spectra have been determined previously by others and subsequently by the authors. They find that in Re/sub 2/F/sub 8//sup 2 -/ the Re-Re distance is 2.20 Angstrom and the Re-F distance is 1.95 A. Both of these distances are unexpected considering the corresponding stretching frequencies in the RR spectra.

  19. 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.

  20. 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

  1. Evaluation of thermal stability in Li0.2NixMn(1-x)/2Co(1-x)/2O2 (x = 1/3, 0.6, and 0.8) through X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Konishi, Hiroaki; Yoshikawa, Masanori; Hirano, Tatsumi; Hidaka, Kishio

    2014-05-01

    High-Ni-content layer-structured cathode materials for lithium-ion secondary batteries have high capacity but they suffer from poor thermal stability. We studied the mechanism responsible for their thermal stability to make them more stable. We used X-ray absorption fine structure (XAFS) spectra to clarify the changes in the oxidation states and the local structures for each transition metal in Li0.2NixMn(1-x)/2Co(1-x)/2O2 (x = 1/3, 0.6, and 0.8) at high temperature. The X-ray absorption near edge structure (XANES) spectra indicated that the oxidation state of Ni and Co changed due to heating. Although, pre-edge of XANES spectra indicated that the occupation sites of Co ions changed from octahedral to tetrahedral, Mn ions remained in the octahedral sites at high temperature. The extended X-ray absorption fine structure (EXAFS) results supported the change in the occupation sites of Co and Mn ions due to heating. It can be concluded that Co and Mn affected thermal stability of those Ni-based cathode materials differently. The Co ions migrated from octahedral to tetrahedral sites, and they stably occupy tetrahedral sites. Hence, so the structural change from spinel to rock-salt is suppressed. The oxidation state of Mn is stable and remains unchanged in layer structure at high temperature.

  2. Sulfur 1s near-edge x-ray absorption fine structure (NEXAFS) of thiol and thioether compounds

    SciTech Connect

    Beyhan, Shirin; Urquhart, Stephen G.; Hu Yongfeng

    2011-06-28

    The speciation and quantification of sulfur species based on sulfur K-edge x-ray absorption spectroscopy is of wide interest, particularly for biological and petroleum science. These tasks require a firm understanding of the sulfur 1s near-edge x-ray absorption fine structure (NEXAFS) spectra of relevant species. To this end, we have examined the gas phase sulfur 1s NEXAFS spectra of a group of simple thiol and thioether compounds. These high-resolution gas phase spectra are free of solid-state broadening, charging, and saturation effects common in the NEXAFS spectra of solids. These experimental data have been further analyzed with the aid of improved virtual orbital Hartree-Fock ab initio calculations. The experimental sulfur 1s NEXAFS spectra show fine features predicted by calculation, and the combination of experiment and calculation has been used to improve assignment of spectroscopic features relevant for the speciation and quantification of the sulfur compounds.

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

    NASA Astrophysics Data System (ADS)

    Ohata, Masaki; Matsubayashi, Nobuyuki

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

  4. 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.

  5. 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.

  6. Local environment of Mn dopant in ZnO by near-edge x-ray absorption fine structure analysis

    NASA Astrophysics Data System (ADS)

    Kunisu, Masahiro; Oba, Fumiyasu; Ikeno, Hidekazu; Tanaka, Isao; Yamamoto, Tomoyuki

    2005-03-01

    High-resolution near-edge x-ray absorption fine structure (NEXAFS) at MnK edge is employed to probe the local environment of Mn dopant in ZnO. First-principles supercell calculations are systematically made to obtain theoretical NEXAFS. Mn is found to substitute for Zn up to 5at. %Mn in polycrystalline samples sintered at 1623K in air. Presence of Mn3O4 is apparent for samples with higher Mn content. The NEXAFS does not change in the range of Mn concentration from 0.01 to 5at.%, indicating the absence of Mn precipitates. The results are confirmed by examining the polarization dependence of the NEXAFS for a 5at.%-doped ZnO thin film.

  7. 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.

  8. Time-resolved pump and probe x-ray absorption fine structure spectroscopy at beamline P11 at PETRA III.

    PubMed

    Göries, D; Dicke, B; Roedig, P; Stübe, N; Meyer, J; Galler, A; Gawelda, W; Britz, A; Geßler, P; Sotoudi Namin, H; Beckmann, A; Schlie, M; Warmer, M; Naumova, M; Bressler, C; Rübhausen, M; Weckert, E; Meents, A

    2016-05-01

    We report about the development and implementation of a new setup for time-resolved X-ray absorption fine structure spectroscopy at beamline P11 utilizing the outstanding source properties of the low-emittance PETRA III synchrotron storage ring in Hamburg. Using a high intensity micrometer-sized X-ray beam in combination with two positional feedback systems, measurements were performed on the transition metal complex fac-Tris[2-phenylpyridinato-C2,N]iridium(III) also referred to as fac-Ir(ppy)3. This compound is a representative of the phosphorescent iridium(III) complexes, which play an important role in organic light emitting diode (OLED) technology. The experiment could directly prove the anticipated photoinduced charge transfer reaction. Our results further reveal that the temporal resolution of the experiment is limited by the PETRA III X-ray bunch length of ∼103 ps full width at half maximum (FWHM). PMID:27250401

  9. Zinc cysteine active sites of metalloproteins: A density functional theory and x-ray absorption fine structure study

    NASA Astrophysics Data System (ADS)

    Dimakis, Nicholas; Farooqi, Mohammed Junaid; Garza, Emily Sofia; Bunker, Grant

    2008-03-01

    Density functional theory (DFT) and x-ray absorption fine structure (XAFS) spectroscopy are complementary tools for the biophysical study of active sites in metalloproteins. DFT is used to compute XAFS multiple scattering Debye Waller factors, which are then employed in genetic algorithm-based fitting process to obtain a global fit to the XAFS in the space of fitting parameters. Zn-Cys sites, which serve important functions as transcriptional switches in Zn finger proteins and matrix metalloproteinases, previously have proven intractable by this method; here these limitations are removed. In this work we evaluate optimal DFT nonlocal functionals and basis sets for determining optimal geometries and vibrational densities of states of mixed ligation Zn(His)4-n(Cys)n sites. Theoretical results are compared to experimental XAFS measurements and Raman spectra from the literature and tabulated for use.

  10. Characterization of the nitrate complexes of Pu(IV) using absorption spectroscopy, {sup 15}N NMR, and EXAFS

    SciTech Connect

    Veirs, D.K.; Smith, C.A.; Zwick, B.D.; Marsh, S.F.; Conradson, S.D.

    1993-12-01

    Nitrate complexes of Pu(IV) are studied in solutions containing nitrate up to 13 molar (M). Three major nitrato complexes are observed and identified using absorption spectroscopy, {sup 15}N nuclear magnetic resonance (NMR), and extended x-ray absorption fine structure (EXAFS) as Pu(NO{sub 3}){sub 2}{sup 2+}, Pu(NO{sub 3}){sub 4}, and Pu(NO{sub 3}){sub 6}{sup 2{minus}}. The possibility that Pu(NO{sub 3}){sub 1}{sup 3+}, Pu(NO{sub 3}){sub 3}{sup 1+} and Pu(NO{sub 3}){sub 5}{sup 1{minus}} are major species in solution is not consistent with these results and an upper limit of 0.10 can be set on the fraction for each of these three nitrate complexes in nitrate containing solutions. Fraction of the three major species in nitric acid over the 1--13 M range were calculated from absorption spectra data. The fraction of Pu(NO{sub 3}){sub 6}{sup 2{minus}} as a function of nitric acid concentration is in good agreement with the literature, whereas the fraction of Pu(NO{sub 3}){sub 2}{sup 2+} and Pu(NO{sub 3}){sub 4} species differ from previous studies. We have modeled the chemical equilibria up to moderate ionic strength ( < 6 molal) using the specific ion interaction theory (SM. Comparison of our experimental observations to literature stability constants that assume the presence of mononitrate species is poor. Stability constant at zero ionic strength for the dinitrato complex is determined to be log({beta}{sub 2}{sup 0})=3.77 {plus_minus} 0.14 (2{sigma}).

  11. Extended x-ray-absorption fine-structure observation of collinear ordering of Fe-Sn-Fe atoms in the Chevrel-phase superconductor SnFe/sub 0. 05/Mo/sub 6/S/sub 8/

    SciTech Connect

    Vaishnava, P.P.; Kimball, C.W.; Matykiewicz, J.L.; Fradin, F.Y.; Shenoy, G.K.; Montano, P.A.

    1986-10-01

    Extended x-ray-absorption fine-structure (EXAFS) and x-ray-diffraction studies have been conducted on the Chevrel-phase superconductor SnFe/sub 0.05/Mo/sub 6/S/sub 8/. The site symmetry of the iron is found to be similar to that of copper in the high-temperature phase of Cu/sub 1.8/Mo/sub 6/S/sub 8/. EXAFS analysis yielded interatomic distances, e.g., Fe-Sn and Fe-S, in this compound. The Fe-S distances are found to be characteristic of iron sulfides (e.g., FeS and Fe/sub 7/S/sub 8/). Through the observation of focused multiple scattering, a distance corresponding to a linear array of Fe-Sn-Fe atoms was measured. Iron atoms were found to be situated in two different configurations, one where iron has only a tin neighbor and the other where a linear-chain-like configuration of Fe-Sn-Fe atoms occurs.

  12. 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

    PubMed Central

    Younker, Jarod M.; Krest, Courtney M.; Jiang, Wei; Krebs, Carsten; Bollinger, J. Martin; Green, Michael T.

    2009-01-01

    The class Ic ribonucleotide reductase from Chlamydia trachomatis (Ct) uses a stable Mn(IV)/Fe(III) 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 Å. The Mn data also suggest the presence of a short 1.74 Å 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(III/III) form of the protein. Models are differentiated by the protonation states of their bridging and terminal OHX ligands as well as the location of the Mn(IV) ion (site 1 or 2). The models that agree best with experimental observation feature a µ-1,3-carboxylate bridge (E120), terminal solvent (H2O/OH) to site 1, one µ-O bridge, and one µ-OH bridge. The site-placement of the metal ions cannot be discerned from the available data. PMID:18937466

  13. 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.

  14. Local structure of Titanium in natural glasses probed by X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Wang, L.; Yoshiasa, A.; Okube, M.; Nakatani, T.; Hayasaka, Y.; Isobe, H.

    2013-04-01

    Synchrotron radiation has been used to collect titanium K-edge absorption spectra of a suite of natural glasses (tektites, impact glasses, fault rocks and volcanic glasses). XANES and XAFS analysis provided the qualitative and quantitative information of Ti oxidation state, Ti-O distance and site geometry. Tektites possess four-, five-, six-coordinated Ti, whereas fault rock-pseudotachylite, volcanic glasses and impact glass only presented five- and six-coordinated Ti. This study indicated that different petrogenesis of natural glasses has different local structures of titanium.

  15. Bounds on the fine structure constant variability from Fe ii absorption lines in QSO spectra

    NASA Astrophysics Data System (ADS)

    Molaro, P.; Reimers, D.; Agafonova, I. I.; Levshakov, S. A.

    2008-10-01

    The Single Ion Differential α Measurement (SIDAM)method for measuring Δα/α and its figures of merit are illustrated together withthe results produced by means of Fe ii absorption linesof QSO intervening systems. The method providesΔα/α = -0.12 ±1.79 ppm (parts-per-million) at zabs = 1.15towards HE 0515-4414 and Δα/α = 5.66±2.67 ppm at zabs = 1.84towards Q 1101-264, which are so far the most accurate measurementsfor single systems. SIDAM analysis for 3 systems from the Chand et al. [1]sample provides inconsistent results which we interpret as due tocalibration errors of the Chand et al. data at the level ≈10 ppm.In one system evidence for photo-ionization Dopplershift between Mg ii and Fe ii lines is found.This evidence has important bearings on the Many Multipletmethod where the signal for Δα/αvariabilityis carried mainly by systems involving Mg ii absorbers.Some correlations are also found in the Murphy et al. [10] sample which suggestlarger errors than previously reported.Thus, we consider unlikely that both the Chand et al.and Murphy et al. datasets could providean estimate of Δα/α with an accuracy at the level of 1 ppm.A new spectrograph like the ESPRESSO projectwill be crucial to make progress in the astronomical determination of Δα/α.

  16. Probing the spontaneous reduction mechanism of platinum ions confined in the nanospace by X-ray absorption fine structure spectroscopy.

    PubMed

    Jiang, Fangling; Li, Cheng; Fu, Haiying; Guo, Xiaojing; Wu, Guozhong; Chen, Shimou

    2016-07-28

    The reduction mechanism of Pt(4+) ions confined in the channel of multi-walled carbon nanotubes was mainly investigated using X-ray absorption fine structure (XAFS) spectroscopy, with the aid of TEM, Raman, XRD and ICP-AES studies. The XAFS spectra revealed the spontaneous formation of Pt nanoparticles when H2PtCl6 was confined in multi-walled carbon nanotubes (MWCNTs). The Pt L3-edge X-ray absorption near edge structure (XANES) coupled with the C K-edge NEXAFS results indicated that the reduction of Pt(4+) from tetravalent to zerovalent was attributed to the electron transfer from MWCNTs. The Fourier transform R-space of the Pt L3-edge XAFS data displayed that the nanoconfinement effect of MWCNTs promoted the formation of Pt nanoparticles. Moreover, the Pt-Pt bond length in confined Pt nanoparticles became shorter than that of Pt in the bulk state. Furthermore, by varying the inner diameter of MWCNTs from 15 nm to 10 nm and 5 nm, the Pt-Pt bond length of nanoconfined Pt nanoparticles decreased gradually. The results clearly revealed that MWCNTs acting as enriched electron donors can continuously reduce the confined Pt ions to Pt nanoparticles, thereby showing a great potential for the design of a new type of confined nanocatalysts. PMID:27373466

  17. Dynamics of femtosecond laser ablation studied with time-resolved x-ray absorption fine structure imaging

    SciTech Connect

    Oguri, Katsuya; Okano, Yasuaki; Nishikawa, Tadashi; Nakano, Hidetoshi

    2009-04-01

    We studied the dynamics of the femtosecond laser ablation of aluminum in an energy range well above the ablation threshold with the ultrafast time-resolved x-ray-absorption fine structure imaging technique. Analyzing the spectral structures near the L absorption edge that appeared in one-dimensional images of soft-x-ray absorbance, we successfully identified doubly and singly charged ions, neutral atoms, liquid nanoparticles, and possible atomic clusters in the expanding ablation plume. We also clarified that the ejected particles depend strongly on the laser irradiation intensity. The spatiotemporal evolution of the ablation particles allows us to estimate the spatial distribution of atomic density and the ejection velocity of each type of particle. In particular, we discuss the temporal sequence of the particle ejection in the early stages of plume expansion. Our experimental results strongly support the idea that photomechanical fragmentation and vaporization are dominant mechanisms for the production of liquid nanoparticles and neutral atoms, respectively, in femtosecond laser ablation induced in an irradiation intensity range of 10{sup 14}-10{sup 15} W/cm{sup 2}.

  18. 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

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

    SciTech Connect

    Gann, Eliot; McNeill, Christopher R.; Szumilo, Monika; Sirringhaus, Henning; Sommer, Michael; Maniam, Subashani; Langford, Steven J.; Thomsen, Lars

    2014-04-28

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

  20. 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., Jr.

    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.

  1. 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.

  2. 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.

  3. Curium analysis in plutonium uranium mixed oxide by x-ray fluorescence and absorption fine structure spectroscopy.

    PubMed

    Degueldre, C; Borca, C; Cozzo, C

    2013-10-15

    Plutonium uranium mixed oxide (MOX) fuels are being used in commercial nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regards to their environment and the coolant. In this work the study of the local occurrence, speciation and next-neighbour environment of curium (Cm) in the (Pu,U)O2 lattice within an irradiated (60 MW d kg(-1) average burn-up) MOX sample was performed employing micro-x-ray fluorescence (µ-XRF) and micro-x-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Cm (≈ 0.7 wt% in the rim and ≈ 0.03 wt% in the centre) are determined from the experimental data gained for the irradiated fuel material examined in its centre and peripheral (rim) zones of the fuel. Curium occurrence is also reduced from the centre (hot) to the periphery (colder) because of the condensation of these volatile oxides. In the irradiated sample Cm builds up as Cm(3+) species (>90%) within a [CmO8](13-) or [CmO7](11-) coordination environment and no (<10%) Cm(IV) can be detected in the rim zone. Curium dioxide is reduced because of the redox buffering activity of the uranium dioxide matrix and of its thermodynamic instability. PMID:24054692

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

    SciTech Connect

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

    2008-10-07

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

  5. 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.

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

    NASA Astrophysics Data System (ADS)

    Murphy, Michael T.; Malec, Adrian L.; Prochaska, J. Xavier

    2016-09-01

    The strongest transitions of Zn and Cr II are the most sensitive to relative variations in the fine-structure constant (Δα/α) among the transitions commonly observed in quasar absorption spectra. They also lie within just 40 Å of each other (rest frame), so they are resistant to the main systematic error affecting most previous measurements of Δα/α: long-range distortions of the wavelength calibration. While Zn and Cr II absorption is normally very weak in quasar spectra, we obtained high signal-to-noise, high-resolution echelle spectra from the Keck and Very Large Telescopes of nine rare systems where it is strong enough to constrain Δα/α from these species alone. These provide 12 independent measurements (three quasars were observed with both telescopes) at redshifts 1.0-2.4, 11 of which pass stringent reliability criteria. These 11 are all consistent with Δα/α = 0 within their individual uncertainties of 3.5-13 parts per million (ppm), with a weighted mean Δα/α = 0.4 ± 1.4stat ± 0.9sys ppm (1σ statistical and systematic uncertainties), indicating no significant cosmological variations in α. This is the first statistical sample of absorbers that is resistant to long-range calibration distortions (at the <1 ppm level), with a precision comparable to previous large samples of ˜150 (distortion-affected) absorbers. Our systematic error budget is instead dominated by much shorter range distortions repeated across echelle orders of individual spectra.

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

    NASA Astrophysics Data System (ADS)

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

    2001-12-01

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

  8. Quantitative Evaluation of the Carbon Hybridization State by Near Edge X-ray Absorption Fine Structure Spectroscopy.

    PubMed

    Mangolini, Filippo; McClimon, J Brandon; Carpick, Robert W

    2016-03-01

    The characterization of the local bonding configuration of carbon in carbon-based materials is of paramount importance since the properties of such materials strongly depend on the distribution of carbon hybridization states, the local ordering, and the degree of hydrogenation. Carbon 1s near edge X-ray absorption fine structure (NEXAFS) spectroscopy is one of the most powerful techniques for gaining insights into the bonding configuration of near-surface carbon atoms. The common methodology for quantitatively evaluating the carbon hybridization state using C 1s NEXAFS measurements, which is based on the analysis of the sample of interest and of a highly ordered pyrolytic graphite (HOPG) reference sample, was reviewed and critically assessed, noting that inconsistencies are found in the literature in applying this method. A theoretical rationale for the specific experimental conditions to be used for the acquisition of HOPG reference spectra is presented together with the potential sources of uncertainty and errors in the correctly computed fraction of sp(2)-bonded carbon. This provides a specific method for analyzing the distribution of carbon hybridization state using NEXAFS spectroscopy. As an illustrative example, a hydrogenated amorphous carbon film was analyzed using this method and showed good agreement with X-ray photoelectron spectroscopy (which is surface sensitive). Furthermore, the results were consistent with analysis from Raman spectroscopy (which is not surface sensitive), indicating the absence of a structurally different near-surface region in this particular thin film material. The present work can assist surface scientists in the analysis of NEXAFS spectra for the accurate characterization of the structure of carbon-based materials. PMID:26814796

  9. 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.

  10. Adsorption of dopamine on rutile TiO2 (110): a photoemission and near-edge X-ray absorption fine structure study.

    PubMed

    Jackman, Mark J; Syres, Karen L; Cant, David J H; Hardman, Samantha J O; Thomas, Andrew G

    2014-07-29

    Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) techniques have been used to study the adsorption of dopamine on a rutile TiO2 (110) single crystal. Photoemission results suggest that dopamine bonds through the oxygen molecules in a bidentate fashion. From the data, it is ambiguous whether the oxygens bond to the same 5-fold coordinated surface titanium atom or bridges across two, although based on the bonding of pyrocatechol on rutile TiO2 (110), it is likely that the dopamine bridges two titanium atoms. Using the searchlight effect, the carbon K-edge near-edge X-ray absorption fine structure NEXAFS spectra recorded for dopamine on rutile TiO2 (110) show the phenyl ring to be oriented at 78° ± 5° from the surface and twisted 11 ± 10° relative to the (001) direction. PMID:25003716

  11. Dynamical Study of Femtosecond-Laser-Ablated Liquid-Aluminum Nanoparticles Using Spatiotemporally Resolved X-Ray-Absorption Fine-Structure Spectroscopy

    SciTech Connect

    Oguri, Katsuya; Okano, Yasuaki; Nishikawa, Tadashi; Nakano, Hidetoshi

    2007-10-19

    We study the temperature evolution of aluminum nanoparticles generated by femtosecond laser ablation with spatiotemporally resolved x-ray-absorption fine-structure spectroscopy. We successfully identify the nanoparticles based on the L-edge absorption fine structure of the ablation plume in combination with the dependence of the edge structure on the irradiation intensity and the expansion velocity of the plume. In particular, we show that the lattice temperature of the nanoparticles is estimated from the L-edge slope, and that its spatial dependence reflects the cooling of the nanoparticles during plume expansion. The results reveal that the emitted nanoparticles travel in a vacuum as a condensed liquid phase with a lattice temperature of about 2500 to 4200 K in the early stage of plume expansion.

  12. Structural features and the reaction mechanism of cytochrome oxidase: iron and copper X-ray absorption fine structure.

    PubMed Central

    Powers, L; Chance, B; Ching, Y; Angiolillo, P

    1981-01-01

    X-ray edge absorption of copper and extended fine structure studies of both copper and iron centers have been made of cytochrome oxidase from beef heart, Paracoccus dentrificans, and HB-8 thermophilic bacteria (1-2.5 mM in heme). The desired redox state (fully oxidized, reduced CO, mixed valence formate and CO) in the x-ray beam was controlled by low temperature (-140 degrees C) and was continuously monitored by simultaneous optical spectroscopy and by electron paramagnetic resonance (EPR) monitoring every 30 min of x-ray exposure. The structure of the active site, a cytochrome a3-copper pair in fully oxidized and in mixed valence formate states where they are spin coupled, contains a sulphur bridge with three ligands 2.60 +/- 0.03 A from Fea3 and 2.18 +/- 0.03 A from Cua3. The distance between Fea3 and Cua3 is 3.75 +/- 0.05 A, making the sulphur bond angle 103 degrees reasonable for sp3 sulphur bonding. The Fea3 first shell has four typical heme nitrogens (2.01 +/- 0.03 A) with a proximal nitrogen at 2.14 +/- 0.03 A. The sixth ligand is the bridging sulphur. The Cua3 first shell is identical to oxidized stellacyanin containing two nitrogens and a bridging sulphur. Upon reduction with CO, the active site is identical to reduced stellacyanin for the Cua3 first shell and contains the sulphur that forms the bridge in fully oxidized and mixed valence formate states. The Fea3 first shell is identical to oxyhemoglobin but has CO instead of O2. The other redox centers, Fea and the other "EPR detectable" Cu are not observed in higher shells of Fea3. Fea has six equidistant nitrogens and Cua has one (or two) nitrogens and three (or two) sulphurs with typical distances; these ligands change only slight on reduction. These structures afford the basis for an oxygen reduction mechanism involving oxy- and peroxy intermediates. Images FIGURE 2 PMID:6264990

  13. 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}.

  14. 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.

  15. EXAFS study of structural disorder in carbonate-containing hydroxyapatites.

    PubMed

    Harries, J E; Hasnain, S S; Shah, J S

    1987-12-01

    A structural characterization of pure hydroxyapatite and partially carbonated hydroxyapatites has been performed using EXAFS spectroscopy, X-ray diffraction, and infrared spectroscopy. Our findings show that marked structural changes within the hydroxyapatite unit cell accompany the substitution of the phosphate anion. Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy has shown that the incorporation of carbonate into the phosphate site alters the structural geometry beyond the nearest neighbor oxygen coordination to calcium in a manner consistent with an increase in structural disorder. The nearest neighbor coordination to calcium is not detectably affected by the presence of carbonate. PMID:2830003

  16. Local structure of copper nitride revealed by EXAFS spectroscopy and a reverse Monte Carlo/evolutionary algorithm approach

    NASA Astrophysics Data System (ADS)

    Timoshenko, Janis; Anspoks, Andris; Kalinko, Aleksandr; Kuzmin, Alexei

    2016-05-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy combined with reverse Monte Carlo (RMC) and evolutionary algorithm (EA) modelling is used to advance the understanding of the local structure and lattice dynamics of copper nitride (Cu3N). The RMC/EA-EXAFS method provides a possibility to probe correlations in the motion of neighboring atoms and allows us to analyze the influence of anisotropic motion of copper atoms in Cu3N.

  17. 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

  18. Mechanism of the CO oxidation reaction on O-precovered Pt(111) surfaces studied with near-edge x-ray absorption fine structure spectroscopy

    SciTech Connect

    Nakai, I.; Kondoh, H.; Amemiya, K.; Nagasaka, M.; Shimada, T.; Yokota, R.; Nambu, A.; Ohta, T.

    2005-04-01

    The mechanism of CO oxidation reaction on oxygen-precovered Pt(111) surfaces has been studied by using time-resolved near-edge x-ray absorption fine structure spectroscopy. The whole reaction process is composed of two distinct paths: (1) a reaction of isolated oxygen atoms with adsorbed CO, and (2) a reaction of island-periphery oxygen atoms after the CO saturation. CO coadsorption plays a role to induce the dynamic change in spatial distribution of O atoms, which switches over the two reaction paths. These mechanisms were confirmed by kinetic Monte Carlo simulations. The effect of coadsorbed water in the reaction mechanism was also examined.

  19. C 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) of substituted benzoic acids: a theoretical and experimental study

    SciTech Connect

    Baldea,I.; Schimmelpfennig, B.; Plaschke, M.; Rothe, J.; Schirmer, J.; Trofimov, A.; Fanghaenel, T.

    2007-01-01

    Ab initio calculations are performed to explain the discrete transitions in experimental C 1s-NEXAFS (near edge X-ray absorption fine structure) spectra of various benzoic acid derivates. Transition energies and oscillator strengths of the contributing C 1s-{pi}* excitations are computed using the ADC(2) (second-order algebraic-diagrammatic construction) method. This method is demonstrated to be well suited for the finite electronic systems represented by these simple organic acids. There is good agreement between experiment and theory reproducing all the relevant spectral features. Some transitions can only be assigned based on a theoretical foundation. Remaining discrepancies between experimental and computed spectra are discussed.

  20. Structural properties of rutile TiO2 nanoparticles accumulated in a model of gastrointestinal epithelium elucidated by micro-beam x-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Veronesi, G.; Brun, E.; Fayard, B.; Cotte, M.; Carrière, M.

    2012-05-01

    Micro-beam x-ray absorption fine structure spectroscopy was used to investigate rutile TiO2 nanoparticles internalized into gastrointestinal cells during their crossing of a gut model barrier. Nanoparticles diluted in culture medium tend to accumulate in cells after 48 h exposure; however, no spectral differences arise between particles in cellular and in acellular environments, as corroborated by quantitative analysis. This finding establishes that no modification of the lattice properties of the nanoparticles occurs upon interaction with the barrier. These measurements demonstrate the possibility of interrogating nanoparticles in situ within cells, suggesting a way to investigate their fate when incorporated in biological hosts.

  1. L-edge x-ray absorption fine structure study of growth and morphology of ultrathin nickel films deposited on copper

    SciTech Connect

    Nietubyc, Robert; Foehlisch, Alexander; Glaser, Leif; Lau, Julian Tobias; Martins, Michael; Reif, Matthias; Wurth, Wilfried

    2004-12-15

    We have studied the Ni L edge x-ray absorption fine structure for thin Ni films evaporated on a Cu(001) substrate. The measurements have been carried out for films having coverages ranging from 0.07 monolayers (ML) up to 3.1 ML. The coverage has been calibrated using the ratio of the Ni L{sub 3} to Cu L{sub 3} edge jump heights and independently verified with titration experiments. We have found a clear evolution of the x-ray absorption fine structure at the Ni L{sub 3} edge with coverage. To interpret the measured spectra first-principles calculations have been performed modeling a two-dimensional growth. The calculations reproduced all features observed experimentally. From the comparison between experiment and theory we can conclude that submonolayer films contain a large number of small islands. Deposition of an amount of nickel corresponding to a single layer results in the formation of an almost perfect flat layer. Our studies show that L edge x-ray absorption spectroscopy can provide useful information on thin-film growth and morphology.

  2. A new limit on the variation of the fine-structure constant using absorption line multiplets in the early universe

    NASA Astrophysics Data System (ADS)

    Thong, Le Duc

    2015-08-01

    One of the key questions of modern physics concerns the possibility that physical constants vary over space and time during the history of the universe. The Standard Model of physics is built on these constants, but it does not provide any explanation for their values, nor requires their constancy over space and time. Here we set a new limit on possible spatial and temporal variations of the fine-structure constant , by comparing transitions line multiplets in an ensemble of Fe II 1608, 2344, 2374, 2383, 2587 and 2600 observed in the early universe with those measured in the laboratory. Based on the optical spectra observations of QSO HE 0515-4414, we deduced a constraint of at redshift z = 1.15. This is at present the tightest limit on at early cosmological epochs compared to the published results in the literature.

  3. 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.

  4. A Stringent Limit on Variation of the Fine-Structure Constant Using Absorption Line Multiplets in the Early Universe

    NASA Astrophysics Data System (ADS)

    Le, T. D.

    2016-06-01

    One of the key questions of modern physics concerns the possibility that physical constants have varied throughout the history of the Universe. The standard model of physics is built on these constants, but it does not provide any explanation for their values, nor does it require their constancy over space and time. Here, we set a new limit on possible spatial and temporal variations of the fine-structure constant α = e 2/4πɛ0 ħc by comparing transitions and line multiplets in an ensemble of Fe II λ 1608, λ 2344, λ 2374, λ 2383, λ 2587, and λ 2600 observed in the early Universe with those measured in the laboratory. Based on the optical spectrum observations of QSO HE 0515-4414, we deduce a constraint of Δα/α = (-0.157± 0.300)×10-6 at redshift z = 1.15. At present, this represents the tightest limit on Δα/α in early cosmological epochs compared to the published results in the literature.

  5. Core-hole effects on theoretical electron-energy-loss near-edge structure and near-edge x-ray absorption fine structure of MgO

    NASA Astrophysics Data System (ADS)

    Mizoguchi, Teruyasu; Tanaka, Isao; Yoshiya, Masato; Oba, Fumiyasu; Ogasawara, Kazuyoshi; Adachi, Hirohiko

    2000-01-01

    First-principles molecular orbital calculations using model clusters are made in order to reproduce and interpret experimental electron-energy-loss near-edge structure and near-edge x-ray absorption fine structure of MgO at Mg K, L2,3 and O K edges. Ground-state calculations using a model cluster composed of 125 atoms and by a band-structure method are in good agreement, but they do not reproduce the experimental spectra satisfactory. They are well reproduced only by the cluster calculations for the Slater transition state, where a half-electron is removed from a core orbital and placed into the lowest unoccupied molecular orbital. The core-hole effect is therefore essential for theoretical reproduction of the spectral shapes. A large supercell is required to reproduce the experimental spectra when one uses a band-structure method. The origin of peaks appearing in the experimental spectra is interpreted in terms of orbital interactions using overlap-population diagrams. Some features of the spectra at different edges are pointed out to have common origins. Experimental spectra are aligned accordingly. The transition energies and qualitative features of experimental spectra are found to be reproduced even using a smaller cluster composed of 27 atoms, although some of fine structure is missing.

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

    SciTech Connect

    Niibe, Masahito; Miyamoto, Kazuyoshi; Mitamura, Tohru; Mochiji, Kozo

    2010-09-15

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

  7. Full-potential theoretical investigations of electron inelastic mean free paths and extended x-ray absorption fine structure in molybdenum.

    PubMed

    Chantler, C T; Bourke, J D

    2014-04-01

    X-ray absorption fine structure (XAFS) spectroscopy is one of the most robust, adaptable, and widely used structural analysis tools available for a range of material classes from bulk solids to aqueous solutions and active catalytic structures. Recent developments in XAFS theory have enabled high-accuracy calculations of spectra over an extended energy range using full-potential cluster modelling, and have demonstrated particular sensitivity in XAFS to a fundamental electron transport property-the electron inelastic mean free path (IMFP). We develop electron IMFP theory using a unique hybrid model that simultaneously incorporates second-order excitation losses, while precisely accounting for optical transitions dictated by the complex band structure of the solid. These advances are coupled with improved XAFS modelling to determine wide energy-range absorption spectra for molybdenum. This represents a critical test case of the theory, as measurements of molybdenum K-edge XAFS represent the most accurate determinations of XAFS spectra for any material. We find that we are able to reproduce an extended range of oscillatory structure in the absorption spectrum, and demonstrate a first-time theoretical determination of the absorption coefficient of molybdenum over the entire extended XAFS range utilizing a full-potential cluster model. PMID:24651638

  8. Study of hard disk and slider surfaces using X-ray photoemission electron microscopy and near-edge X-ray absorption fine structure spectroscopy

    SciTech Connect

    Anders, S.; Stammler, T.; Bhatia, C.S.; Fong, W.; Chen, C.Y.; Bogy, D.B.

    1998-04-01

    X-ray Photo Emission Electron Microscopy (X-PEEM) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy were applied to study the properties of amorphous hard carbon overcoats on disks and sliders, and the properties of the lubricant. The modification of lubricants after performing thermal desorption studies was measured by NEXAFS, and the results are compared to the thermal desorption data. The study of lubricant degradation in wear tracks is described. Sliders were investigated before and after wear test, and the modification of the slider coating as well as the transfer of lubricant to the slider was studied. The studies show that the lubricant is altered chemically during the wear. Fluorine is removed and carboxyl groups are formed.

  9. Studies of Mn/GaAs digital alloys using x-ray absorption fine structure and x-ray diffraction methods

    NASA Astrophysics Data System (ADS)

    Soo, Y. L.; Kioseoglou, G.; Kim, S.; Chen, X.; Luo, H.; Kao, Y. H.; Sasaki, Y.; Liu, X.; Furdyna, J. K.

    2002-04-01

    Local structure and effective chemical valency of Mn atoms in Mn/GaAs digital alloys have been investigated using the x-ray absorption fine structure techniques. The samples were prepared by molecular-beam epitaxy with different thickness of GaAs layers separating the nominal Mn monolayers. Lattice constants of the digital alloys are found by x-ray diffraction to increase linearly in a very narrow range (about 0.3%) with the Mn/GaAs ratio in the samples. Our data show that Mn atoms in the nominal Mn monolayers actually combine with GaAs to form (Ga, Mn)As alloys with Mn atoms substituting for the Ga sites in GaAs. This result clearly rules out the possibility of dominant MnAs formation.

  10. A high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure measurement.

    PubMed

    Murata, Naoyoshi; Kobayashi, Makoto; Okada, Yukari; Suzuki, Takuya; Nitani, Hiroaki; Niwa, Yasuhiro; Abe, Hitoshi; Wada, Takahiro; Mukai, Shingo; Uehara, Hiromitsu; Ariga, Hiroko; Takakusagi, Satoru; Asakura, Kiyotaka

    2015-03-01

    We present the design and performance of a high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure (XAFS) spectra. The cell has a large fluorescence XAFS window (116 mm(ϕ)) near the sample in the cell, realizing a large half-cone angle of 56°. We use a small heater (25 × 35 mm(2)) to heat the sample locally to 873 K. We measured a Pt-SnO2 thin layer on a Si substrate at reaction conditions having a high activity. In situ measurement enables the analysis of the difference XAFS spectra between before and during the reaction to reveal the structure change during the operation. PMID:25832248

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

    PubMed

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

    2009-02-19

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

  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. 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.

  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. Near edge X-ray absorption fine structure spectroscopy as a tool to probe electronic and structural properties of thin organic films and liquids.

    PubMed

    Hähner, Georg

    2006-12-01

    Synchrotron-based spectroscopic techniques have contributed significantly to a better understanding of the properties of materials on the macroscopic and microscopic scale over the last decades. They can be applied to samples from a diversity of fields, including Biology, Life Sciences, Chemistry and Materials. One of these techniques is Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy, revealing electronic structure and information on the orientation of adsorbed molecules. The present article describes the basics of the technique and the progress it has made over the last three decades, and summarizes some of its more recent developments and applications. This tutorial review article should be accessible for novices to the field from Physics, Chemistry, Biology, Materials, and the Life Sciences, interested in thin organic films and liquid systems. PMID:17225886

  16. Local atomic structure around Ni, Nb, and Zr atoms in Ni-Nb-Zr-H glassy alloys studied by x-ray absorption fine structure method

    NASA Astrophysics Data System (ADS)

    Oji, H.; Handa, K.; Ide, J.; Honma, T.; Yamaura, S.; Inoue, A.; Umesaki, N.; Emura, S.; Fukuhara, M.

    2009-06-01

    To elucidate hydrogen effects on the atomic configuration of Ni-Nb-Zr-H glassy alloys exhibiting proton-tunneling-induced Coulomb oscillation, we investigated the local atomic configuration around the Ni, Nb, and Zr atoms by x-ray absorption fine structure (XAFS) method. The analysis of the XAFS spectra indicates that there is the significant difference in structural response between the Zr 30 and the Zr 40 at. % alloys when hydrogen atoms are charged; charging the hydrogen atoms basically does not alter the local structures around the three atoms for the Zr 30 at. % alloy but induces the elongation of the Zr-Zr, Zr-Nb, and Nb-Ni distances for the Zr 40 at. % alloy. The distorted icosahedral Zr5Ni5Nb3 clusters assembled in randomly packed manners for the possible models in the Ni-Nb-Zr glassy alloy are proposed. The sites where hydrogen atoms occupy are also inferred.

  17. X-ray absorption fine structure combined with fluorescence spectrometry for monitoring trace amounts of lead adsorption in the environmental conditions.

    PubMed

    Izumi, Yasuo; Kiyotaki, Fumitaka; Minato, Taketoshi; Seida, Yoshimi

    2002-08-01

    The local structure of trace amounts of lead in an adsorbent matrix that contains a high concentration of iron and magnesium (Mg6Fe2(OH)16(CO3) x 3H2O) was successfully monitored by means of X-ray absorption fine structure spectroscopy combined with fluorescence spectrometry. A eutectic mixture of PbCO3 and Pb(OH)2 coagulated when Pb2+ was adsorbed from a 1.0 ppm aqueous solution, and in contrast, the major species was ion-exchanged Pb2+ in the case of adsorption from a 100 ppb aqueous solution. The difference was ascribed to the balance between the precipitation equilibrium for coagulation and the rate of the ion exchange reaction with surface hydroxyl groups. PMID:12175171

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  19. Combined small-angle x-ray scattering/extended x-ray absorption fine structure study of coated Co nanoclusters in bis(2-ethylhexyl)sulfosuccinate

    NASA Astrophysics Data System (ADS)

    Longo, A.; Giordano, F.; Giannici, F.; Martorana, A.; Portale, G.; Ruggirello, A.; Turco Liveri, V.

    2009-06-01

    Chemically stable cobalt nanostructures have been prepared with Co(II) reduction in the confined space of cobalt bis(2-ethylhexyl)sulfosuccinate, Co(AOT)2, reverse micelles dispersed in n-heptane. The reaction was carried out by adding a solution of sodium borohydride in ethanol (1% weight) to a 0.2M micellar solution of Co(AOT)2 in n-heptane at a reductant to Co(II) molar ratio of 4. This procedure involves the rapid formation of surfactant-coated Co nanoparticles followed by their slow separation as nanostructures embedded in a sodium bis(2-ethylhexyl)sulfosuccinate matrix. The resulting composites, characterized by extended x-ray absorption fine structure and small-angle x-ray scattering, showed the presence of subnanometer sized cobalt nanoparticles aggregated together to form elongated structures coated by the surfactant molecules.

  20. Effect of gas residence time on near-edge X-ray absorption fine structures of hydrogenated amorphous carbon films grown by plasma-enhanced chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Jia, Lingyun; Sugiura, Hirotsugu; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Oda, Osamu; Sekine, Makoto; Hiramatsu, Mineo; Hori, Masaru

    2016-04-01

    In hydrogenated amorphous carbon films, deposited using a radical-injection plasma-enhanced chemical vapor deposition system, the chemical bonding structure was analyzed by near-edge X-ray absorption fine-structure spectroscopy. With a change in the residence times of source gases in a reactor, whereby total gas flow rates of H2/CH4 increased from 50 to 400 sccm, sp2-C fractions showed the minimum value at 150 sccm, while H concentration negligibly changed according to the results of secondary ion mass spectroscopy. On the other hand, widths of σ* C-C peaks increased with decreasing gas residence time, which indicates an increase in the fluctuation of bonding structures.

  1. Extended x-ray absorption fine structure study of MnFeP0.56Si0.44 compound

    NASA Astrophysics Data System (ADS)

    Li, Ying-Jie; Haschaolu, W.; Wurentuya; Song, Zhi-Qiang; Ou, Zhi-Qiang; Tegus, O.; Nakai, Ikuo

    2015-08-01

    The MnFeP0.56Si0.44 compound is investigated by x-ray diffraction, magnetic measurements, and x-ray absorption fine structure spectroscopy. It crystallizes in Fe2P-type structure with the lattice parameters a = b = 5.9823(0) Å and c = 3.4551(1) Å and undergoes a first-order phase transition at the Curie temperature of 255 K. The Fe K edge and Mn K edge x-ray absorption fine structure spectra show that Mn atoms mainly reside at 3g sites, while 3f sites are occupied by Fe atoms. The distances between the absorbing Fe atom and the first and second nearest neighbor Fe atoms in a 3f-layer shift from 2.65 Å and 4.01 Å in the ferromagnetic state to 2.61 Å and 3.96 Å in the paramagnetic phase. On the other hand, the distance between the 3g-layer and 3f-layer changes a little as 2.66 Å-2.73 Å below the Curie temperature and 2.68 Å-2.75 Å above it. Project supported by the National Natural Science Foundation of China (Grant Nos. 51461035, 51161017, and 11404176), the Scientific Research Projects of the Higher Educational Department of Inner Mongolian Autonomous Region (Grant No. NJZZ14033). The XAFS measurement was performed under the approval of Photon Factory Program Advisory Committee (Proposal Nos. 2012G095 and 2014G047).

  2. The determination of interfacial structure and phase transitions in Al/Cu and Al/Ni interfaces by means of surface extended x-ray absorption fine structure

    SciTech Connect

    Barrera, E.V. . Dept. of Mechanical Engineering and Materials Science); Heald, S.M. )

    1991-01-01

    Surface extended x-ray absorption fine structure (SEXAFS) was used to investigate the interfacial conditions of Al/Cu and Al/Ni shallow buried interfaces. Previous studies using glancing angle extended x-ray absorption fine structure, x-ray reflectivity, photoemission, and SEXAFS produced conflicting results as to whether or not the interfaces between Al and Cu and Al and Ni were reacted upon room temperature deposition. In this study polycrystalline bilayers of Al/Cu and Al/Ni and trilayers of Al/Cu/Al and Al/Ni/Al were deposited on tantalum foil at room temperature in ultra high vacuum and analyzed to evaluate the reactivity of these systems on a nanometer scale. It become overwhelming apparent that the interfacial phase reactions were a function of the vacuum conditions. Samples deposited with the optimum vacuum conditions showed reaction products upon deposition at room temperature which were characterized by comparisons to standards and by least squares fitting the be CuAl{sub 2} and NiAl{sub 3} respectively. The results of this study that the reacted zone thicknesses were readily dependent on the deposition parameters. For both Al on Cu and Al on Ni as well as the metal on Al conditions 10{Angstrom} reaction zones were observed. These reaction zones were smaller than that observed for bilayers of Al on Cu (30{Angstrom}) and Al on Ni (60{Angstrom}) where deposition rates were much higher and samples were much thicker. The reaction species are evident by SEXAFS, where the previous photoemission studies only indicated that changes had occurred. Improved vacuum conditions as compared to the earlier experiments is primarily the reason reactions on deposition were seen in this study as compared to the earlier SEXAFS studies.

  3. The determination of interfacial structure and phase transitions in Al/Cu and Al/Ni interfaces by means of surface extended x-ray absorption fine structure

    SciTech Connect

    Barrera, E.V.; Heald, S.M.

    1991-12-31

    Surface extended x-ray absorption fine structure (SEXAFS) was used to investigate the interfacial conditions of Al/Cu and Al/Ni shallow buried interfaces. Previous studies using glancing angle extended x-ray absorption fine structure, x-ray reflectivity, photoemission, and SEXAFS produced conflicting results as to whether or not the interfaces between Al and Cu and Al and Ni were reacted upon room temperature deposition. In this study polycrystalline bilayers of Al/Cu and Al/Ni and trilayers of Al/Cu/Al and Al/Ni/Al were deposited on tantalum foil at room temperature in ultra high vacuum and analyzed to evaluate the reactivity of these systems on a nanometer scale. It become overwhelming apparent that the interfacial phase reactions were a function of the vacuum conditions. Samples deposited with the optimum vacuum conditions showed reaction products upon deposition at room temperature which were characterized by comparisons to standards and by least squares fitting the be CuAl{sub 2} and NiAl{sub 3} respectively. The results of this study that the reacted zone thicknesses were readily dependent on the deposition parameters. For both Al on Cu and Al on Ni as well as the metal on Al conditions 10{Angstrom} reaction zones were observed. These reaction zones were smaller than that observed for bilayers of Al on Cu (30{Angstrom}) and Al on Ni (60{Angstrom}) where deposition rates were much higher and samples were much thicker. The reaction species are evident by SEXAFS, where the previous photoemission studies only indicated that changes had occurred. Improved vacuum conditions as compared to the earlier experiments is primarily the reason reactions on deposition were seen in this study as compared to the earlier SEXAFS studies.

  4. 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.

  5. 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.

  6. 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 Central

    2015-01-01

    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 13CO 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. PMID:25275608

  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. 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. PMID:23360082

  9. Al K-edge extended fine structures in X-ray emission spectra of aluminum metal and aluminum oxide measured by an electron probe microanalyzer (EPMA)

    NASA Astrophysics Data System (ADS)

    Tanuma, S.; Nishio, M.

    1998-03-01

    The radiative Auger satellite peaks of Al Kα for aluminum metal and aluminum oxide were measured over a small area using an electron probe microanalyzer (EPMA). The oscillation was found to be similar to the extended X-ray absorption fine structure (EXAFS) in the EPMA spectra, oscillation which was recently discovered by Hayashi et al. (1997) in the X-ray fluorescence (XRF) spectra. The measured EXAFS spectra with EPMA are in good agreement with those by Hayashi et al., but here the oscillation structure could be obtained in a few minutes over a small area by using EPMA.

  10. EXAFS study on dynamic structural property of porous morph-genetic SiC

    NASA Astrophysics Data System (ADS)

    Ding, J.; Sun, B. H.; Fan, T. X.; Zhang, D.; Kamada, M.; Ogawa, H.; Guo, Q. X.

    2005-08-01

    Novel porous morph-genetic silicon carbide has been fabricated through sintering treatment, after infiltrating the methyl organic silicone resin to the bio-template. Its dynamic transition of structure during sintering process is investigated by extended X-ray absorption fine structure (EXAFS) for the first time. By analyzing Si K-edge EXAFS, it is found that the coordination number of the nearest C shell remains almost unchanged while that of the nearest Si shell dramatically changes when the structure is transformed from amorphous into crystalline state.

  11. EXAFS and DFT study of the cadmium and lead adsorption on modified silica nanoparticles.

    PubMed

    Arce, Valeria B; Gargarello, Romina M; Ortega, Florencia; Romañano, Virginia; Mizrahi, Martín; Ramallo-López, José M; Cobos, Carlos J; Airoldi, Claudio; Bernardelli, Cecilia; Donati, Edgardo R; Mártire, Daniel O

    2015-12-01

    Silica nanoparticles of 7 nm diameter were modified with (3-aminopropyl) triethoxysilane (APTES) and characterized by CP-MAS (13)C and (29)Si NMR, FTIR, zeta potential measurements, and thermogravimetry. The particles were shown to sorb successfully divalent lead and cadmium ions from aqueous solution. Lead complexation with these silica nanoparticles was clearly confirmed by EXAFS (Extended X-ray Absorption Fine Structure) with synchrotron light measurements. Predicted Pb-N and Pb-C distances obtained from quantum-chemical calculations are in very good agreement with the EXAFS determinations. The calculations also support the higher APTES affinity for Pb(2+) compared to Cd(2+). PMID:26135536

  12. EXAFS measurements on Mn doped CaF2 phosphor with different Mn concentrations

    NASA Astrophysics Data System (ADS)

    Patra, N.; Bakshi, A. K.; Bhattacharyya, D.

    2016-05-01

    Extended X-ray Absorption Fine Structure (EXAFS) measurements have been carried out on Mn doped CaF2 phosphors with synchrotron radiation at the Mn K edge. Measurements have been carried out on samples prepared with different concentrations of Mn dopants. The data have been analyzed to find out the Mn-F bond lengths and % of Mn doped CaF2 phase in the samples. The change in thermoluminescence glow peak temperature in CaF2:Mn phosphor with variation in Mn concentration has been correlated to the parameters obtained from EXAFS measurements.

  13. X-ray diffraction and EXAFS analysis of materials for lithium-based rechargeable batteries

    SciTech Connect

    Sharkov, M. D. Boiko, M. E.; Bobyl, A. V.; Ershenko, E. M.; Terukov, E. I.; Zubavichus, Y. V.

    2013-12-15

    Lithium iron phosphate LiFePO{sub 4} (triphylite) and lithium titanate Li{sub 4}Ti{sub 5}O{sub 12} are used as components of a number of active materials in modern rechargeable batteries. Samples of these materials are studied by X-ray diffraction and extended X-ray absorption fine structure (EXAFS) spectroscopy. Hypotheses about the phase composition of the analyzed samples are formulated.

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

    PubMed

    Schmidt, Norman; Fink, Rainer; Hieringer, Wolfgang

    2010-08-01

    The C 1s and N 1s near-edge x-ray absorption fine structure (NEXAFS) spectra of three prototype tetraphenyl porphyrin (TPP) molecules are discussed in the framework of a combined experimental and theoretical study. We employ time-dependent density-functional theory (TDDFT) to compute the NEXAFS spectra of the open- and closed-shell metalloporphyrins CoTPP and ZnTPP as well as the free-base 2HTPP in realistic nonplanar conformations. Using Becke's well-known half-and-half hybrid functional, the computed core excitation spectra are mostly in good agreement with the experimental data in the low-energy region below the appropriate ionization threshold. To make these calculations feasible, we apply a new, simple scheme based on TDDFT using a modified single-particle input spectrum. This scheme is very easy to implement in standard codes and allows one to compute core excitation spectra at a similar cost as ordinary UV/vis spectra even for larger molecules. We employ these calculations for a detailed assignment of the NEXAFS spectra including subtle shifts in certain peaks of the N 1s spectra, which depend on the central coordination of the TPP ligand. We furthermore assign the observed NEXAFS resonances to the individual molecular subunits of the investigated TPP molecules. PMID:20707545

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

    NASA Astrophysics Data System (ADS)

    Schmidt, Norman; Fink, Rainer; Hieringer, Wolfgang

    2010-08-01

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

  16. Towards atomic resolution in sodium titanate nanotubes using near-edge X-ray-absorption fine-structure spectromicroscopy combined with multichannel multiple-scattering calculations

    PubMed Central

    Krüger, Peter; Lagos, Maureen J; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Ewels, Chris; Umek, Polona; Guttmann, Peter

    2012-01-01

    Summary Recent advances in near-edge X-ray-absorption fine-structure spectroscopy coupled with transmission X-ray microscopy (NEXAFS–TXM) allow large-area mapping investigations of individual nano-objects with spectral resolution up to E/ΔE = 104 and spatial resolution approaching 10 nm. While the state-of-the-art spatial resolution of X-ray microscopy is limited by nanostructuring process constrains of the objective zone plate, we show here that it is possible to overcome this through close coupling with high-level theoretical modelling. Taking the example of isolated bundles of hydrothermally prepared sodium titanate nanotubes ((Na,H)TiNTs) we are able to unravel the complex nanoscale structure from the NEXAFS–TXM data using multichannel multiple-scattering calculations, to the extent of being able to associate specific spectral features in the O K-edge and Ti L-edge with oxygen atoms in distinct sites within the lattice. These can even be distinguished from the contribution of different hydroxyl groups to the electronic structure of the (Na,H)TiNTs. PMID:23213642

  17. Towards atomic resolution in sodium titanate nanotubes using near-edge X-ray-absorption fine-structure spectromicroscopy combined with multichannel multiple-scattering calculations.

    PubMed

    Bittencourt, Carla; Krüger, Peter; Lagos, Maureen J; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Ewels, Chris; Umek, Polona; Guttmann, Peter

    2012-01-01

    Recent advances in near-edge X-ray-absorption fine-structure spectroscopy coupled with transmission X-ray microscopy (NEXAFS-TXM) allow large-area mapping investigations of individual nano-objects with spectral resolution up to E/ΔE = 10(4) and spatial resolution approaching 10 nm. While the state-of-the-art spatial resolution of X-ray microscopy is limited by nanostructuring process constrains of the objective zone plate, we show here that it is possible to overcome this through close coupling with high-level theoretical modelling. Taking the example of isolated bundles of hydrothermally prepared sodium titanate nanotubes ((Na,H)TiNTs) we are able to unravel the complex nanoscale structure from the NEXAFS-TXM data using multichannel multiple-scattering calculations, to the extent of being able to associate specific spectral features in the O K-edge and Ti L-edge with oxygen atoms in distinct sites within the lattice. These can even be distinguished from the contribution of different hydroxyl groups to the electronic structure of the (Na,H)TiNTs. PMID:23213642

  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. Extended X-ray absorption fine structure investigation of Sn local environment in strained and relaxed epitaxial Ge1-xSnx films

    NASA Astrophysics Data System (ADS)

    Gencarelli, F.; Grandjean, D.; Shimura, Y.; Vincent, B.; Banerjee, D.; Vantomme, A.; Vandervorst, W.; Loo, R.; Heyns, M.; Temst, K.

    2015-03-01

    We present an extended X-ray absorption fine structure investigation of the local environment of Sn atoms in strained and relaxed Ge1-xSnx layers with different compositions. We show that the preferred configuration for the incorporation of Sn atoms in these Ge1-xSnx layers is that of a α-Sn defect, with each Sn atom covalently bonded to four Ge atoms in a classic tetrahedral configuration. Sn interstitials, Sn-split vacancy complexes, or Sn dimers, if present at all, are not expected to involve more than 2.5% of the total Sn atoms. This finding, along with a relative increase of Sn atoms in the second atomic shell around a central Sn atom in Ge1-xSnx layers with increasing Sn concentrations, suggests that the investigated materials are homogeneous random substitutional alloys. Within the accuracy of the measurements, the degree of strain relaxation of the Ge1-xSnx layers does not have a significant impact on the local atomic surrounding of the Sn atoms. Finally, the calculated topological rigidity parameter a** = 0.69 ± 0.29 indicates that the strain due to alloying in Ge1-xSnx is accommodated via bond stretching and bond bending, with a slight predominance of the latter, in agreement with ab initio calculations reported in literature.

  20. 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

  1. Silver speciation in liver of marine mammals by synchrotron X-ray absorption fine structure and X-ray fluorescence spectroscopies.

    PubMed

    Nakazawa, Emiko; Ikemoto, Tokutaka; Hokura, Akiko; Terada, Yasuko; Kunito, Takashi; Yamamoto, Takahito; Yamada, Tadasu K; Rosas, Fernando C W; Fillmann, Gilberto; Tanabe, Shinsuke; Nakai, Izumi

    2011-06-01

    The chemical form of Ag in the livers of five species of marine mammals was examined using X-ray absorption fine structure (XAFS) and X-ray fluorescence (XRF) spectroscopies. The XAFS analysis suggested that Ag(2)Se was present in the livers of the Franciscana dolphin (Pontoporia blainvillei), Dall's porpoise (Phocoenoides dalli), and Baird's beaked whale (Berardius bairdii), whereas Ag(2)S was present in the livers of the striped dolphin (Stenella coeruleoalba) and pygmy killer whale (Feresa attenuata). XRF spectroscopy results revealed that the distribution patterns of Ag and Se in a thin section of the liver of the Franciscana dolphin were the same; this also implied that Ag was associated with Se in the liver. Thus, the interaction of Ag with Se or S may offer significant protection against the toxicity of Ag in marine mammals. The formation of either Ag(2)Se or Ag(2)S might depend on the Hg levels in the liver. Ag(2)Se was observed in liver samples with relatively high Ag/Hg ratio, whereas liver samples with low Ag/Hg ratio contained Ag(2)S. PMID:21491037

  2. Probing the Ordering of Semiconducting Fluorene-Thiophene Copolymer Surfaces on Rubbed Polyimide Substrates by Near-Edge X-ray Absorption Fine Structure

    SciTech Connect

    Pattison,L.; Hexemer, A.; Kramer, E.; Krishnan, S.; Petroff, P.; Fischer, D.

    2006-01-01

    The temperature-dependent alignment of semiconducting liquid crystalline fluorene-thiophene copolymer (F8T2) thin film surfaces was investigated using the near-edge X-ray absorption fine structure (NEXAFS) technique. Partial electron yield spectra were recorded over a range of temperatures in order to observe directly the surface orientation as the polymer is heated and cooled through glass, crystal, and liquid crystal phases. In addition, samples annealed under varying processing conditions and quenched to room temperature were analyzed. The NEXAFS data show that (a) in thin F8T2 films at all temperatures the polymer backbone lies in the plane of the substrate, (b) the fluorene and thiophene rings are rotated randomly about the molecular axis, (c) orientation of the polymer backbone can be controlled using a rubbed polyimide alignment layer as a template for liquid crystal orientation, and (d) under proper annealing conditions there is strong temperature-dependent alignment of the copolymer main-chain axis to the rubbing direction which extends from the polyimide/F8T2 interface all the way to the F8T2 surface. The surface alignment does not disappear after annealing at temperatures {approx}30 K above the bulk nematic to isotropic transition.

  3. 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.

  4. Adsorption of cadmium to Bacillus subtilis bacterial cell walls: a pH-dependent X-ray absorption fine structure spectroscopy study

    NASA Astrophysics Data System (ADS)

    Boyanov, M. I.; Kelly, S. D.; Kemner, K. M.; Bunker, B. A.; Fein, J. B.; Fowle, D. A.

    2003-09-01

    The local atomic environment of Cd bound to the cell wall of the gram-positive bacterium Bacillus subtilis was determined by X-ray absorption fine structure (XAFS) spectroscopy. Samples were prepared at six pH values in the range 3.4 to 7.8, and the bacterial functional groups responsible for the adsorption were identified under each condition. Under the experimental Cd and bacterial concentrations, the spectroscopy results indicate that Cd binds predominantly to phosphoryl ligands below pH 4.4, whereas at higher pH, adsorption to carboxyl groups becomes increasingly important. At pH 7.8, we observe the activation of an additional binding site, which we tentatively ascribe to a phosphoryl site with smaller Cd-P distance than the one that is active at lower pH conditions. XAFS spectra of several cadmium acetate, phosphate, and perchlorate solutions were measured and used as standards for fingerprinting, as well as to assess the ability of FEFF8 and FEFFIT to model carboxyl, phosphoryl, and hydration environments, respectively. The results of this XAFS study in general corroborate existing surface complexation models; however, some binding mechanism details could only be detected with the XAFS technique.

  5. Searching for variations in the fine-structure constant and the proton-to-electron mass ratio using quasar absorption lines

    NASA Astrophysics Data System (ADS)

    King, Julian A.

    2012-02-01

    (abridged) Quasar absorption lines provide a precise test of the assumed constancy of the fundamental constants of physics. We have investigated potential changes in the fine-structure constant, alpha, and the proton-to-electron mass ratio, mu. The many-multiplet method allows one to use optical fine-structure transitions to constrain (Delta alpha)/alpha at better than the 10^(-5) level. We present a new analysis of 154 quasar absorbers with 0.2 < z <3.7 in VLT/UVES spectra. From these absorbers we find 2.2 sigma evidence for angular variations in alpha under a dipole+monopole model. Combined with previous Keck/HIRES observations, we find 4.1 sigma evidence for angular (and therefore spatial) variations in alpha, with maximal increase of alpha occurring in the direction RA=(17.3 +/- 1.0) hr, dec=(-61 +/- 10) deg. Under a model where the observed effect is proportional to the lookback-time distance the significance increases to 4.2 sigma. Dipole models fitted to the VLT and Keck samples and models fitted to z<1.6 and z>1.6 sub-samples independently yield consistent estimates of the dipole direction, which suggests that the effect is not caused by telescope systematics. We consider a number of systematic effects and show that they are unable to explain the observed dipole effect. We have used spectra of the quasars Q0405-443, Q0347-383 and Q0528-250 from VLT/UVES to investigate the absorbers at z=2.595, 3.025 and 2.811 in these spectra respectively. We find that (Delta mu)/mu=(10.1 +/- 6.6) x 10^(-6), (8.2 +/- 7.5) x 10^(-6) and (-1.4 +/- 3.9) x 10^(-6) in these absorbers respectively. A second spectrum of Q0528-250 provides an additional constraint of (Delta mu)/mu=(0.2 +/- 3.2_stat +/- 1.9_sys) x 10^(-6). The weighted mean of these values yields (Delta mu)/mu=(1.7 +/- 2.4) x 10^(-6), the most precise constraint on evolution in mu at z>1.

  6. 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.

  7. Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

    SciTech Connect

    Darab, J.G.; Linehan, J.C.; Matson, D.W.; Ma, Y.

    1993-06-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ({alpha}-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.

  8. Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

    SciTech Connect

    Darab, J.G.; Linehan, J.C.; Matson, D.W. ); Ma, Y. . Dept. of Physics)

    1993-06-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ([alpha]-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.

  9. Impacts of chemical amendment and plant growth on lead speciation and enzyme activities in a shooting range soil: an x-ray absorption fine structure investigation.

    PubMed

    Hashimoto, Yohey; Matsufuru, Hiroki; Takaoka, Masaki; Tanida, Hajime; Sato, Takeshi

    2009-01-01

    In situ chemical immobilization is a practical remediation technology for metal-contaminated soils because of its capability to reduce cost and environmental impacts. We assessed the immobilization effects of poultry waste amendment and plant growth (Panicum maximum Jacq.) on Pb speciation and enzyme activities in shooting range soils. Soil contaminated with Pb was obtained from the top 20 cm of a shooting range. To evaluate Pb mobility in the soil profile treated with plants and immobilizing amendment, we used large columns filled with Pb-contaminated soil (0-20 cm, surface soils) and non-contaminated soil (20-75 cm, subsurface soils). The column study demonstrated that the amendment reduced the toxicity characteristic leaching procedure-extractable Pb in the surface soil by 90% of the Control soil. Lead mobility from the surface to subsurface profiles was significantly attenuated by plant growth but was promoted by the amendment without plant application. The extended X-ray absorption fine structure analysis revealed that the amendment reduced the proportion of PbCO(3) and Pb-organic complexes and transformed them into a more geochemically stable species of Pb(5)(PO(4))(3)Cl with 30 to 35% of the total Pb species. Applications of plant and amendment increased activities of dehydrogenase and phosphatase in the surface soil with 2.7- and 1.1-fold greater than those in Control, respectively. The use of amendments in combination with plant growth may have potential as an integrated remediation strategy that enables Pb immobilization and soil biological restoration in shooting range soils. PMID:19465717

  10. 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.

  11. Studies of cation binding in ZnCl2-regenerated bacteriorhodopsin by x-ray absorption fine structures: effects of removing water molecules and adding Cl- ions.

    PubMed Central

    Zhang, K; Song, L; Dong, J; El-Sayed, M A

    1997-01-01

    The binding of Zn2+ in Zn2+-regenerated bacteriorhodopsin (bR) was studied under various conditions by x-ray absorption fine structures (XAFS). The 0.9:1 and 2:1 Zn2+:bR samples gave similar XAFS spectra, suggesting that Zn2+ might have only one strong binding site in bR. It was found that in aqueous bR solution, Zn2+ has an average of six oxygen or nitrogen ligands. Upon drying, two ligands are lost, suggesting the existence of two weakly bound water ligands near the cation-binding site in bacteriorhodopsin. When excess Cl- ions were present before drying in the Zn2+-regenerated bR samples, it was found that two of the ligands were replaced by Cl- ions in the dried film, whereas two remain unchanged. The above observations suggest that Zn2+ has three types of ligands in regenerated bR (referred to as types I, II, and III). Type I ligands are strongly bound. These ligands cannot be removed by drying or by exchanging with Cl- ions. Type II ligands cannot be removed by drying, but can be replaced by Cl- ligands. Type III ligands are weakly bound to the metal cation and are most likely water molecules that can be removed by evaporation under vacuum or by drying with anhydrous CaSO4. The results are discussed in terms of the possible structure of the strongly binding site of Zn2+ in bR. PMID:9336205

  12. 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.

  13. 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.

  14. 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.

  15. The C 1s and N 1s near edge x-ray absorption fine structure spectra of five azabenzenes in the gas phase.

    PubMed

    Vall-llosera, G; Gao, B; Kivimäki, A; Coreno, M; Alvarez Ruiz, J; de Simone, M; Agren, H; Rachlew, E

    2008-01-28

    Near edge x-ray absorption fine structure spectra have been measured and interpreted by means of density functional theory for five different azabenzenes (pyridine, pyridazine, pyrimidine, pyrazine, and s-triazine) in the gas phase. The experimental and theoretical spectra at the N 1s and C 1s edges show a strong resonance assigned to the transition of the 1s electron in the respective N or C atoms to the lowest unoccupied molecular orbital with pi(*) symmetry. As opposed to the N 1s edge, at the C 1s edge this resonance is split due to the different environments of the core hole atom in the molecule. The shift in atomic core-level energy due to a specific chemical environment is explained with the higher electronegativity of the N atom compared to the C atom. The remaining resonances below the ionization potential (IP) are assigned to sigma or pi [corrected] orbitals with mixed valence/Rydberg [corrected] character. Upon N addition, a reduction of intensity is observed in the Rydberg region at both edges as compared to the intensity in the continuum. Above the IP one or more resonances are seen and ascribed here to transitions to sigma(*) orbitals. Calculating the experimental and theoretical Delta(pi) term values at both edges, we observe that they are almost the same within +/-1 eV as expected for isoelectronic bonded pairs. The term values of the pi(*) and sigma(*) resonances are discussed in terms of the total Z number of the atoms participating in the bond. PMID:18247958

  16. 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. PMID:25306525

  17. EXAFS Study of Semimetal-Semiconductor Transition of Bismuth Clusters

    SciTech Connect

    Ikemoto, H.; Yoshida, S.; Sogoh, J.; Miyanaga, T.

    2007-02-02

    Extended X-ray absorption fine structure (EXAFS) measurements of bismuth clusters in the temperature range of 23 -300 K have been performed using synchrotron radiation in order to investigate the size dependent phase transition. The inter-atomic distances around 3.0 A and 3.6 A are attributed to the nearest neighbors within the layer and between layers, respectively. EXAFS functions were analysed by the curve fitting method within a symmetric distribution approximation. The nearest neighbor distance of the 0.5 nm thick films is shorter than that of the 300 nm thick films at all the temperatures, which is related to the reduction of the inter-layer correlation.

  18. EXAFS studies of prostate cancer cell lines

    NASA Astrophysics Data System (ADS)

    Czapla, J.; Kwiatek, W. M.; Lekki, J.; Kisiel, A.; Steininger, R.; Goettlicher, J.

    2013-04-01

    Sulphur plays a vital role in every human organism. It is known, that sulphur-bearing compounds, such as for example cysteine and glutathione, play critical roles in development and progression of many diseases. Any alteration in sulphur's biochemistry could become a precursor of serious pathological conditions. One of such condition is prostate cancer, the most frequently diagnosed malignancy in the western world and the second leading cause of cancer related death in men. The purpose of presented studies was to examine what changes occur in the nearest chemical environment of sulphur in prostate cancer cell lines in comparison to healthy cells. The Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy was used, followed by theoretical calculations. The results of preliminary analysis is presented.

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

    SciTech Connect

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

    2009-12-01

    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

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

    SciTech Connect

    Willey, T; Willey, T

    2004-03-24

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

  1. Characterization of functionalized self-assembled monolayers and surface-attached interlocking molecules using near-edge X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Willey, Trevor Michael

    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

  2. The pH dependence of Am(III) complexation with acetate: an EXAFS study.

    PubMed

    Fröhlich, Daniel R; Skerencak-Frech, Andrej; Bauer, Nicole; Rossberg, André; Panak, Petra J

    2015-01-01

    The complexation of acetate with Am(III) is studied as a function of the pH (1-6) by extended X-ray absorption fine-structure (EXAFS) spectroscopy. The molecular structure of the Am(III)-acetate complexes (coordination numbers, oxygen and carbon distances) is determined from the raw k(3)-weighted Am LIII-edge EXAFS spectra. The results show a continuous shift of Am(III) speciation with increasing pH value towards the complexed species. Furthermore, it is verified that acetate coordinates in a bidentate coordination mode to Am(III) (Am-C distance: 2.82 ± 0.03 Å). The EXAFS data are analyzed by iterative transformation factor analysis to further verify the chemical speciation, which is calculated on the basis of thermodynamic constants, and the used structural model. The experimental results are in very good agreement with the thermodynamic modelling. PMID:25537594

  3. Local Structure of La1-xSrxCoO3 determined from EXAFS and neutron PDF studies

    SciTech Connect

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

    2009-01-26

    The combined local structure techniques, extended x-ray absorption fine structure (EXAFS) and neutron pair distribution function analysis, have been used for temperatures 4<= T<= 330 K to rule out a large Jahn-Teller (JT) distortion of the Co-O bond in La1?xSrxCoO3 for a significant fraction of Co sites (x<= 0.35), indicating few, if any, JT-active, singly occupied eg Co sites exist.

  4. Forensic Identification of Automobile Window Glass Manufacturers in Japan Based on the Refractive Index, X-ray Fluorescence, and X-ray Absorption Fine Structure.

    PubMed

    Funatsuki, Atsushi; Takaoka, Masaki; Shiota, Kenji; Kokubu, Daisuke; Suzuki, Yasuhiro

    2016-01-01

    In this study, 3 automobile window glass manufacturers were identified based on refractive index, XRF, and XAFS analyses. The samples were classified into the corresponding groups using XRF, which should be the first step for identification. Samples having different manufacturing times showed differences in the refractive index. Based on XAFS, the amplitude of the EXAFS spectra and the intensities of Fourier transforms differed between manufacturers. In the scheme for manufacturer identification proposed in this study, performing XRF and refractive index studies is the first step. The concentrations of CeO2, MgO, Al2O3, and K2O allowed us to distinguish among manufacturers. Secondly, for samples containing cerium, we discriminated between manufacturer based on the amplitude of the EXAFS spectra and the intensities of Fourier transforms. As a result, the manufacturers of the 75 samples used in this study were multilaterally identified. PMID:26860567

  5. 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

  6. The Fe-heme structure of met-indoleamine 2,3-dioxygenase-2 determined by X-ray absorption fine structure

    SciTech Connect

    Aitken, Jade B.; Austin, Christopher J.D.; Hunt, Nicholas H.; Ball, Helen J.; Lay, Peter A.

    2014-07-18

    Highlights: • IDO2 is a newly discovered tryptophan metabolising enzyme with a role in immunity. • IDO2’s active site contains a heme moiety for tryptophan binding and catabolism. • EXAFS/XANES analysis provides the first data of an IDO2 Fe-heme environment. • IDO2 Fe-heme exists as a low spin bis(His) form at 10 K; mixed spin-state at RT. - Abstract: Multiple-scattering (MS) analysis of EXAFS data on met-indoleamine 2,3-dioxygenase-2 (IDO2) and analysis of XANES have provided the first direct structural information about the axial donor ligands of the iron center for this recently discovered protein. At 10 K, it exists in a low-spin bis(His) form with Fe–N{sub p}(av) = 1.97 Å, the Fe–N{sub Im} bond lengths of 2.11 Å and 2.05 Å, which is in equilibrium with a high-spin form at room temperature. The bond distances in the low-spin form are consistent with other low-spin hemeproteins, as is the XANES spectrum, which is closer to that of the low-spin met-Lb than that of the high-spin met-Mb. The potential physiological role of this spin equilibrium is discussed.

  7. 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.

  8. Interacting Thin Film Systems Probed by Electron Induced Extended Fine Structure

    NASA Astrophysics Data System (ADS)

    Idzerda, Yves Ulrich

    In order to obtain information on the structure and dynamics of various systems including interacting thin films, it is necessary to be able to measure local structure information with surface sensitivity. Three techniques of Electron Induced Extended Fine Structure (EIEFS), the electron analog of Extended X-ray Absorption Fine Structure (EXAFS), are described, compared, and applied to thin film systems. Surface Extended Electron Loss Fine Structure (SEELFS), Extended Appearence Potential Fine Structure (EAPFS) and Auger-Monitored Extended Fine Structure (AMEFS), are all local structure probes with varying degrees of surface sensitivity, and all yield similar information. Our results show that each technique can be measured by commercially available electron optics, SEELFS and AMEFS by either a cylindrical mirror analyzer (CMA) or by low energy electron diffraction (LEED) optics and EAPFS by the LEED optics. We have addressed questions concerning proper phase shifts for the analysis, short data ranges, required use of undifferentiated data, and experimental difficulties. Investigations of carbon, oxygen, sodium, potassium, cesium, and sulfur on Cu(111) and titanium on silicon demonstrate that SEELFS is applicable to single monolayer coverages of very low Z adsorbates and thin films. Many of the theoretical difficulties surrounding the analysis of SEELFS can be circumvented by the use of standards and the ratio technique analysis developed for EXAFS. We also find in our studies of silicon, titanium, and aluminum oxide that systems with plasmon losses in the region of interest cannot be analyzed, but systems with other characteristic losses which are very sharp or very broad can be. Examination of EAPFS shows that it is more surface sensitive and is applicable to single monolayer coverages (of a broader range of elements than SEELFS) and thin films. Unfortunately, EAPFS is not applicable to single crystal systems with low electron binding energies where diffraction

  9. Structural investigations in helium implanted cubic zirconia using grazing incidence XRD and EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Kuri, G.; Degueldre, C.; Bertsch, J.; Döbeli, M.

    2010-06-01

    The crystal structure and local atom arrangements surrounding Zr atoms were determined for a helium implanted cubic stabilized zirconia (CSZ) using X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, respectively, measured at glancing angles. The implanted specimen was prepared at a helium fluence of 2 × 10 16 cm -2 using He + beams at two energies (2.54 and 2.74 MeV) passing through a 8.0 μm Al absorber foil. XRD results identified the formation of a new rhombohedral phase in the helium embedded layer, attributed to internal stress as a result of expansion of the CSZ-lattice. Zr K-edge EXAFS data suggested loss of crystallinity in the implanted lattice and disorder of the Zr atoms environment. EXAFS Fourier transforms analysis showed that the average first-shell radius of the Zr sbnd O pair in the implanted sample was slightly larger than that of the CSZ standard. Common general disorder features were explained by rhombohedral type short-range ordered clusters. The average structural parameters estimated from the EXAFS data of unimplanted and implanted CSZ are compared and discussed. Potential of EXAFS as a local probe of atomic-scale structural modifications induced by helium implantation in CSZ is demonstrated.

  10. Structural determination of fluorite-type oxygen excess uranium oxides using EXAFS spectroscopy

    SciTech Connect

    Jones, D.J.; Roziere, J.; Allen, G.C.; Tempest, P.A.

    1986-06-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been carried out at 77 K at the uranium L/sub III/ edge for UO/sub 2/, ..beta..-U/sub 3/O/sub 7/, and U/sub 4/O/sub 9/ with the aim of determining the structure of these highly defective (oxygen excess) uranium oxide phases, which are of industrial importance. Use has been made of a difference Fourier technique for U/sub 3/O/sub 7/, in which the EXAFS of a perfect lattice model is subtracted. U--O bond lengths calculated from the remaining EXAFS signal, assumed to result only from interstitial oxygens, have been used to determine the atomic coordinates of these interstitials. The analysis of EXAFS data in terms of coordination number has allowed an insight into the defect aggregate arrangement of oxygens in U/sub 3/O/sub 7/ and U/sub 4/O/sub 9/. Furthermore, EXAFS data indicate that the uranium sublattice is perturbed by the incorporation of additional oxygen atoms.

  11. Performance of a four-element Si drift detector for X-ray absorption fine-structure spectroscopy: resolution, maximum count rate, and dead-time correction with incorporation into the ATHENA data analysis software

    SciTech Connect

    Woicik, J.C.; Newburgh, W.; Ravel, B.; Fischer, D.A.

    2010-03-09

    The performance of a four-element Si drift detector for energy-dispersive fluorescence-yield X-ray absorption fine-structure measurements is reported, operating at the National Institute of Standards and Technology beamline X23A2 at the National Synchrotron Light Source. The detector can acquire X-ray absorption fine-structure spectra with a throughput exceeding 4 x 10{sup 5} counts per second per detector element (>1.6 x 10{sup 6} total counts per second summed over all four channels). At this count rate the resolution at 6 keV is approximately 220 eV, which adequately resolves the Mn K{sub {alpha}} and K{sup {beta}} fluorescence lines. Accurate dead-time correction is demonstrated, and it has been incorporated into the ATHENA data analysis program. To maintain counting efficiency and high signal to background, it is suggested that the incoming count rate should not exceed {approx}70% of the maximum throughput.

  12. Communication: Coordination structure of bromide ions associated with hexyltrimethylammonium cations at liquid/liquid interfaces under potentiostatic control as studied by total-reflection X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Nagatani, Hirohisa; Harada, Makoto; Tanida, Hajime; Sakae, Hiroki; Imura, Hisanori

    2014-03-01

    Total-reflection X-ray absorption fine structure (TR-XAFS) technique was applied for the first time to an interface between two immiscible electrolyte solutions under potentiostatic control. The hydration structure of bromide ions was investigated at polarized 2-octanone/water interfaces. TR-XAFS spectra at Br K-edge measured in the presence of hexyltrimethylammonium bromide (C6TAB) were slightly modified depending on the Galvani potential difference ({Δ }_o^w φ). The extended X-ray absorption fine structure analysis exposed hydration structure changes of bromide ions at the polarized interface. The coordination structure of bromide ions at the interface could be analyzed as compared with bromide ions dissolved in aqueous solution and Br--exchanged resin having quaternary ammonium groups. The results indicated that bromide ions were associated with C6TA+ at the polarized interface. The relative contribution of ion association form of bromide ions with quaternary ammonium groups was enhanced at a potential close to the ion transfer of C6TA+, where the interfacial concentration of C6TA+ is increased as a function of {Δ }_o^w φ.

  13. Vibrational properties of Ge nanocrystals determined by EXAFS

    SciTech Connect

    Araujo, L. L.; Kluth, P.; Azevedo, G. de M; Ridgway, M. C.

    2006-11-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy was applied to probe the vibrational properties of bulk crystalline Ge (c-Ge) and Ge nanocrystals (Ge NCs) of 4.4 nm mean diameter produced by ion implantation in SiO{sub 2} followed by thermal annealing. EXAFS measurements around the Ge K edge were carried out in the temperature range from 8 to 300 K at beam line 10-2 of the Stanford Synchrotron Radiation Laboratory (SSRL). Original information about thermal and static disorder, thermal expansion, and anharmonicity effects have been obtained for c-Ge and Ge NCs from temperature dependent EXAFS measurements using a correlated anharmonic Einstein model and thermodynamic perturbation theory. It was observed that the Ge NCs were stiffer (showed a stronger bond force constant) than both amorphous Ge (a-Ge) and c-Ge. Also, the values of the linear thermal expansion (thermal evolution of the mean interatomic distance) obtained for the Ge NCs were smaller than the ones obtained for c-Ge. These results were compared to the ones obtained for other nanocrystalline systems. They suggest that the increased surface to volume ratio of the nanocrystalline form and the presence of the surrounding SiO{sub 2} matrix might be responsible for the different vibrational properties of c-Ge and Ge NCs.

  14. EXAFS Study of Uranyl Complexation at Pseudomonas fluorescens Cell Surfaces

    NASA Astrophysics Data System (ADS)

    Bencheikh, R.; Bargar, J. R.; Tebo, B. M.

    2002-12-01

    Little is known about the roles of microbial biomass as a sink and source for uranium in contaminated aquifers, nor of the impact of bacterial biochemistry on uranium speciation in the subsurface. A significant role is implied by the high affinities of both Gram positive and Gram negative cells for binding uranyl (UO2{ 2+}). In the present study, Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy was used to identify membrane functional groups involved in uranyl binding to the Gram negative bacterium Pseudomonas fluorescens from pH 3 to pH 8. Throughout this pH-range, EXAFS spectra can be described primarily in terms of coordination of carboxylic groups to uranyl. U-C distances characteristic of 4-, 5- and 8- membered rings were observed, as well as the possibility of phosphato groups. Both shell-by-shell fits and principle component analyses indicate that the functional groups involved in binding of uranyl to the cell surface do not vary systematically across the pH range investigated. This result contrasts with EXAFS results of uranyl sorbed to Gram positive bacteria, and suggests an important role for long-chain carboxylate-terminated membrane functional groups in binding uranyl.

  15. The electronic structure of Fe2+ in reaction centers from Rhodopseudomonas sphaeroides. II. Extended x-ray fine structure studies.

    PubMed Central

    Eisenberger, P; Okamura, M Y; Feher, G

    1982-01-01

    Extended x-ray absorption fine structure (EXAFS) studies were performed on reaction centers (RC) of the photosynthetic bacterium Rhodopseudomonas sphaeroides R-26. RC containing two, one, and no quinones (2Q, 1Q, 0Q) samples were studied. The average ligand distance of the first coordination shell was determined to be 2.10 +/- 0.02 A with a more distant shell at 4.14 +/- 0.05 A. The Fe2+ site in RC was found to have a very large structural disorder parameter, from which a spread in ligand distance per iron site of approximately +/- 0.1 A was deduced. The most likely coordination number of the first shell is six, with a mixture of oxygens and nitrogens as ligands. The edge absorption results are consistent with the Fe2+ being in distorted octahedral environment. The EXAFS spectra of the 2Q and 1Q samples with and without O-phenanthroline were found to be the same. This indicates that either the secondary quinone and o-phenanthroline do not bind to Fe2+ or that they replace an equivalent ligand. The 0Q sample showed a 12% decrease in the EXAFS amplitude, which was restored upon addition of o-phenanthroline. These results can be explained by either a loss of a ligand or a severe conformational change when the primary quinone was removed. PMID:6977381

  16. 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.

  17. Commissioning and first results of scanning type EXAFS beamline (BL-09) at INDUS-2 synchrotron source

    SciTech Connect

    Poswal, A. K. Agrawal, A. Yadav, A. K. Nayak, C. Basu, S. Bhattachryya, D.; Jha, S. N.; Sahoo, N. K.; Kane, S. R.; Garg, C. K.

    2014-04-24

    An Energy Scanning X-ray Absorption Fine Structure spectroscopy beamline has recently been installed and commissioned at BL-09 bending magnet port of INDUS-2 synchrotron source, Indore. The beamline uses an UHV compatible fixed exit double crystal monochromator (DCM) with two Si (111) crystals. Two grazing incidence cylindrical mirrors are also used in this beamline; the pre-mirror is used as a collimating mirror while the post mirror is used for vertical focusing and higher harmonic rejection. In this beamline it is possible to carry out EXAFS measurements both in transmission and fluorescence mode on various types of samples, using Ionization chamber detectors and solid state drift detector respectively. In this paper, results from first experiments of the Energy Scanning EXAFS beamline are presented.

  18. Structural evolution of Ga-Ge-Te glasses by combined EXAFS and XPS analysis

    SciTech Connect

    Golovchak, R.; Calvez, L.; Bureau, B.; Jain, H.

    2013-08-07

    The structural evolution of Ga{sub x}Ge{sub y}Te{sub 100−x−y} glasses in the vicinity of GeTe{sub 4}-GaTe{sub 3} pseudo-binary tie-line is determined with high-resolution X-ray photoelectron (XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopies. The analysis of XPS data is complicated by similar electronegativity values for the constituent chemical elements, but then the interpretation is facilitated by information from complementary EXAFS analysis of the structure around each element independently. The results show 4/4/2 coordination for Ga/Ge/Te atoms and absence of Ga(Ge)-Ge(Ga) bonds or extended Te clusters in significant concentrations within the whole range of studied composition. The observed structural features correlate well with the measured basic physical properties of Ga-containing germanium telluride glasses.

  19. New fine structure cooling rate

    NASA Technical Reports Server (NTRS)

    Hoegy, W. R.

    1976-01-01

    One of the dominant electron cooling processes in the ionosphere is caused by electron impact induced fine structure transitions among the ground state levels of atomic oxygen. This fine structure cooling rate is based on theoretical cross sections. Recent advances in the numerical cross section determinations to include polarization effects and more accurate representations of the atomic target result in new lower values. These cross sections are employed in this paper to derive a new fine structure cooling rate which is between 40% and 60% of the currently used rate. A new generalized formula is presented for the cooling rate (from which the fine structure cooling rate is derived), valid for arbitrary mass and temperature difference of the colliding particles and arbitrary inelastic energy difference.

  20. Experimental study of germanium adsorption on goethite and germanium coprecipitation with iron hydroxide: X-ray absorption fine structure and macroscopic characterization

    NASA Astrophysics Data System (ADS)

    Pokrovsky, O. S.; Pokrovski, G. S.; Schott, J.; Galy, A.

    2006-07-01

    Adsorption of germanium on goethite was studied at 25 °C in batch reactors as a function of pH (1-12), germanium concentration in solution (10 -7 to 0.002 M) and solid/solution ratio (1.8-17 g/L). The maximal surface site density determined via Ge adsorption experiments at pH from 6 to 10 is equal to 2.5 ± 0.1 μmol/m 2. The percentage of adsorbed Ge increases with pH at pH < 9, reaches a maximum at pH ˜ 9 and slightly decreases when pH is further increased to 11. These results allowed generation of a 2-p K Surface Complexation Model (SCM) which implies a constant capacitance of the electric double layer and postulates the presence of two Ge complexes, >FeO-Ge(OH)30 and >FeO-GeO(OH)2-, at the goethite-solution interface. Coprecipitation of Ge with iron oxy(hydr)oxides formed during Fe(II) oxidation by atmospheric oxygen or by Fe(III) hydrolysis in neutral solutions led to high Ge incorporations in solid with maximal Ge/Fe molar ratio close to 0.5. The molar Ge/Fe ratio in precipitated solid is proportional to that in the initial solution according to the equation (Ge/Fe) solid = k × (Ge/Fe) solution with 0.7 ⩽ k ⩽ 1.0. The structure of adsorbed and coprecipitated Ge complexes was further characterized using XAFS spectroscopy. In agreement with previous data on oxyanions adsorption on goethite, bi-dentate bi-nuclear surface complexes composed of tetrahedrally coordinated Ge attached to the corners of two adjacent Fe octahedra represent the dominant contribution to the EXAFS signal. Coprecipitated samples with Ge/Fe molar ratios >0.1, and samples not aged in solution (<1 day) having intermediate Ge/Fe ratios (0.01-0.1) show 4 ± 0.3 oxygen atoms at 1.76 ± 0.01 Å around Ge. Samples less concentrated in Ge (0.001 < Ge/Fe < 0.10) and aged longer times in solution (up to 280 days) exhibit a splitting of the first atomic shell with Ge in both tetrahedral ( R = 1.77 ± 0.02 Å) and octahedral ( R = 1.92 ± 0.03 Å) coordination with oxygen. In these samples

  1. MULTI ELEMENT SI SENSOR WITH READOUT ASIC FOR EXAFS SPECTROSCOPY.

    SciTech Connect

    DE GERONIMO,G.; O CONNOR,P.; BEUTTENMULLER,R.H.; LI,Z.; KUCZEWSKI,A.J.; SIDDONS,D.P.

    2002-09-09

    Extended X-ray Absorption Fine Structure (EXAFS) experiments impose stringent requirements on a detection system, due to the need for processing ionizing events at a high rate, typically above of 10Mcps/cm{sup 2}, and with a high resolution, typically better than 300eV. The detection system here presented is being developed targeting these stringent requirements. It is the result of a cooperation between the Instrumentation Division and the National Synchrotron Light Source (NSLS) of the Brookhaven National Laboratory (BNL). The system is composed of a multi-element Si sensor with dedicated per pixel electronics. The combination of high rate, high resolution and moderate complexity makes this system attractive when compared to other multi-element solutions. In sections 2, 3 and 4 the sensor, the interconnect and the electronics are briefly described. Section 5 reports on the first experimental results.

  2. Vibrational Properties of Ge Nanocrystals Determined by EXAFS

    SciTech Connect

    Araujo, L. L.; Kluth, P.; Ridgway, M. C.; Azevedo, G. de M.

    2007-02-02

    The vibrational properties of Ge nanocrystals (NCs) produced by ion implantation in SiO2 followed by thermal annealing were determined from temperature dependent Extended X-Ray Absorption Fine Structure (EXAFS) spectroscopy measurements. Using a correlated anharmonic Einstein model and thermodynamic perturbation theory it was possible to extract information about thermal and static disorder, thermal expansion and anharmonicity effects for the Ge NCs. Comparison with results for bulk crystalline and amorphous Ge indicates that the Ge NCs bonds are stiffer than those of both bulk phases of Ge. Also, the values of the anharmonic linear thermal expansion and the thermal expansion coefficient obtained for the Ge NCs were considerably smaller those for bulk crystalline Ge. Similar trends are reported in the literature for other semiconductor NC systems. They suggest that the increased surface to volume ratio of nanocrystals and the presence of the surrounding SiO2 matrix might be responsible for the different vibrational properties of the nanocrystal phase.

  3. Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution.

    PubMed

    Müller, Oliver; Nachtegaal, Maarten; Just, Justus; Lützenkirchen-Hecht, Dirk; Frahm, Ronald

    2016-01-01

    The quick-EXAFS (QEXAFS) method adds time resolution to X-ray absorption spectroscopy (XAS) and allows dynamic structural changes to be followed. A completely new QEXAFS setup consisting of monochromator, detectors and data acquisition system is presented, as installed at the SuperXAS bending-magnet beamline at the Swiss Light Source (Paul Scherrer Institute, Switzerland). The monochromator uses Si(111) and Si(311) channel-cut crystals mounted on one crystal stage, and remote exchange allows an energy range from 4.0 keV to 32 keV to be covered. The spectral scan range can be electronically adjusted up to several keV to cover multiple absorption edges in one scan. The determination of the Bragg angle close to the position of the crystals allows high-accuracy measurements. Absorption spectra can be acquired with fast gridded ionization chambers at oscillation frequencies of up to 50 Hz resulting in a time resolution of 10 ms, using both scan directions of each oscillation period. The carefully developed low-noise detector system yields high-quality absorption data. The unique setup allows both state-of-the-art QEXAFS and stable step-scan operation without the need to exchange whole monochromators. The long-term stability of the Bragg angle was investigated and absorption spectra of reference materials as well as of a fast chemical reaction demonstrate the overall capabilities of the new setup. PMID:26698072

  4. Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution

    PubMed Central

    Müller, Oliver; Nachtegaal, Maarten; Just, Justus; Lützenkirchen-Hecht, Dirk; Frahm, Ronald

    2016-01-01

    The quick-EXAFS (QEXAFS) method adds time resolution to X-ray absorption spectroscopy (XAS) and allows dynamic structural changes to be followed. A completely new QEXAFS setup consisting of monochromator, detectors and data acquisition system is presented, as installed at the SuperXAS bending-magnet beamline at the Swiss Light Source (Paul Scherrer Institute, Switzerland). The monochromator uses Si(111) and Si(311) channel-cut crystals mounted on one crystal stage, and remote exchange allows an energy range from 4.0 keV to 32 keV to be covered. The spectral scan range can be electronically adjusted up to several keV to cover multiple absorption edges in one scan. The determination of the Bragg angle close to the position of the crystals allows high-accuracy measurements. Absorption spectra can be acquired with fast gridded ionization chambers at oscillation frequencies of up to 50 Hz resulting in a time resolution of 10 ms, using both scan directions of each oscillation period. The carefully developed low-noise detector system yields high-quality absorption data. The unique setup allows both state-of-the-art QEXAFS and stable step-scan operation without the need to exchange whole monochromators. The long-term stability of the Bragg angle was investigated and absorption spectra of reference materials as well as of a fast chemical reaction demonstrate the overall capabilities of the new setup. PMID:26698072

  5. EXAFS: New tool for study of battery and fuel cell materials

    NASA Technical Reports Server (NTRS)

    Mcbreen, James; Ogrady, William E.; Pandya, Kaumudi I.

    1987-01-01

    Extended X ray absorption fine structure (EXAFS) is a powerful technique for probing the local atomic structure of battery and fuel cell materials. The major advantages of EXAFS are that both the probe and the signal are X rays and the technique is element selective and applicable to all states of matter. This permits in situ studies of electrodes and determination of the structure of single components in composite electrodes, or even complete cells. EXAFS specifically probes short range order and yields coordination numbers, bond distances, and chemical identity of nearest neighbors. Thus, it is ideal for structural studies of ions in solution and the poorly crystallized materials that are often the active materials or catalysts in batteries and fuel cells. Studies on typical battery and fuel cell components are used to describe the technique and the capability of EXAFS as a structural tool in these applications. Typical experimental and data analysis procedures are outlined. The advantages and limitations of the technique are also briefly discussed.

  6. An EXAFS spectroscopic study of Am(III) complexation with lactate.

    PubMed

    Fröhlich, Daniel R; Skerencak-Frech, Andrej; Kaplan, Ugras; Koke, Carsten; Rossberg, André; Panak, Petra J

    2015-11-01

    The pH dependence (1-7) of Am(III) complexation with lactate in aqueous solution is studied using extended X-ray absorption fine-structure (EXAFS) spectroscopy. Structural data (coordination numbers, Am--O and Am--C distances) of the formed Am(III)-lactate species are determined from the raw k(3)-weighted Am LIII-edge EXAFS spectra. Between pH 1 and pH 6, Am(III) speciation shifts continuously towards complexed species with increasing pH. At higher pH, the amount of complexed species decreases due to formation of hydroxo species. The coordination numbers and distances (3.41-3.43 Å) of the coordinating carbon atoms clearly point out that lactate is bound `side-on' to Am(III) through both the carboxylic and the α-hydroxy function of lactate. The experimentally determined coordination numbers are compared with speciation calculations on the basis of tabulated thermodynamic stability constants. Both EXAFS data and thermodynamic modelling are in very good agreement. The EXAFS spectra are also analyzed by iterative transformation factor analysis to further verify the determined Am(III) speciation and the used structural model. PMID:26524312

  7. 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

  8. Atomic structure relaxation in nanocrystalline NiO studied by EXAFS spectroscopy: Role of nickel vacancies

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

    Nanocrystalline NiO samples have been studied using the Ni K-edge extended x-ray absorption fine structure (EXAFS) spectroscopy and recently developed modeling technique, combining classical molecular dynamics with ab initio multiple-scattering EXAFS calculations (MD-EXAFS). Conventional analysis of the EXAFS signals from the first two coordination shells of nickel revealed that (i) the second shell average distance R(Ni-Ni2) expands in nanocrystalline NiO compared to microcrystalline NiO, in agreement with overall unit cell volume expansion observed by x-ray diffraction; (ii) on the contrary, the first shell average distance R(Ni-O1) in nanocrystalline NiO shrinks compared to microcrystalline NiO; (iii) the thermal contribution into the mean-square relative displacement σ2 is close in both microcrystalline and nanocrystalline NiO and can be described by the Debye model; (iv) the static disorder is additionally present in nanocrystalline NiO in both the first Ni-O1 and second Ni-Ni2 shells due to nanocrystal structure relaxation. Within the MD-EXAFS method, the force-field potential models have been developed for nanosized NiO using as a criterion the agreement between the experimental and theoretical EXAFS spectra. The best solutions have been obtained for the 3D cubic-shaped nanoparticle models with nonzero Ni vacancy concentration Cvac: Cvac≈0.4-1.2% for NiO nanoparticles having the cube size of L≈3.6-4.2 nm and Cvac≈1.6-2.0% for NiO thin film composed of cubic nanograins with a size of L≈1.3-2.1 nm. Thus our results show that the Ni vacancies in nanosized NiO play important role in its atomic structure relaxation along with the size reduction effect.

  9. Line strengths, A-factors and absorption cross-sections for fine structure lines in multiplets and hyperfine structure components in lines in atomic spectrometry—a user's guide

    NASA Astrophysics Data System (ADS)

    Axner, Ove; Gustafsson, Jörgen; Omenetto, Nicolò; Winefordner, James D.

    2004-01-01

    This work summarizes and elucidates a number of fundamental concepts in atomic spectrometry regarding the 'strengths' of transitions between various energy levels and states in atoms. Although several of the expressions and rules for line strengths of transitions reported here can be found, in one way or another, in various books dealing with atomic structure, atomic spectrometry or quantum mechanics, the treatment in such books can be variously complex and difficult to follow for a non-experienced reader. In addition, detailed information about transition-specific 'strengths' of transitions used to be restricted to line strengths, whereas most experiments rather need transition-specific A-factors or transition-specific absorption cross-sections. This work therefore aims at pointing out the most important aspects of the concept of 'strengths' of transitions between various energy levels and states in atoms by presenting explicit expressions for not only relative and absolute line strengths but also oscillator strengths ( f-values), A-factors and absorption cross-sections, for transitions between fine structure levels within a multiplet as well as for hyperfine structure components within a line (i.e. between hyperfine structure levels), including their mutual relations, in a consistent and user-friendly manner. The work also recapitulates the most important summation rules for line strengths, oscillator strengths ( f-values), A-factors and absorption cross-sections for lines within multiplets and hyperfine structure components within lines. Many of the expressions are illustrated with clear and intelligible examples. For the sake of clarity and completeness, the work also comprises a short review of the nomenclature for atomic structure and transitions.

  10. Combined sulfur K-edge XANES-EXAFS study of the effect of protonation on the sulfate tetrahedron in solids and solutions.

    PubMed

    Pin, S; Huthwelker, T; Brown, M A; Vogel, F

    2013-09-01

    Sulfur K-edge X-ray absorption spectroscopy (XAS) has been used to distinguish between aqueous and solid sulfates and to investigate changes in their speciation. Data have been collected for tetrahedrally coordinated S in K2SO4 and KHSO4 solids and aqueous solutions. With a first qualitative analysis of the X-ray absorption near-edge structure (XANES) spectra, it has been observed that those for solids are much more structured and distinguishable from those of aqueous solutions. The protonation state has a strong effect on the white line of sulfates and has been assigned to the different charge delocalization in the samples, the effect of the solvating water molecules and multiple scattering effects. In the extended X-ray absorption fine structure (EXAFS) spectra, the backscattering from the first O shell dominated the EXAFS fine structure function, χ(k), but the nonlinear multiple scattering contributions occurring in the first coordination shell are significant and must be considered in the EXAFS analysis. The intensity of these contributions strongly depend on the symmetry of the system. For a distorted tetrahedron, the intensity of the multiple scattering contributions is less than that found in a regular tetrahedron. The FEFF code has been used to model the contributions of the multiple-scattering processes. The observed experimental evidence in the XAS data can be used to distinguish between sulfates in solids and liquids. This is applicable to many chemical, geochemical, and biological systems. PMID:23924171

  11. SAXS and EXAFS studies of ion beam synthesized Au nanocrystals

    NASA Astrophysics Data System (ADS)

    Kluth, P.; Johannessen, B.; Cookson, D. J.; Foran, G. J.; Ridgway, M. C.

    2006-05-01

    We have used small-angle X-ray scattering (SAXS) and extended X-ray absorption fine structure (EXAFS) spectroscopy to investigate Au nanocrystals (NCs) fabricated by high dose ion implantation into thin SiO 2 and subsequent annealing at different temperatures. Size distributions were determined from SAXS and structural parameters were extracted from EXAFS measurements, the latter analyzed as a function of NC size. Increasing implantation dose leads to an increasing average NC size and broadening of the size distribution. A significant size-dependent bond length contraction with respect to bulk material was observed. For samples annealed at 1100 °C our analysis suggests that an increased structural disorder is predominantly located at the NC surface. Post-implantation annealing at temperatures of 500 °C and 800 °C for 1 h in forming gas had no detectable influence on the NC size distribution, however, a significant influence on the structural parameters, in particular increased disorder was observed. This is potentially the result of stress induced disorder due to the different thermal expansion of the NC and matrix materials.

  12. Zn-K edge EXAFS study of human nails

    NASA Astrophysics Data System (ADS)

    Katsikini, M.; Mavromati, E.; Pinakidou, F.; Paloura, E. C.; Gioulekas, D.

    2009-11-01

    Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Zn - K edge is applied for the study of the bonding geometry of Zn in human nails. The studied nail clippings belong to healthy donors and donors who suffer from lung diseases. Fitting of the first nearest neighboring shell of Zn reveals that it is bonded with N and S, at distances that take values in the ranges 2.00-2.04 Å and 2.23-2.28Å, respectively. Zn is four - fold coordinated and the ratio of the number of sulfur and nitrogen atoms (NS/NN) in the first coordination shell ranges from 0.52 to 1. The sample that belongs to the donor who suffers from lung fibrosis, a condition that is related to keratinization of the lung tissue, is characterized by the highest number of NS/NN. Simulation, using the FEFF8 code, of the Zn - K edge EXAFS spectra with models of tetrahedrally coordinated Zn with 1 (or 2) cysteine and 3 (or 2) histidines is satisfactory.

  13. 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.

  14. Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

    2015-09-01

    Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

  15. Structural Study of Cu-Deficient Cu2(1-x)ZnSnSe4 Solar Cell Materials by X-ray Diffraction and X-ray Absorption Fine Structure

    NASA Astrophysics Data System (ADS)

    Gao, Feng; Yamazoe, Seiji; Maeda, Tsuyoshi; Wada, Takahiro

    2012-10-01

    Cu-poor Cu2(1-x)ZnSnSe4 powders were prepared from elemental powders. The crystal structure of Cu-poor Cu2(1-x)ZnSnSe4 was examined by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. Kesterite-type Cu2(1-x)ZnSnSe4 could be prepared in the range of 0≤x ≤0.0750. The lattice parameters were refined by the Rietveld analysis of X-ray diffraction data. The lattice constants a and c decreased with a decrease in the Cu/(Zn+Sn) ratio. However, there was little change in c/a value. On the other hand, the position of the Se atom (u parameters) changed considerably. The XAFS study showed that the local structure of Sn in Cu2ZnSnSe4 (CZTSe) changed with a decrease in Cu/(Zn+Sn) ratio and the local structural changes in Cu, Zn, or Se could not be clearly observed. These local structural changes around Sn are due to the disordering of Cu, Zn, and Sn atoms. The diffuse reflectance spectra showed that the band gap of Cu2ZnSnSe4 is 0.98 eV and that the band gaps do not depend on Cu/(Zn+Sn) ratio in the range of 0≤x ≤0.0750.

  16. Detection of ZnS Phases in CZTS Thin-Films by EXAFS

    SciTech Connect

    Hartman, K.; Newman, B. K.; Johnson, J. L.; Du, H.; Fernandes, P. A.; Chawla, V.; Bolin, T.; Clemens, B. M.; Da Cunha, A. F.; Teeter, G.; Scarpulla, M. A.; Buonassisi, T.

    2011-01-01

    Copper zinc tin sulfide (CZTS) is a promising Earth-abundant thin-film solar cell material; it has an appropriate band gap of {approx}1.45 eV and a high absorption coefficient. The most efficient CZTS cells tend to be slightly Zn-rich and Cu-poor. However, growing Zn-rich CZTS films can sometimes result in phase decomposition of CZTS into ZnS and Cu{sub 2}SnS{sub 3}, which is generally deleterious to solar cell performance. Cubic ZnS is difficult to detect by XRD, due to a similar diffraction pattern. We hypothesize that synchrotron-based extended X-ray absorption fine structure (EXAFS), which is sensitive to local chemical environment, may be able to determine the quantity of ZnS phase in CZTS films by detecting differences in the second-nearest neighbor shell of the Zn atoms. Films of varying stoichiometries, from Zn-rich to Cu-rich (Zn-poor) were examined using the EXAFS technique. Differences in the spectra as a function of Cu/Zn ratio are detected. Linear combination analysis suggests increasing ZnS signal as the CZTS films become more Zn-rich. We demonstrate that the sensitive technique of EXAFS could be used to quantify the amount of ZnS present and provide a guide to crystal growth of highly phase pure films.

  17. Conversion of amorphous calcium phosphate into hydroxyapatite investigated by EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Harries, J. E.; Hukins, D. W. L.; Holt, C.; Hasnain, S. S.

    1987-10-01

    Amorphous calcium phosphate (ACP) was precipitated from solution at pH 10. Some samples were allowed to transform to poorly crystalline hydroxyapatite (HAP), at this pH, for periods up to 120 h. All samples were stabilised by freeze-drying and characterised by extended X-ray absorption fine structure (EXAFS) spectroscopy as well as by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. EXAFS spectra, recorded above the K absorption edge of Ca, were interpreted using a model developed previously to explain the features of the EXAFS spectrum of fully crystalline HAP. Eight shells of atoms surrounding Ca out to 0.57 nm were required to explain the appearance of poorly crystalline HAP. In contrast, only the innermost three of these shells were required to interpret the spectrum of the initial ACP. Moreover, these three shells had almost identical radii and Debye-Waller factors as in the poorly crystalline HAP and so the process of crystallisation involves only the development of longer-range order without changing the immediate environment of Ca.

  18. Limitations on the extent of off-center displacements in TbMnO3 from EXAFS measurements

    NASA Astrophysics Data System (ADS)

    Bridges, F.; Downs, C.; O'Brien, T.; Jeong, Il-K.; Kimura, T.

    2007-09-01

    We present extended x-ray-absorption fine structure (EXAFS) data at the MnK and TbL3 edges that provide upper limits on the possible displacements of any atoms in TbMnO3 . The displacements must be less than 0.005 0.01Å for all atoms, which eliminates the possibility of moderate distortions (0.02Å) with a small c -axis component, but for which the displacements in the ab plane average to zero. Assuming the polarization arises from a displacement of the O2 atoms along the c axis, the measured polarization then leads to an O2 displacement that is at least 6×10-4Å , well below our experimental limit. Thus, a combination of the EXAFS and the measured electrical polarization indicate that the atomic displacements likely lie in the range 6×10-4 5×10-3Å .

  19. EXAFS and X-ray diffraction study of LaCoO3 across the spin-state transition

    NASA Astrophysics Data System (ADS)

    Sikolenko, V. V.; Troyanchuk, I. O.; Efimov, V. V.; Efimova, E. A.; Tiutiunnikov, S. I.; Karpinsky, D. V.; Pascarelli, S.; Zaharko, O.; Ignatov, A.; Aquilanti, D.; Selutin, A. G.; Shmakov, A. N.; Prabhakaran, D.

    2016-05-01

    A combined high-resolution Co K-edge extended x-ray absorption fine structure (EXAFS) and high-resolution X-ray powder diffraction (XRD) study has been performed to clarify the detail of anomalous behavior of temperature-dependent magnetic susceptibility curve on the LaCoO3 across the spin-state (∼120 K) transition. According to XRD analysis, the Debye-Waller factor of Co-O bond exhibit rapid growth below 20 K whereas the temperature dependence of the average Co-O bond length shows linear behavior from 10 K to 400 K. The EXAFS data show an anomalous decrease of the Co-O bond lengths with respect to those obtained by XRD. No local distortion of CoO6 octahedral as temperature increases up to 400 K has been detected.

  20. Bayes-Turchin Analysis of Overlapping L-Edges EXAFS Data of Iron

    NASA Astrophysics Data System (ADS)

    Rossner, H. H.; Schmitz, D.; Imperia, P.; Krappe, H. J.; Rehr, J. J.

    2007-02-01

    Spin polarized and spin averaged extended x-ray absorption fine structure ((M)EXAFS) data were measured at temperatures of 180 K and 296 K in the soft x-ray energy regime of the overlapping L-edges of an iron film grown on V(110). The absorption coefficients were analyzed with the Bayes-Turchin procedure. The analysis yields the correction function to the atomic-like background-absorption coefficient calculated by FEFF8 and reveals components of atomic EXAFS oscillations. The EXAFS Debye-Waller (DW) parameters were determined. Their split into a thermal and a structural contribution was not possible without theoretical input since the two temperatures in this experiment were not sufficiently far apart from each other and the k range of the data was too small. The a priori values of the thermal contribution to the DW parameters were therefore derived from a force-field model with two spring constants. They were adjusted to DW parameters calculated from Born-von Karman force constants which had been obtained from inelastic neutron scattering. Those two spring constants also nicely reproduce the unprojected vibrational density of states deduced from phonon dispersion curves. The MEXAFS oscillations can be described by the rigid-band model and the L2- and L3-EXAFS components. A negative exchange-related energy is obtained by fitting the MEXAFS signal in the extended energy region. This is in contrast to the predictions of the Hedin-Lundquist functional and the Dirac-Hara functional used in the FEFF8 code.

  1. Relationship between the adsorption species of cesium and radiocesium interception potential in soils and minerals: an EXAFS study.

    PubMed

    Fan, Qiaohui; Yamaguchi, Noriko; Tanaka, Masato; Tsukada, Hirofumi; Takahashi, Yoshio

    2014-12-01

    This study examined the radiocesium (RCs) interception potential (RIP), cation exchange capacity (CEC), total organic carbon (TOC) content, and adsorption species in soils and minerals by using extended X-ray absorption fine structure (EXAFS) spectroscopy. The RIP related to Cs(+) adsorption by frayed-edge site (FES) has often been used to measure the mobility and bioavailability of RCs in the environment. This study found that the presence of organic matter (OM) can reduce RIP to a certain extent. The adsorption amount (=Q(T)) in soil was obviously correlated to RIP at a small [Cs(+)] region, whereas a linear relationship between Q(T) and CEC was observed at a large [Cs(+)] region. Both the inner-sphere (IS) and outer-sphere (OS) complexes of Cs(+) were observed through EXAFS at a molecular scale. The linear correlation between log (RIP/CEC) and the ratio of the coordination number (CN) of IS (=CNIS) and OS (=CNOS) complexes noted as CNIS/(CNIS + CNOS) suggested that the ratio of CN is very sensitive to Cs(+) adsorption species with variable RIP and CEC. The adsorption species of Cs(+) in soil was mainly dependent on the clay mineral content of soil. RIP was affected not only by FES but also by other strong adsorption sites, such as the interlayers and cavities identified as the IS complex in EXAFS analysis. Findings indicated that the EXAFS approach is a powerful and efficient tool to explore the behavior of Cs(+) in a given environment. PMID:25201086

  2. REDOX state analysis of platinoid elements in simulated high-level radioactive waste glass by synchrotron radiation based EXAFS

    NASA Astrophysics Data System (ADS)

    Okamoto, Yoshihiro; Shiwaku, Hideaki; Nakada, Masami; Komamine, Satoshi; Ochi, Eiji; Akabori, Mitsuo

    2016-04-01

    Extended X-ray Absorption Fine Structure (EXAFS) analyses were performed to evaluate REDOX (REDuction and OXidation) state of platinoid elements in simulated high-level nuclear waste glass samples prepared under different conditions of temperature and atmosphere. At first, EXAFS functions were compared with those of standard materials such as RuO2. Then structural parameters were obtained from a curve fitting analysis. In addition, a fitting analysis used a linear combination of the two standard EXAFS functions of a given elements metal and oxide was applied to determine ratio of metal/oxide in the simulated glass. The redox state of Ru was successfully evaluated from the linear combination fitting results of EXAFS functions. The ratio of metal increased at more reducing atmosphere and at higher temperatures. Chemical form of rhodium oxide in the simulated glass samples was RhO2 unlike expected Rh2O3. It can be estimated rhodium behaves according with ruthenium when the chemical form is oxide.

  3. Thin Film Structure of Tetraceno[2,3-B]thiophene Characterized By Grazing Incidence X-Ray Scattering And Near-Edge X-Ray Absorption Fine Structure Analysis

    SciTech Connect

    Yuan, Q.; Mannsfeld, S.C.B.; Tang, M.L.; Toney, M.F.; Luening, J.; Bao, Z.A.; /Stanford U., Chem. Eng. /SLAC, SSRL

    2009-05-11

    Understanding the structure-property relationship for organic semiconductors is crucial in rational molecular design and organic thin film process control. Charge carrier transport in organic field-effect transistors predominantly occurs in a few semiconductor layers close to the interface in contact with the dielectric layer, and the transport properties depend sensitively on the precise molecular packing. Therefore, a better understanding of the impact of molecular packing and thin film morphology in the first few monolayers above the dielectric layer on charge transport is needed to improve the transistor performance. In this Article, we show that the detailed molecular packing in thin organic semiconductor films can be solved through a combination of grazing incidence X-ray diffraction (GIXD), near-edge X-ray absorption spectra fine structure (NEXAFS) spectroscopy, energy minimization packing calculations, and structure refinement of the diffraction data. We solve the thin film structure for 2 and 20 nm thick films of tetraceno[2,3-b]thiophene and detect only a single phase for these thicknesses. The GIXD yields accurate unit cell dimensions, while the precise molecular arrangement in the unit cell was found from the energy minimization and structure refinement; the NEXAFS yields a consistent molecular tilt. For the 20 nm film, the unit cell is triclinic with a = 5.96 A, b = 7.71 A, c = 15.16 A, alpha = 97.30 degrees, beta = 95.63 degrees, gamma = 90 degrees; there are two molecules per unit cell with herringbone packing (49-59 degree angle) and tilted about 7 degrees from the substrate normal. The thin film structure is significantly different from the bulk single-crystal structure, indicating the importance of characterizing thin film to correlate with thin film device performance. The results are compared to the corresponding data for the chemically similar and widely used pentacene. Possible effects of the observed thin film structure and morphology on

  4. Binding of Iron(III) to Organic Soils: Exafs Spectroscopy And Chemical Equilibrium Modeling

    SciTech Connect

    Gustafsson, J.P.; Persson, I.; Kleja, D.B.; Schaik, J.W.J.van

    2007-07-09

    The complexation of iron(III) to soil organic matter is important for the binding of trace metals in natural environments because of competition effects. In this study, we used extended X-ray absorption fine structure (EXAFS) spectroscopy to characterize the binding mode for iron(III) in two soil samples from organic mor layers, one of which was also treated with iron(III). In most cases the EXAFS spectra had three significant contributions, inner-core Fe-O/N interactions at about 2.02(2) angstroms, Fe-C interactions in the second scattering shell at 3.00(4) angstroms, and a mean Fe-Fe distance at 3.37(3) angstroms. One untreated sample showed features typical for iron (hydr)oxides; however, after treatment of iron(III) the EXAFS spectrum was dominated by organically complexed iron. The presence of a Fe-Fe distance in all samples showed that the major part of the organically complexed iron was hydrolyzed, most likely in a mixture of complexes with an inner core of (O{sub 5}Fe){sub 2}O and (O{sub 5}Fe){sub 3}O. These results were used to constrain a model for metal-humic complexation, the Stockholm Humic Model (SHM). The model was able to describe iron(III) binding very well at low pH considering only one dimeric iron(III)-humic complex. The competition effect on trace metals was also well described.

  5. Towards advanced structural analysis of iron oxide clusters on the surface of γ-Al2O3 using EXAFS

    NASA Astrophysics Data System (ADS)

    Boubnov, Alexey; Roppertz, Andreas; Kundrat, Matthew D.; Mangold, Stefan; Reznik, Boris; Jacob, Christoph R.; Kureti, Sven; Grunwaldt, Jan-Dierk

    2016-11-01

    Iron oxide centres are structurally investigated in 0.1% Fe/γ-Al2O3, which is known as highly active catalyst, for instance in the oxidation of CO. The sample was characterised by using X-ray absorption spectroscopy (XAS) in terms of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), Mössbauer spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). These analyses evidenced high dispersion of the iron oxide entities without significant presence of bulk-like aggregates associated with the low Fe content of the catalyst. A library of structural models of Al2O3-supported surface Fe was created as input for EXAFS fitting. Additionally, several model structures of Fe substituting Al ions in bulk γ-Al2O3 were created with optimised geometry based on density-functional theory (DFT) calculations. From EXAFS refinement of the best 8 out of 24 models, it was found that the trivalent Fe ions are coordinated by 4-5 oxygen atoms and are located on octahedral lattice sites of the exposed surfaces of γ-Al2O3. These iron oxide species exist mainly as a mixture of monomeric and binuclear species and due to the low concentration represent suitable model systems as alternative to single crystal systems for structure-function relationships.

  6. EXAFS and XANES analysis of oxides at the nanoscale

    PubMed Central

    Kuzmin, Alexei; Chaboy, Jesús

    2014-01-01

    Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.). As a consequence, a critical reexamination of the available local-structure characterization methods is needed. This work discusses the real possibilities and limits of X-ray absorption spectroscopy (XAS) analysis at the nanoscale. To this end, the present state of the art for the interpretation of extended X-ray absorption fine structure (EXAFS) is described, including an advanced approach based on the use of classical molecular dynamics and its application to nickel oxide nanoparticles. The limits and possibilities of X-ray absorption near-edge spectroscopy (XANES) to determine several effects associated with the nanocrystalline nature of materials are discussed in connection with the development of ZnO-based dilute magnetic semiconductors (DMSs) and iron oxide nanoparticles. PMID:25485137

  7. Fine structure of plasmaspheric hiss

    NASA Astrophysics Data System (ADS)

    Summers, Danny; Omura, Yoshiharu; Nakamura, Satoko; Kletzing, Craig A.

    2014-11-01

    Plasmaspheric hiss has been widely regarded as a broadband, structureless, incoherent emission. In this study, by examining burst-mode vector waveform data from the Electric and Magnetic Field Instrument Suite and Integrated Science instrument on the Van Allen Probes mission, we show that plasmaspheric hiss is a coherent emission with complex fine structure. Specifically, plasmaspheric hiss appears as discrete rising tone and falling tone elements. Our study comprises the analysis of two 1 h samples within which a total of eight 1 s samples were analyzed. By means of waveform analysis on two samples, we identify typical amplitudes, phase profiles, and sweep rates of the rising and falling tone elements. The exciting new observations reported here can be expected to fuel a reexamination of the properties of plasmaspheric hiss, including a further reanalysis of the generation mechanism for hiss.

  8. THE STATE OF MANGANESE IN THE PHOTOSYNTHETIC APPARATUS. I. EXAFS STUDIES ON CHLOROPLASTS AND di-u-oxo BRIDGED di-MANGANESE MODEL COMPOUNDS

    SciTech Connect

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

    1980-11-01

    Extended X-ray Absorption Fine Structure (EXAFS) studies on the manganese contained in spinach chloroplasts and on certain di-u-oxo bridged manganese dimers of the form (X{sub 2}Mn)O{sub 2}(MnX{sub 2} (X=2,2'-bypyridine 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. Extensive details on the analysis are included.

  9. Fine Structure of Plasmaspheric Hiss

    NASA Astrophysics Data System (ADS)

    Summers, D.; Omura, Y.; Nakamura, S.; Kletzing, C.

    2014-12-01

    Plasmaspheric hiss plays a key role in controlling the structure and dynamics of Earth's radiation belts.The quiet time slot region between the inner and outer belts can be explained as a steady-state balance between earthward radial diffusion and pitch-angle scattering loss of energetic electrons to the atmosphere induced by plasmaspheric hiss. Plasmaspheric hiss can also induce gradual precipitation loss of MeV electrons from the outer radiation belt. Plasmaspheric hiss has been widely regarded as a broadband,structureless,incoherent emission. Here, by examining burst-mode vector waveform data from the EMFISIS instrument on the Van Allen Probes mission,we show that plasmaspheric hiss is a coherent emission with complex fine structure. Specifically, plasmaspheric hiss appears as discrete rising tone and falling tone elements. By means of waveform analysis we identify typical amplitudes,phase profiles,and sweep rates of the rising and falling tone elements. The new observations reported here can be expected to fuel a re-examination of the properties of plasmaspheric hiss, including a further re-analysis of the generation mechanism for hiss.

  10. Gadolinium acetylacetonate tetraphenyl monoporphyrinate complex and some of its derivatives: EXAFS study and molecular dynamics simulation.

    PubMed

    Agondanou, J H; Nicolis, I; Curis, E; Purans, J; Spyroulias, G A; Coutsolelos, A G; Bénazeth, S

    2007-08-20

    Many attempts to obtain single crystals appropriate for X-ray diffraction analysis of the Ln(tpp)(acac) derivatives (where Ln = Gd or Sm, tpp = tetraphenylporphyrin and acac = acetylacetonate) have failed so far. A suitable way to get structural parameters for these monoporphyrinates is to use extended X-ray absorption fine structure (EXAFS) spectroscopy. We recorded spectra of the monoporphyrins, Ln(tpp)(acac) and Gd(tpyp)(acac) (where tpyp = tetrapyridylporphyrin), and the bisporphyrin GdH(tpyp)2 in the solid state. We particularly focused our structural analysis on Gd(tpp)(acac), applying both molecular modeling and EXAFS, which allowed us to get accurate results about the local environment of the central atom. The Gd3+ ion of the complex at room temperature was found to be bonded to four monoporphyrin nitrogen atoms at an average distance R(Gd-N(av)) = 2.48 A and to three or four oxygen atoms at R(Gd-O(ac,w)) = 2.38 A from an acetylacetonato anion and a water molecule. The presence of the second water molecule in the coordination sphere was barely discernible by EXAFS analysis. Molecular modeling has provided further information about the coordination core geometry of the Gd(tpp)(acac) monoporphyrinate, including a bishydrated coordination sphere. Also, it has enabled the construction of a 3D structural model on which multiple scattering analyses were attempted. Monte Carlo simulation was used to validate the adjustments. EXAFS spectra analysis was carried out on the derivatives, displaying slight distortions in the lanthanide central-atom coordination geometry. PMID:17658869

  11. EXAFS Studies and Microwave Magnetic Properties of FeGaB Thin Films and FeCuZr Ball-Milled Alloys

    NASA Astrophysics Data System (ADS)

    Gao, Jinsheng

    X-ray absorption fine structure (XAFS) is a spectroscopic technique which can investigate the physical and chemical structure of materials at the atomic scale. X-rays are applied in this technique to be near and above the binding energy of a particular core electronic level of a particular atomic species. Over the last decades, XAFS has emerged as a highly informative probe of the local structure around selected atomic species in solids, liquids, and molecular gases. It offers both element specificity and local structure sensitivity. Foremost among its strengths are its ability to probe the local atomic environments of different elements in the sample by selecting the corresponding incident X-ray energy. In the first part of this thesis, FeGaB alloys, which are of value as soft magnetic materials having relatively large magnetostriction coefficient, were fabricated in which varying amounts of boron were added to the host FeGa alloy to investigate its impact upon local atomic structure and magnetic and microwave properties. The impact of B upon the local atomic structure in FeGaB films were investigated by extended X-ray absorption fine structure (EXAFS) analysis. EXAFS fitting results revealed a contraction of lattice parameters with the introduction of B. The Debye-Waller factor determined from EXAFS fitting gradually increases as a function of boron addition and abruptly increases during the structural evolution from crystalline to amorphous. Upon the onset of this transition the static and microwave magnetic properties became exceptionally softer, with values of coercivity and ferromagnetic linewidth reducing dramatically. In the second part of this thesis, metastable alloys of the composition FeCuZr were synthesized by high energy ball milling and measured by EXAFS . The fitting results demonstrate that nanocrystalline or amorphous alloys have been obtained depending on the Zr content.

  12. A reinvestigation of EXAFS and EPR spectroscopic measurements of chromium(VI) reduction by coir pith.

    PubMed

    Suksabye, Parinda; Worasith, Niramon; Thiravetyan, Paitip; Nakajima, Akira; Goodman, Bernard A

    2010-08-15

    New measurements using extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) techniques are consistent with Cr in the Cr(III) oxidation state as the main product from the adsorption of Cr(VI) on coir pith. These confirm the previous X-ray measurements, but differ from the results of previous EPR studies, which indicated that Cr(V) was the main form of Cr. The reason for this discrepancy is the presence of a broad signal from Cr(III) in an unsymmetrical environment that was missed previously; the Cr(V) component is in fact only a minor reaction product. As a result of this problem with spectral acquisition and interpretation, some simple recommendations are presented for conducting EPR investigations on natural systems. PMID:20452728

  13. Investigation on species distribution and EXAFS structure of aqueous rubidium pentaborate solutions

    NASA Astrophysics Data System (ADS)

    Miao, J. T.; Fang, C. H.; Fang, Y.; Zhu, F. Y.; Liu, H. Y.; Zhou, Y. Q.; Ge, H. W.; Sun, P. C.; Zhao, X. C.

    2016-04-01

    Based on the measured pH data and reported equilibrium constants, the main polyborate species formation existing in solution was investigated using the Newton iteration method at 298 and 333 K, and checked by the method of 11B nuclear magnetic resonance (NMR) spectroscopy. The neighboring structure of rubidium ion was studied at room temperature, which the structural parameters, including the coordination number, interatomic distance of Rb-O and Debye-Waller factor, were determined by the synchrotron radiation extended X-ray absorption fine structure (EXAFS). The results show that the average interatomic distance of Rb-O is 2.93 ± 0.004 Å and coordination number is 7.7 ± 0.9 in the first hydration shell around rubidium ion.

  14. Unveiling the complex network of interactions in Ionic Liquids: a combined EXAFS and Molecular Dynamics approach

    NASA Astrophysics Data System (ADS)

    Serva, A.; Migliorati, V.; Lapi, A.; D'Angelo, P.

    2016-05-01

    The structural properties of geminal dicationic ionic liquids ([Cn (mim)2]Br2)/water mixtures have been investigated by means of extended X-ray absorption fine structure (EXAFS) spectroscopy and Molecular Dynamics (MD) simulations. This synergic approach allowed us to assess the reliability of the MD results and to provide accurate structural information about the first coordination shell of the Br- ion. We found that the local environment around the anion changes as a function of the water concentration, while it is the same independently from the length of the bridge-alkyl chain. Moreover, as regards the long-range structural organization, no tail-tail aggregation occurs with increasing alkyl chain length.

  15. EXAFS and XANES analysis of plutonium and cerium edges from titanate ceramics for fissile materials disposal.

    SciTech Connect

    Fortner, J. A.; Kropf, A. J.; Bakel, A. J.; Hash, M. C.; Aase, S. B.; Buck, E. C.; Chamerlain, D. B.

    1999-11-16

    We report x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) spectra from the plutonium L{sub III} edge and XANES from the cerium L{sub II} edge in prototype titanate ceramic hosts. The titanate ceramics studied are based upon the hafnium-pyrochlore and zirconolite mineral structures and will serve as an immobilization host for surplus fissile materials, containing as much as 10 weight % fissile plutonium and 20 weight % (natural or depleted) uranium. Three ceramic formulations were studied: one employed cerium as a ''surrogate'' element, replacing both plutonium and uranium in the ceramic matrix, another formulation contained plutonium in a ''baseline'' ceramic formulation, and a third contained plutonium in a formulation representing a high-impurity plutonium stream. The cerium XANES from the surrogate ceramic clearly indicates a mixed III-IV oxidation state for the cerium. In contrast, XANES analysis of the two plutonium-bearing ceramics shows that the plutonium is present almost entirely as Pu(IV) and occupies the calcium site in the zirconolite and pyrochlore phases. The plutonium EXAFS real-space structure shows a strong second-shell peak, clearly distinct from that of PuO{sub 2}, with remarkably little difference in the plutonium crystal chemistry indicated between the baseline and high-impurity formulations.

  16. Microsecond time-resolved energy-dispersive EXAFS measurement and its application to film the thermolysis of (NH4)2[PtCl6

    NASA Astrophysics Data System (ADS)

    Kong, Qingyu; Baudelet, Francois; Han, Jun; Chagnot, Sebastien; Barthe, Laurent; Headspith, Jon; Goldsbrough, Roger; Picca, Frederic E.; Spalla, Olivier

    2012-12-01

    Microsecond (μs) time-resolved extended X-ray absorption fine structure spectroscopy (EXAFS) has been developed using an energy-dispersive EXAFS (EDE) setup equipped with a silicon Quantum Detector ULTRA. The feasibility was investigated with a prototypical thermally driven redox reaction, the thermal decomposition of (NH4)2[PtCl6]. EXAFS data were collected with snapshots every 60 μs during the course of the thermolysis reaction, then averaged for 100 times along the reaction to get better signal to noise ratio which reduces the time resolution to 6 millisecond (ms). Our results provide direct structural evidence of cis-PtCl2(NH3)2 as the intermediate, together with continuous electronic and geometric structure dynamics of the reactant, intermediate and final product during the course of the thermolysis of (NH4)2[PtCl6]. The thermal effect on EXAFS signals at high temperatures is considered in the data analysis, which is essential to follow the reaction process correctly. This method could also be applied to other reaction dynamics.

  17. Microsecond time-resolved energy-dispersive EXAFS measurement and its application to film the thermolysis of (NH4)2[PtCl6

    PubMed Central

    Kong, Qingyu; Baudelet, Francois; Han, Jun; Chagnot, Sebastien; Barthe, Laurent; Headspith, Jon; Goldsbrough, Roger; Picca, Frederic E.; Spalla, Olivier

    2012-01-01

    Microsecond (μs) time-resolved extended X-ray absorption fine structure spectroscopy (EXAFS) has been developed using an energy-dispersive EXAFS (EDE) setup equipped with a silicon Quantum Detector ULTRA. The feasibility was investigated with a prototypical thermally driven redox reaction, the thermal decomposition of (NH4)2[PtCl6]. EXAFS data were collected with snapshots every 60 μs during the course of the thermolysis reaction, then averaged for 100 times along the reaction to get better signal to noise ratio which reduces the time resolution to 6 millisecond (ms). Our results provide direct structural evidence of cis-PtCl2(NH3)2 as the intermediate, together with continuous electronic and geometric structure dynamics of the reactant, intermediate and final product during the course of the thermolysis of (NH4)2[PtCl6]. The thermal effect on EXAFS signals at high temperatures is considered in the data analysis, which is essential to follow the reaction process correctly. This method could also be applied to other reaction dynamics. PMID:23264880

  18. The Fine-Structure Constant and Wavelength Calibration

    NASA Astrophysics Data System (ADS)

    Whitmore, Jonathan

    The fine-structure constant is a fundamental constant of the universe--and widely thought to have an unchanging value. However, the past decade has witnessed a controversy unfold over the claimed detection that the fine-structure constant had a different value in the distant past. These astrophysical measurements were made with spectrographs at the world's largest optical telescopes. The spectrographs make precise measurements of the wavelength spacing of absorption lines in the metals in the gas between the quasar background source and our telescopes on Earth. The wavelength spacing gives a snapshot of the atomic physics at the time of the interaction. Whether the fine-structure constant has changed is determined by comparing the atomic physics in the distant past with the atomic physics of today. We present our contribution to the discussion by analyzing three nights data taken with the HIRES instrument (High Resolution Echelle Spectrograph) on the Keck telescope. We provide an independent measurement on the fine-structure constant from the Damped Lyman alpha system at a redshift of z =2.309 (10.8 billion years ago) quasar PHL957. We developed a new method for calibrating the wavelength scale of a quasar exposure to a much higher precision than previously achieved. In our subsequent analysis, we discovered unexpected wavelength calibration errors that has not been taken into account in the previously reported measurements. After characterizing the wavelength miscalibrations on the Keck-HIRES instrument, we obtained several nights of data from the main competing instrument, the VLT (Very Large Telescope) with UVES (Ultraviolet and Visual Echelle Spectrograph). We applied our new wavelength calibration method and uncovered similar in nature systematic errors as found on Keck-HIRES. Finally, we make a detailed Monte Carlo exploration of the effects that these miscalibrations have on making precision fine-structure constant measurements.

  19. X-ray absorption studies of yeast copper metallothionein

    SciTech Connect

    George, G.N.; Byrd, J.; Winge, D.R.

    1988-06-15

    The local structures of the metal sites in copper metallothionein from Saccharomyces cerevisiae have been investigated by x-ray absorption spectroscopy at the copper and sulfur K edges. Analysis of the EXAFS (extended x-ray absorption fine structure) data indicates that each copper is trigonally coordinated to sulfur at a distance of 2.23 A. Cu-Cu interactions at 2.7 and 3.9 A have also been tentatively identified. Sulfur K edge data are compatible with cysteinyl thiolates bridging each of the eight Cu(I) ions. The data support a model for the copper cluster in yeast metallothionein consisting of a Cu8S12 core. EXAFS data on two specifically engineered carboxyl-terminal truncated mutants reveal that the copper coordination in the mutants is similar to that observed in the wild-type protein.

  20. In situTransmission X-Ray Absorption Fine Structure Analysis of the Charge-Discharge Process in LiMn 2O 4, a Rechargeable Lithium Battery Material

    NASA Astrophysics Data System (ADS)

    Shiraishi, Youhei; Nakai, Izumi; Tsubata, Toshio; Himeda, Takuhiro; Nishikawa, Fumishige

    1997-11-01

    Thein situXAFS technique has been applied for the first time to reveal variations in the local structures of Mn atoms during the charge-discharge process of LiMn2O4, Li(Mn1.93Li0.07)O4, and Li(Mn1.85Li0.15)O4cathode materials of lithium-ion secondary batteries. It has been demonstrated that the valence state of manganese is in a linear correlation with the peak energy of the MnK-edge XANES spectrum. EXAFS analysis disclosed the coexistence of Mn3+and Mn4+in LiMn2O4, with two distinct Mn-O bond distances of 1.98 and 1.88 Å for the Mn3+-O6and Mn4+-O6octahedra, respectively. Li deintercalation leads to the oxidation of Mn3+to Mn4+and finally to MnO2, in which the Mn atom exhibits a uniform octahedral oxygen coordination, with a Mn-O distance of approximately. 1.9 Å The large variation in the local structure around the Mn atom during the charge-discharge process may be responsible for the cyclic instability of the battery material.

  1. Variation of local atomic structure due to devitrification of Ni-Zr alloy thin films probed by EXAFS measurements

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Debarati; Tiwari, Nidhi; Bhattacharyya, Dibyendu; Jha, S. N.; Basu, S.

    2016-05-01

    Thin film metallic glasses (TFMGs) exhibit properties superior to their bulk counterparts allowing them to be potentially useful in many practical applications. Apart from their technological interest, when converted to crystallized state (devitrification) TFMGs can also act as precursors for partially crystallized or fully crystallized forms. Such devitrified forms are attractive due to their novel structural and magnetic properties. The amorphous-to-crystalline transformation of co-sputtered Ni-Zr alloy thin films through annealing was studied using EXAFS (Extended X-ray Absorption Fine Structure) measurements. Investigation through an atomic probe gives a better insight into the local environment of the atomic species, rendering a deeper understanding of thermal evolution of such materials.

  2. Preparation, spectroscopy, EXAFS, electrochemistry and pharmacology of new ruthenium(II) carbonyl complexes containing ferrocenylthiosemicarbazone and triphenylphosphine/arsine

    NASA Astrophysics Data System (ADS)

    Prabhakaran, R.; Anantharaman, S.; Thilagavathi, M.; Kaveri, M. V.; Kalaivani, P.; Karvembu, R.; Dharmaraj, N.; Bertagnolli, H.; Dallemer, F.; Natarajan, K.

    2011-02-01

    A new series of new hetero-bimetallic complexes containing iron and ruthenium of the general formula [RuCl(CO)(B)(EPh 3)(L)] (where E = P or As; B = PPh 3, AsPh 3, py or pip; L = ferrocene derived monobasic bidentate thiosemicarbazone ligand) have been synthesized by the reaction between ferrocene-derived thiosemicarbazones and ruthenium(II) complexes of the type [RuHCl(CO)(B)(EPh 3) 2] (where E = P or As; B = PPh 3, AsPh 3, py or pip). The new complexes have been characterized by elemental analyses, IR, electronic, NMR ( 1H, 13C and 31P), EXAFS (extended X-ray absorption fine structure spectroscopy) and cyclic voltammetric techniques. Antibacterial activity of the new complexes has been screened against Escherichia coli, Vibrio cholerae, and Pseudomonas aeruginosa species.

  3. A XANES and EXAFS Study of Hydration and Ion Pairing in Ambient Aqueous MnBr[subscript 2] Solutions

    SciTech Connect

    Chen, Yongsheng; Fulton, John L.; Partenheimer, Walter

    2008-09-25

    Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure of Mn(II) in aqueous MnBr{sub 2} solutions at ambient conditions from very dilute to the near saturation limit. The Mn K-edge EXAFS spectra for 0.05 and 0.2 m solutions showed that there was no Br(-I) in the first shell, and that the Mn(II) was fully hydrated with six water molecules in an octahedral arrangement. In contrast, for 6 m solution, the coordination number of water was reduced to about 5, and an average of about one bromine atom was present in the first shell as a contact ion pair. The 1s {yields} 4p transition at 6545.5 eV confirmed the observation of Mn-Br contact ion pairs at high concentrations and the 1s {yields} 3d transition at 6539.5 eV showed that the first shell coordination symmetry remained octahedral even in the presence of Mn-Br ion pairs.

  4. 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.

  5. μ-EXAFS, μ-XRF, and μ-PL characterization of a multi-quantum-well electroabsorption modulated laser realized via selective area growth.

    PubMed

    Mino, Lorenzo; Gianolio, Diego; Agostini, Giovanni; Piovano, Andrea; Truccato, Marco; Agostino, Angelo; Cagliero, Stefano; Martinez-Criado, Gema; d'Acapito, Francesco; Codato, Simone; Lamberti, Carlo

    2011-04-01

    In the past few years, strong efforts have been devoted to improving the frequency of optical-fiber communications. In particular, the use of a special kind of integrated optoelectronic device called an electroabsorption modulated laser (EML) allows communication at 10 Gb s(-1) or higher over long propagation spans (up to 80 km). Such devices are realized using the selective area growth (SAG) technique and are based on a multiple quantum well (MQW) distributed-feedback laser (DFB) monolithically integrated with a MQW electroabsorption modulator (EAM). Since the variation in the chemical composition between these two structures takes place on the micrometer scale, in order to study the spatial variation of the relevant parameters of the MQW EML structures, the X-ray microbeam available at the ESRF ID22 beamline is used. The effectiveness of the SAG technique in modulating the chemical composition of the quaternary alloy is proven by a micrometer-resolved X-ray fluorescence (μ-XRF) map. Here, reported micrometer-resolved extended X-ray absorption fine structure (μ-EXAFS) spectra represent the state of the art of μ-EXAFS achievable at third-generation synchrotron radiation sources. The results are in qualitative agreement with X-ray diffraction (XRD) and micrometer-resolved photoluminescence (μ-PL) data, but a technical improvement is still crucial in order to make μ-EXAFS really quantitative on such complex heterostructures. PMID:21404439

  6. 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.

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

    NASA Astrophysics Data System (ADS)

    Gaur, A.; Shrivastava, B. D.

    2014-09-01

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

  8. Local structures around 3d metal dopants in topological insulator Bi2Se3 studied by EXAFS measurements

    NASA Astrophysics Data System (ADS)

    Liu, Zhen; Wei, Xinyuan; Wang, Jiajia; Pan, Hong; Ji, Fuhao; Xi, Fuchun; Zhang, Jing; Hu, Tiandou; Zhang, Shuo; Jiang, Zheng; Wen, Wen; Huang, Yuying; Ye, Mao; Yang, Zhongqin; Qiao, Shan

    2014-09-01

    Transition-metal-doped Bi2Se3 crystals, X0.05Bi2Se3 (X =Cr, Co, Ni, and Cu), are prepared and studied by powder x-ray diffraction and extended x-ray absorption fine structure (EXAFS) measurements to get the local structures around the dopants. Cr atoms substitute Bi atoms and Co atoms may substitute Bi atoms or form Co3Se4 (C2/m) clusters. Cu is also found taking the Bi substitutional site, which differs from the reported superconductor phase of Cu-doped Bi2Se3, suggesting the dependence of site occupancy of Cu in Bi2Se3 on the process of sample growing. For Ni0.05Bi2Se3, Ni atoms form Ni3Se4 (C2/m) clusters. The nearest neighbors of X (X =Cr, Co, and Cu) are Se atoms, and the X-Se bond lengths are extracted from EXAFS as 2.50 Å for Cr-Se, 2.40 Å for Co-Se, and 2.38 Å for Cu-Se, which show the direct evidences of dramatic structural relaxations around 3d dopants. The bond information of local structures around dopants is valuable for subsequent theoretical studies, and can hardly be obtained from other techniques.

  9. Metal incorporation in sputter-deposited MoS{sub 2} films studied by extended x-ray adsorption fine structure

    SciTech Connect

    Lince, J.R.; Hilton, M.R.; Bommannavar, A.S.

    1995-08-01

    Solid lubricant films produced by cosputtering metals with MoS{sub 2} and by forming metal/MoS{sub 2} multilayers are being planned for use in the next generation of solid lubricated devices on spacecraft, including gimbal and sensor bearings, actuators, and sliding electrical contacts. The films exhibit increased densities and wear lives compared to films without additives, but the mechanism of density enhancement is not well understood. The extended x-ray absorption fine structure (EXAFS) technique is ideal for elucidating the structure of these poorly crystalline films. We analyzed MoS{sub 2} films cosputtered with 0, 2, and 10% Ni, as well as Ni/MoS{sub 2} and Au(Pd)/MoS{sub 2} multilayer films. The results obtained at the Mo-K absorption edge showed that the metal-containing films comprised predominantly the same nanocrystalline phases present in similar films without added metals: pure MoS{sub 2} and a MoS{sub 2{minus}{ital x}}O{sub {ital x}} phase. MoS{sub 2{minus}{ital x}}O{sub {ital x}} is isostructural with MoS{sub 2}, with O atoms substituting for S atoms in the MoS{sub 2} crystal lattice. For all Ni-containing films, EXAFS data obtained at the Ni--K absorption edge showed that the Ni had not chemically reacted with the MoS{sub 2{minus}{ital x}}O{sub {ital x}} and MoS{sub 2}, but formed a disordered NiO{sub {ital x}} phase. However, Ni-cosputtered films showed decreasing Mo--Mo bond lengths in the MoS{sub 2{minus}{ital x}}O{sub {ital x}} phase with increasing Ni content, probably due to preferential oxidation of Ni compared to MoS{sub 2}. EXAFS of these Ni-cosputtered films showed only a small decrease in short-range order with Ni content, while x-ray diffraction showed a concurrent large decrease in long-range order. The results indicate that film densification in Ni-cosputtered films is caused by NiO{sub {ital x}} formation at the edges of nucleating MoS{sub 2{minus}{ital x}}O{sub {ital x}} /MoS{sub 2} crystallites.

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

    SciTech Connect

    Westre, T.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{yields}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. An X-ray absorption spectroscopy study of Cd binding onto bacterial consortia

    NASA Astrophysics Data System (ADS)

    Mishra, Bhoopesh; Boyanov, Maxim I.; Bunker, Bruce A.; Kelly, Shelly D.; Kemner, Kenneth M.; Nerenberg, Robert; Read-Daily, Brenda L.; Fein, Jeremy B.

    2009-08-01

    In this study, we use extended X-ray absorption fine structure (EXAFS) spectroscopy measurements to examine the atomic environment of Cd bound onto two experimental bacterial consortia: one grown from river water, and one grown from a manufacturing gas plant site. The experiments were conducted as a function of pH and demonstrate that the complex mixtures of bacteria, containing both Gram-positive and Gram-negative species, yield relatively simple EXAFS spectra, a result which indicates that only a limited number of functional group types contribute to Cd binding for each bacterial consortium. The EXAFS spectra indicate that the average Cd binding environment in the river water consortium varies significantly with pH, but the manufacturing gas plant consortium exhibits a Cd binding environment that remains relatively constant over the pH range examined. The EXAFS data for the river water consortium were modeled using carboxyl, phosphoryl and sulfhydryl sites. However, only carboxyl and phosphoryl sites were required to model the manufacturing gas plant consortium data under similar experimental conditions. This is the first EXAFS study to identify and quantify the relative importance of metal binding sites in bacterial consortia. Although our results indicate differences in the binding environments of the two consortia, the data suggest that there are broad similarities in the binding environments present on a wide range of bacterial cell walls.

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

    SciTech Connect

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

    1996-07-01

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

  13. Single crystalline and rare earth substituted La{sub 2}RuO{sub 5} investigated by x-ray diffraction and EXAFS spectroscopy

    SciTech Connect

    Riegg, S.; Reller, A.; Ebbinghaus, S.G.

    2012-04-15

    Single crystals of La{sub 2}RuO{sub 5} were obtained from a BaCl{sub 2} flux. The structure was determined by single crystal x-ray diffraction and compared to earlier x-ray and neutron powder diffraction results. The local structures of Ru and La/Ln in pure La{sub 2}RuO{sub 5} and the rare earth substituted La{sub 2-x}Ln{sub x}RuO{sub 5} (Ln=Pr, Nd, Sm, Gd, Dy) polycrystalline samples were determined from the extended x-ray absorption fine structures (EXAFS) of the K- and L{sub III}-edges of Ru, La, and Ln, respectively. A four shell model was developed to reduce the number of refinable parameters in the fit of the EXAFS spectra. The distribution of the Ln-ions in the layered crystal structure was determined by a comparison of the coordination spheres obtained from the Ln-edges with the unsubstituted La{sub 2}RuO{sub 5}. Interatomic distances were compared to the values obtained from the single crystal diffraction and were found to agree very well. - Graphical abstract: The crystal structure of La{sub 2-x}Ln{sub x}RuO{sub 5} (Ln=Pr, Nd, Sm, Gd, Dy) is shown viewed along the c-axis. The alternating stacking of LaRuO{sub 4} and LnO layers leads to the formation of zig-zag layers of corner sharing RuO{sub 6} octahedra. The La sites in the LaRuO{sub 4} layers are represented by light blue spheres, while the La/Ln sites in the LnO layers are colored dark blue. EXAFS investigations reveal a cationic ordering with roughly 65% of the substituting Ln ions occupying the LnO layers. Highlights: Black-Right-Pointing-Pointer Structure determination of La{sub 2}RuO{sub 5} by single crystal x-ray diffraction. Black-Right-Pointing-Pointer Ru-K EXAFS investigations of La{sub 2-x}Ln{sub x}RuO{sub 5} powder samples. Black-Right-Pointing-Pointer EXAFS of La and Ln in La{sub 2-x}Ln{sub x}RuO{sub 5} powder samples using K- and L{sub III}-absorption edges. Black-Right-Pointing-Pointer Good agreement of EXAFS results and crystal structure data despite low symmetry space group. Black

  14. EXAFS/XANES studies of plutonium-loaded sodalite/glass waste forms

    NASA Astrophysics Data System (ADS)

    Richmann, Michael K.; Reed, Donald T.; Kropf, A. Jeremy; Aase, Scott B.; Lewis, Michele A.

    2001-09-01

    A sodalite/glass ceramic waste form is being developed to immobilize highly radioactive nuclear wastes in chloride form, as part of an electrochemical cleanup process. Two types of simulated waste forms were studied: where the plutonium was alone in an LiCl/KCl matrix and where simulated fission-product elements were added representative of the electrometallurgical treatment process used to recover uranium from spent nuclear fuel also containing plutonium and a variety of fission products. Extended X-ray absorption fine structure spectroscopy (EXAFS) and X-ray absorption near-edge spectroscopy (XANES) studies were performed to determine the location, oxidation state, and particle size of the plutonium within these waste form samples. Plutonium was found to segregate as plutonium(IV) oxide with a crystallite size of at least 4.8 nm in the non-fission-element case and 1.3 nm with fission elements present. No plutonium was observed within the sodalite in the waste form made from the plutonium-loaded LiCl/KCl eutectic salt. Up to 35% of the plutonium in the waste form made from the plutonium-loaded simulated fission-product salt may be segregated with a heavy-element nearest neighbor other than plutonium or occluded internally within the sodalite lattice.

  15. Fine-structure line deficit in S 140

    NASA Astrophysics Data System (ADS)

    Ossenkopf, V.; Koumpia, E.; Okada, Y.; Mookerjea, B.; van der Tak, F. F. S.; Simon, R.; Pütz, P.; Güsten, R.

    2015-08-01

    Aims: We try to understand the gas heating and cooling in the S 140 star-forming region by spatially and spectrally resolving the distribution of the main cooling lines with GREAT/SOFIA and combining our data with existing ground-based and Herschel observations that trace the energy input and the density and temperature structure of the source. Methods: We mapped the fine-structure lines of [O i] (63 μm) and [C ii] (158 μm) and the rotational transitions of CO 13-12 and 16-15 with GREAT/SOFIA and analyzed the spatial and velocity structure to assign the emission to individual heating sources. We measure the optical depth of the [C ii] line and perform radiative transfer computations for all observed transitions. By comparing the line intensities with the far-infrared continuum we can assess the total cooling budget and measure the gas heating efficiency. Results: The main emission of fine-structure lines in S 140 stems from a 8.3'' region close to the infrared source IRS 2 that is not prominent at any other wavelength. It can be explained by a photon-dominated region (PDR) structure around the embedded cluster if we assume that the [O i] line intensity is reduced by a factor of seven owing to self-absorption. The external cloud interface forms a second PDR at an inclination of 80-85 degrees illuminated by a UV field of 60 times the standard interstellar radiation field. The main radiation source in the cloud, IRS 1, is not prominent at all in the fine-structure lines. We measure line-to-continuum cooling ratios below 10-4, i.e. values lower than in any other Galactic source, actually matching the far-IR line deficit seen in ULIRGs. In particular, the low intensity of the [C ii] line can only be modeled by an extreme excitation gradient in the gas around IRS 1. We found no explanation for why IRS 1 shows no associated fine-structure line peak, while IRS 2 does. Conclusions: The inner part of S 140 mimics the far-IR line deficit in ULIRGs thereby providing a

  16. The fine structure constant and habitable planets

    NASA Astrophysics Data System (ADS)

    Sandora, McCullen

    2016-08-01

    We use the existence of habitable planets to impose anthropic requirements on the fine structure constant, α. To this effect, we present two considerations that restrict its value to be very near the one observed. The first, that the end product of stellar fusion is iron and not one of its neighboring elements, restricts α‑1 to be 145± 50. The second, that radiogenic heat in the Earth's interior remains adequately productive for billions of years, restricts it to be 145±9. A connection with the grand unified theory window is discussed, effectively providing a route to probe ultra-high energy physics with upcoming advances in planetary science.

  17. Universal fine structure of nematic hedgehogs

    NASA Astrophysics Data System (ADS)

    Kralj, Samo; Virga, Epifanio G.

    2001-02-01

    We study in a Landau-de Gennes approach the biaxial structure of a nematic point defect with topological charge M = + 1. We aim to illuminate the role of the confining boundaries in determining the fine structure of the defect. We show that there are different regimes associated with different values of the ratio between the typical size R of the region in space occupied by the material and the biaxial correlation length ξb. For R/ξb>20 the core structure is already qualitatively universal, that is, independent of the confining geometry, while also for R/ξb>200 any quantitative difference is unlikely to be detected.

  18. EXAFS study on yttrium oxide thin films deposited by RF plasma enhanced MOCVD under the influence of varying RF self-bias

    NASA Astrophysics Data System (ADS)

    Chopade, S. S.; Nayak, C.; Bhattacharyya, D.; Jha, S. N.; Tokas, R. B.; Sahoo, N. K.; Patil, D. S.

    2014-09-01

    Extended X-ray absorption fine structure (EXAFS) and atomic force microscopy (AFM) studies are carried out on yttrium oxide (Y2O3) thin films deposited by radio frequency plasma assisted metalorganic chemical vapor deposition (MOCVD) process at different RF self-bias (-50 V to -175 V with a step of -25 V) on silicon substrates. A (2,2,6,6-tetramethyl-3,5-heptanedionate) yttrium (commonly known as Y(thd)3) precursor is used in a plasma of argon and oxygen gases at a substrate temperature of 350 °C for deposition. To gain profound understanding about influence of RF self-bias on the properties of the deposited Y2O3 thin films, the films are characterized by EXAFS and AFM measurements. From the EXAFS measurements it is observed that oxygen co-ordination is high for the film deposited at the lowest self bias (-50 V) which is due to presence of higher amount of hydroxyl group in the sample. Oxygen coordination however decrease to lower values for the films deposited at self bias of -75 V. Ysbnd O bond length decreases gradually with increase in self bias indicating reduction in hydroxyl content. However there is reduction in bond length for the film deposited at -100 V as compared to other films resulting from structural changes. The disorder factor obtained from EXAFS measurement increases for films deposited at voltages beyond -125 V due to degradation in crystallinity of the films caused by increased bombardment by incident ions. From AFM measurements, it is observed that the surface morphology of the films also change with self bias. The root mean square roughness value and the entropy factor are found to be low for films deposited at lower bias values and increase for films deposited at bias voltages above -100 V.

  19. 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

    SciTech Connect

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

    2014-07-15

    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., CaF{sub 2}, MgF{sub 2}, diamond) a 500 μm carbon filled hole is laser drilled in the center of a CaF{sub 2} 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/Al{sub 2}O{sub 3} catalyst are obtained in concentration modulation experiments where CO (or H{sub 2}) pulses are alternated to O{sub 2} 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.

  20. X-ray absorption spectroscopy elucidates the impact of structural disorder on electron mobility in amorphous zinc-tin-oxide thin films

    SciTech Connect

    Siah, Sin Cheng E-mail: buonassisi@mit.edu; Lee, Yun Seog; Buonassisi, Tonio E-mail: buonassisi@mit.edu; Lee, Sang Woon; Gordon, Roy G.; Heo, Jaeyeong; Shibata, Tomohiro; Segre, Carlo U.

    2014-06-16

    We investigate the correlation between the atomic structures of amorphous zinc-tin-oxide (a-ZTO) thin films grown by atomic layer deposition (ALD) and their electronic transport properties. We perform synchrotron-based X-ray absorption spectroscopy at the K-edges of Zn and Sn with varying [Zn]/[Sn] compositions in a-ZTO thin films. In extended X-ray absorption fine structure (EXAFS) measurements, signal attenuation from higher-order shells confirms the amorphous structure of a-ZTO thin films. Both quantitative EXAFS modeling and X-ray absorption near edge spectroscopy (XANES) reveal that structural disorder around Zn atoms increases with increasing [Sn]. Field- and Hall-effect mobilities are observed to decrease with increasing structural disorder around Zn atoms, suggesting that the degradation in electron mobility may be correlated with structural changes.

  1. What is Fine-structure Constant?

    NASA Astrophysics Data System (ADS)

    Goradia, Shantilal

    2008-10-01

    Equation in [1] α>= 1/ ln λ, linking fine-structure constant and cosmological constant derived by using S = k ln W, the total number of microstates used (W) is 10^60, justified based on a unique age tag attached to each Planck time. The OPEN and CLOSED states of the particle's mouth illustrated in [1] could be two different types of entropic repositioning pulses, say attractive and repulsive. They need not be confused as affecting the number of microstates. The characteristics of a microstate need not change the number of microstates. Mathematically then, W = N! / n!(N-n)!; where N = 10^60 and n =1; giving W = 10^60, used in [1]. There are reasons to consider each Planck time as unique microstate based on its unique age. While investigating the proposal in terms of other theories, one has to be to keep in mind that the knowledge that created one problem cannot solve another. Refer to [1] Goradia, Shantilal, ``What is Fine-structure Constant?'' http://www.arXiv.org/pdf/physics/0210040v3.

  2. Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation.

    PubMed

    Sheng, Guodong; Shen, Runpu; Dong, Huaping; Li, Yimin

    2013-06-01

    This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)2Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment. PMID:23143822

  3. Local Arsenic Structure in Shallow Implants in Si following SPER: an EXAFS and MEIS study

    SciTech Connect

    Pepponi, G.; Giubertoni, D.; Gennaro, S.; Bersani, M.; Anderle, M.; Grisenti, R.; Werner, M.; Berg, J. A. van den

    2006-11-13

    Solid phase epitaxial regrowth (SPER) has been investigated in the last few years as a possible method to form ultra shallow dopant distributions in silicon with a high level of electrical. Despite the interest for this process, few investigations were related to arsenic. Apart from the fact that it is easier to form shallow distribution with arsenic than with boron, it is also well known that at the moderate temperatures implied by SPER (500-700 deg. C) arsenic easily deactivates, probably by forming inactive clusters around point defects in silicon. In order to have a better understanding of the SPER process for arsenic implanted silicon in shallow regime, an EXAFS (extended x-ray absorption fine structure) and MEIS (medium energy ion scattering) study is reported in this paper. Silicon samples were implanted at 3 keV with arsenic ions (dose was 2E15 at/cm2 producing a 11 nm amorphous layer) and then annealed in nitrogen at temperatures ranging from 500 to 700 deg. C to have different levels of recrystallisation. From the comparison of the recrystallised fraction as measured by MEIS with the electrical activation measured by Hall effect it results evident that a full regrowth of the lattice is not reflected by a high electrical activation. The activated arsenic corresponds to less than one third of the apparently substitutional dopant for all the samples analyzed. This lack of activation was further investigated by EXAFS: the samples that according to MEIS are fully recrystallised do not reveal a clear local order around As atoms suggesting that either the As atoms are not yet completely relocated within the lattice sites or a deactivation occurred resulting in a more disordered local structure.

  4. EXAFS Study on the Reactions Between Iron And Fulvic Acid in Acid Aqueous Solutions

    SciTech Connect

    Schaik, J.W.J.van; Persson, I.; Kleja, D.B.; Gustafsson, J.P.

    2009-05-26

    Iron(III) competes with trace metals for binding sites on organic ligands. We used X-ray absorption fine structure (EXAFS) spectroscopy to determine the binding mode and oxidation state of iron in solutions initially containing only iron(III) and fulvic acid at pHs 2 and 4. EXAFS spectra were recorded at different times after sample preparation. Iron was octahedrally configured with inner-sphere Fe-O interactions at 1.98-2.10 {angstrom}, depending on the oxidation state of iron. Iron(III) formed complexes with fulvic acid within 15 min. Iron(III) was reduced to iron(II) with time at pH 2, whereas no significant reduction occurred at pH 4. No signs of dimeric/trimeric hydrolysis products were found in any of the solution samples (<0.45 {mu}m). However, the isolated precipitate of the pH 2 sample (>0.45 {mu}m) showed Fe{hor_ellipsis}Fe distances, indicating the presence of tightly packed iron(III) trimers and/or clusters of corner-sharing octahedra. It is suggested that the binding mode of iron(III) to fulvic acid at low pH may be phase-dependent: in solution mononuclear complexes predominate, whereas in the solid phase hydrolyzed polynuclear iron(III) complexes form, even at very low pH values. The observed pH dependence of iron(III) reduction was consistent with expected results based on thermodynamic calculations for model ligands.

  5. 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.

  6. Molecular conformation changes in alkylthiol ligands as a function of size in gold nanoparticles: X-ray absorption studies

    SciTech Connect

    Ramallo-Lopez, J. M.; Giovanetti, L. J.; Requejo, F. G.; Isaacs, S. R.; Shon, Y. S.; Salmeron, M.

    2006-08-15

    The bonding of hexanethiols to gold nanoparticles of 1.5, 2.0, and 3 nm was studied using x-ray absorption near-edge spectroscopy (XANES) and extended x-ray absorption fine structure (EXAFS). The XANES spectra revealed that a substantial fraction of weakly bound hexanethiol molecules are present in addition to those forming covalent bonds with Au atoms. The weakly bound molecules can be removed by washing in dichloromethane. After removal of the weakly bound molecules the S K-edge XANES reveals peaks due to S-Au and S-C bonds with intensities that change as a function of particle size. Au L{sub 3}-edge EXAFS results indicate that these changes follow the changes in coordination number of Au to the S atoms at the surface of the particles.

  7. Angle-resolved photoemission extended fine structure

    SciTech Connect

    Barton, J.J.

    1985-03-01

    Measurements of the Angle-Resolved Photoemission Extended Fine Structure (ARPEFS) from the S(1s) core level of a c(2 x 2)S/Ni(001) are analyzed to determine the spacing between the S overlayer and the first and second Ni layers. ARPEFS is a type of photoelectron diffraction measurement in which the photoelectron kinetic energy is swept typically from 100 to 600 eV. By using this wide range of intermediate energies we add high precision and theoretical simplification to the advantages of the photoelectron diffraction technique for determining surface structures. We report developments in the theory of photoelectron scattering in the intermediate energy range, measurement of the experimental photoemission spectra, their reduction to ARPEFS, and the surface structure determination from the ARPEFS by combined Fourier and multiple-scattering analyses. 202 refs., 67 figs., 2 tabs.

  8. Solar Prominence Fine Structure and Dynamics

    NASA Astrophysics Data System (ADS)

    Berger, Thomas

    2014-01-01

    We review recent observational and theoretical results on the fine structure and dynamics of solar prominences, beginning with an overview of prominence classifications, the proposal of possible new ``funnel prominence'' classification, and a discussion of the recent ``solar tornado'' findings. We then focus on quiescent prominences to review formation, down-flow dynamics, and the ``prominence bubble'' phenomena. We show new observations of the prominence bubble Rayleigh-Taylor instability triggered by a Kelvin-Helmholtz shear flow instability occurring along the bubble boundary. Finally we review recent studies on plasma composition of bubbles, emphasizing that differential emission measure (DEM) analysis offers a more quantitative analysis than photometric comparisons. In conclusion, we discuss the relation of prominences to coronal magnetic flux ropes, proposing that prominences can be understood as partially ionized condensations of plasma forming the return flow of a general magneto-thermal convection in the corona.

  9. 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.

  10. EXAFS Study of Sr sorption to Illite, Goethite, Chlorite, and Mixed Sediment under Hyperalkaline Conditions.

    PubMed

    Fuller, Adam J; Shaw, Samuel; Peacock, Caroline L; Trivedi, Divyesh; Burke, Ian T

    2016-03-29

    Strontium is an important contaminant radionuclide at many former nuclear sites. This paper investigates the effect of changing pH and ionic strength on the sorption of Sr to a range of common soil minerals. Specifically it focuses on the sorption of Sr onto illite, chlorite, goethite, and a mixed sediment. The interplay between ionic strength and pH was determined by varying the background ionic strength of the system using both NaCl (for a constant pH) and NaOH (to also vary pH). Under conditions of moderate pH, Sr sorption decreased with increasing ionic strength, due to competition between the Na and Sr atoms for the outer-sphere complexes. However, where increasing ionic strength was accompanied by increasing pH, Sr sorption remained high. This suggested that Sr was sorbed to the minerals without competition from background Na ions. Extended X-ray absorption fine structure (EXAFS) spectra confirmed that at highly alkaline pH (>12.5) Sr was forming inner-sphere complexes on the surfaces of all minerals. This specific adsorption of the Sr (as SrOH(+)) explains why it was still adsorbed to the minerals under very high ionic strength conditions and was not out-competed by Na. PMID:26938867

  11. EXAFS determinations of uranium structures: The uranyl ion complexed with tartaric, citric, and malic acids

    SciTech Connect

    Allen, P.G.; Shuh, D.K.; Bucher, J.J.

    1996-01-31

    Studies of the coordination chemistry of uranium in aqueous solutions are increasingly important for understanding the behavior of uranium in the environment. Actinide speciation information is essential for assessing and developing long-term strategies addressing problems such as migration in nuclear waste repositories or improvements in the processing of nuclear waste and materials. Relative to the latter, one method for removing uranium contamination from soils involves extraction using a chelating agent such as Tiron, or citrate. These types of extractants are quite efficient at binding the uranyl ion and thus are suitable for removing uranium contamination when it is in the hexavalent uranyl ion form. Martell et al. and Markovits et al. have published a series of articles detailing the complexation of the uranyl ion with tartaric, malic, and citric acids as a function of pH. Using the functional dependencies of potentiometric titration results, they showed that, in the pH range 2-4, the uranyl ion forms a 2:2 dimeric species, (UO{sub 2}){sub 2-} (L){sub 2}, where L = tartrate, malate, or citrate ligands. The authors have reinvestigated the solution structures of the uranyl complexes formed in these systems with the structural technique extended X-ray absorption fine-structure (EXAFS) spectroscopy.

  12. Nano-structured Pt embedded in acidic salts of heteropolymolybdate matrices: MS EXAFS study

    NASA Astrophysics Data System (ADS)

    Witkowska, Agnieszka; Dsoke, Sonia; Marassi, Roberto; Di Cicco, Andrea

    2015-12-01

    A structural study of Pt nano-catalysts is presented in the paper. The innovation in the case of the considered catalytic materials resides in the use a meso-microporous inorganic matrix of heteropolyacid salt of composition X2.5H0.5YMo12O40 where X = Rb, Cs and Y = P, Si as a catalyst support. Metallic nanoparticles were created by platinum ions reduction in a hot H2/Argon stream and were mainly located into matrix pores. As the porous structure can be controlled by the type and content of the cation used, the desired/optimal Pt nanoparticle size can be precisely defined by using a proper heteropolyacid salt composition. Multiple-scattering extended X-ray absorption fine structure (MS EXAFS) analysis was applied to obtain the relation between the matrix composition and the size of the catalyst nanoparticles. The results showed that it was only the secondary structure form of the heteropolymolybdate salt (i.e. Rb or Cs cations) that influenced the metallic nanoparticle size. The smaller the X atom ionic radii, the larger the mean diameter of the embedded Pt nanoparticles.

  13. Zinc adsorption on clays inferred from atomistic simulations and EXAFS spectroscopy.

    PubMed

    Churakov, Sergey V; Dähn, Rainer

    2012-06-01

    Clay minerals are efficient sinks for heavy metals in the geosphere. Knowing the uptake mechanism of these elements on clays can help to protect the natural environment from industrial pollution. In this study ab initio molecular dynamics (MD) calculations were applied to simulate the uptake of Zn on the edge surfaces of montmorillonite, a dioctahedral clay, and to explain the measured K-edge extended X-ray absorption fine structure (EXAFS) spectra of adsorbed Zn. These experiments were carried out using a high ionic strength Na background electrolyte that enables one to block cation exchange processes and to restrict the Zn uptake to the sorption complexation at the edge sites of clay. The analysis of the experimental data and simulation results suggest that structurally incorporated Zn preferentially substitutes for Al(III) in the trans-symmetric sites of the octahedral layer. At low loading, Zn is incorporated into the outermost trans-octahedra on (010) and (110) edges. At medium loading, Zn forms mono- and bidentate inner-sphere surface complexes attached to the octahedral layer of (010) and (110) edge sites. The maximal site density of inner-sphere sorption sites inferred from molecular simulations agrees well with site capacities of surface complexation sites derived from macroscopic studies and modeling. PMID:22536748

  14. Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

    USGS Publications Warehouse

    Helz, G.R.; Miller, C.V.; Charnock, J.M.; Mosselmans, J.F.W.; Pattrick, R.A.D.; Garner, C.D.; Vaughan, D.J.

    1996-01-01

    Molybdenum K-edge EXAFS (extended X-ray absorption fine structure) spectra yield new structural information about the chemical environment of Mo in high-Mo black shales and sediments. Two spectral types are found. The less common one, associated with Mo ores developed in shale in China, is that of a MoS2 phase, possibly X-ray amorphous jordisite. The other, associated with Cretaceous deep sea sediments and with other black shales, is characterized by short Mo-O distances (1.69-1.71 A??), by Mo-S distances of 2.30-2.38 A??, and in some cases by second shell Mo and Fe interactions, which suggests that some Mo resides in transition metal-rich phases. EXAFS spectra of synthetic amorphous materials, prepared by scavenging Mo from HS solutions with Fe(II), FeOOH, and humic acid, suggest that the second spectral type arises from Mo present chiefly in two forms. One is a compact, Mo-Fe-S "cubane" type compound with Mo-S distances of ???2.36 A?? and Mo-Fe distances of ???2.66 A??, while the other is probably an organic form containing some Mo-O double bonds (???1.69 A??). Laboratory products, that were prepared by scavenging dissolved Mo from sulfidic solutions with humic acid, yield spectra quite similar to the second spectral type observed in shales and sediments, including unexpected indications of Mo-Fe interactions. Molybdenum L-edge spectra indicate that the mean oxidation state in the sediments and shales lies between IV and VI. This work demonstrates the merit of EXAFS for obtaining structural information on natural materials containing X-ray amorphous components which defeat conventional mineralogical characterization. The implications of these findings regarding Mo scavenging from sulfidic natural waters are considered. We introduce the concept of a geochemical switch, in which HS- transforms the marine behavior of Mo from that of a conservative element to that of a particle reactive element. The action point of the HS- switch is calculated to be, aHS- = 10

  15. 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.

  16. 21-cm radiation: a new probe of variation in the fine-structure constant.

    PubMed

    Khatri, Rishi; Wandelt, Benjamin D

    2007-03-16

    We investigate the effect of variation in the value of the fine-structure constant (alpha) at high redshifts (recombination > z > 30) on the absorption of the cosmic microwave background (CMB) at 21 cm hyperfine transition of the neutral atomic hydrogen. We find that the 21 cm signal is very sensitive to the variations in alpha and it is so far the only probe of the fine-structure constant in this redshift range. A change in the value of alpha by 1% changes the mean brightness temperature decrement of the CMB due to 21 cm absorption by >5% over the redshift range z < 50. There is an effect of similar magnitude on the amplitude of the fluctuations in the brightness temperature. The redshift of maximum absorption also changes by approximately 5%. PMID:17501040

  17. Cell fine structure and function - Past and present

    NASA Technical Reports Server (NTRS)

    Fernandez-Moran, H.

    1970-01-01

    Electron microscopic studies of nerve membrane fine structure, discussing cell membrane multienzyme and macromolecular energy and information transduction, protein synthesis and nucleic acids interrelations

  18. Fine Structure and Dynamics of Sunspot Penumbra

    NASA Astrophysics Data System (ADS)

    Ryutova, M.; Berger, T.; Title, A.

    2007-08-01

    A mature sunspot is usually surrounded by a penumbra: strong vertical magnetic field in the umbra, the dark central region of sunspot, becomes more and more horizontal toward the periphery forming an ensemble of a thin magnetic filaments of varying inclinations. Recent high resolution observations with the 1-meter Swedish Solar Telescope (SST) on La Palma revealed a fine substructure of penumbral filaments and new regularities in their dynamics.1 These findings provide both the basis and constraints for an adequate model of the penumbra whose origin still remains enigmatic. We present results of recent observations obtained with the SST. Our data, taken simultaneously in 4305 Å G-band and 4396 Å continuum bandpasses and compiled in high cadence movies, confirm previous results and reveal new features of the penumbra. We find e.g. that individual filaments are cylindrical helices with a pitch/radius ratio providing their dynamic stability. We propose a mechanism that may explain the fine structure of penumbral filaments, the observed regularities, and their togetherness with sunspot formation. The mechanism is based on the anatomy of sunspots in which not only penumbra has a filamentary structure but umbra itself is a dense conglomerate of twisted interlaced flux tubes.

  19. Internal Fine Structure of Ellerman Bombs

    NASA Astrophysics Data System (ADS)

    Hashimoto, Yuki; Kitai, Reizaburo; Ichimoto, Kiyoshi; Ueno, Satoru; Nagata, Shin'ichi; Ishii, Takako T.; Hagino, Masaoki; Komori, Hiroyuki; Nishida, Keisuke; Matsumoto, Takuma; Otsuji, Kenichi; Nakamura, Tahei; Kawate, Tomoko; Watanabe, Hiroko; Shibata, Kazunari

    2010-08-01

    We conducted coordinated observations of Ellerman bombs (EBs) between Hinode Satellite and Hida Observatory (HOP12). CaII H broad-band filter images of NOAA 10966 on 2007 August 9 and 10 were obtained with the Solar Optical Telescope (SOT) aboard the Hinode Satellite, and many bright points were observed. We identified a total of 4 bright points as EBs, and studied the temporal variation of their morphological fine structures and spectroscopic characteristics. With high-resolution CaII H images of SOT, we found that the EBs, thus far thought of as single bright features, are composed of a few of fine subcomponents. Also, by using Stokes I/V filtergrams with Hinode/SOT, and CaII H spectroheliograms with Hida/Domeless Solar Telescope (DST), our observation showed: (1) The mean duration, the mean width, the mean length, and the mean aspect ratio of the subcomponents were 390 s, 170 km, 450 km, and 2.7, respectively. (2) Subcomponents started to appear on the magnetic neutral lines, and extended their lengths from the original locations. (3) When the CaII H line of EBs showed the characteristic blue asymmetry, they are associated with the appearance or re-brightening of subcomponents. Summarizing our results, we obtained an observational view that elementary magnetic reconnections take place one by one successively and intermittently in EBs, and that their manifestation is the fine subcomponents of the EB phenomena.

  20. Molecular Eigensolution Symmetry Analysis and Fine Structure

    PubMed Central

    Harter, William G.; Mitchell, Justin C.

    2013-01-01

    Spectra of high-symmetry molecules contain fine and superfine level cluster structure related to J-tunneling between hills and valleys on rovibronic energy surfaces (RES). Such graphic visualizations help disentangle multi-level dynamics, selection rules, and state mixing effects including widespread violation of nuclear spin symmetry species. A review of RES analysis compares it to that of potential energy surfaces (PES) used in Born–Oppenheimer approximations. Both take advantage of adiabatic coupling in order to visualize Hamiltonian eigensolutions. RES of symmetric and D2 asymmetric top rank-2-tensor Hamiltonians are compared with Oh spherical top rank-4-tensor fine-structure clusters of 6-fold and 8-fold tunneling multiplets. Then extreme 12-fold and 24-fold multiplets are analyzed by RES plots of higher rank tensor Hamiltonians. Such extreme clustering is rare in fundamental bands but prevalent in hot bands, and analysis of its superfine structure requires more efficient labeling and a more powerful group theory. This is introduced using elementary examples involving two groups of order-6 (C6 and D3~C3v), then applied to families of Oh clusters in SF6 spectra and to extreme clusters. PMID:23344041

  1. EXAFS Studies of Amorphous MoGe

    NASA Astrophysics Data System (ADS)

    Boyce, J. B.; Carter, W. L.; Geballe, T. H.; Claeson, T.

    1982-06-01

    Extended X-ray Absorption Fine Structure of amorphous and crystalline Mo-Ge samples sputter deposited on glass or kapton substrates was studied. Small local distortions were found in a substitutional b.c.c. Mo rich sample. A coordination in the range 5-7 and Ge-Mo distance of 2.65 A were estimated for an amorphous, intermediate composition Mo-Ge sample. The lack of superconductivity of some samples deposited on kapton was correlated to the presence of oxygen in the material.

  2. Substitution behavior of x(Na{sub 0.5}K{sub 0.5})NbO{sub 3}-(1 − x)BaTiO{sub 3} ceramics for multilayer ceramic capacitors by a near edge x-ray absorption fine structure analysis

    SciTech Connect

    Ha, Jooyeon; Ryu, Jiseung; Lee, Heesoo

    2014-06-30

    The doping effect of (Na{sub 0.5}K{sub 0.5})NbO{sub 3} (NKN) as alternatives for rare-earth elements on the electrical properties of BaTiO{sub 3} 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 BaTiO{sub 3}, 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 Nb{sup 5+} ion for Ti-sites. Therefore, the simultaneous substitution of Na{sup +}/K{sup +} and Nb{sup 5+} ions into BaTiO{sub 3} can improve dielectric properties, based on the charge-transfer process.

  3. EXAFS study on the cause of enrichment of heavy REEs on bacterial cell surfaces

    NASA Astrophysics Data System (ADS)

    Takahashi, Yoshio; Yamamoto, Mika; Yamamoto, Yuhei; Tanaka, Kazuya

    2010-10-01

    Rare earth element (REE) pattern is a unique geochemical tracer and has been measured for various natural materials. Among these, the REE distribution pattern between bacteria and water exhibits anomalous enrichment in the heavy REE (HREE) part, which can act as a signature of bacteria-related materials in natural samples. In this study, the REE binding site on the cell surface of a Gram-positive bacterium ( Bacillus subtilis) responsible for HREE enrichment has been identified using extended X-ray absorption fine structure (EXAFS) coupled with a study of the variation in REE distribution patterns. The EXAFS data showed that the HREEs form complexes with multiple phosphate site (including phosphoester site) with a larger coordination number (CN) at lower REE-bacteria ratios ([REE]/[bac]), while light and middle REEs form complexes to the phosphate site with a lower CN. The fraction coordinated to carboxylate increased for all REEs with increasing [REE]/[bac] ratio. On the other hand, the enrichment of HREE in the REE distribution patterns of the bacteria was less marked with increasing [REE]/[bac] ratio. This result is consistent with the EXAFS data, because the REE pattern of surface complex with multiple phosphate in a reference material exhibits a monotonous increase for heavier REE, while phosphate surface complex with a low CN and a carboxylate site reach a maximum around Sm and Eu. Based on these results, it is clear that the REE are primarily bound to the phosphate site and subsequently to the carboxylate site on the bacterial cell surface. Regarding the pH dependence in the range (3 < pH < 7), both the EXAFS and REE pattern data indicate that the fraction of REE-carboxylate increased as the pH increases. The results above obtained for B. subtilis were also valid for Escherichia coli, a Gram-negative bacterium, showing that similar phosphate and carboxylate sites are also available in the cell walls of E. coli, or other Gram negative bacteria. In all our

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    PubMed

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

    2016-08-01

    Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. PMID:27379398

  7. 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.

  8. Role of extracellular polymeric substances in metal ion complexation on Shewanella oneidensis: Batch uptake, thermodynamic modeling, ATR-FTIR, and EXAFS study

    NASA Astrophysics Data System (ADS)

    Ha, Juyoung; Gélabert, Alexandre; Spormann, Alfred M.; Brown, Gordon E., Jr.

    2010-01-01

    The effect of cell wall-associated extracellular polymeric substances (EPS) of the Gram-negative bacterium Shewanella oneidensis strain MR-1 on proton, Zn(II), and Pb(II) adsorption was investigated using a combination of titration/batch uptake studies, surface complexation modeling, attenuated total reflectance - Fourier transform infrared (ATR-FTIR) spectroscopy, and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. Both unmodified (wild-type (WT) strain) and genetically modified cells with inhibited production of EPS (ΔEPS strain) were used. Three major types of functional groups (carboxyl, phosphoryl, and amide groups) were identified in both strains using ATR-FITR spectroscopy. Potentiometric titration data were fit using a constant capacitance model (FITEQL) that included these three functional groups. The fit results indicate less interaction of Zn(II) and Pb(II) with carboxyl and amide groups and a greater interaction with phosphoryl groups in the ΔEPS strain than in the WT strain. Results from Zn(II) and Pb(II) batch adsorption studies and surface complexation modeling, assuming carboxyl and phosphoryl functional groups, also indicate significantly lower Zn(II) and Pb(II) uptake and binding affinities for the ΔEPS strain. Results from Zn K-edge EXAFS spectroscopy show that Zn(II) bonds to phosphoryl and carboxyl ligands in both strains. Based on batch uptake and modeling results and EXAFS spectral analysis, we conclude that the greater amount of EPS in the WT strain enhances Zn(II) and Pb(II) uptake and hinders diffusion of Zn(II) to the cell walls relative to the ΔEPS strain.

  9. 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.

  10. Composition-dependent structure of polycrystalline magnetron-sputtered V-Al-C-N hard coatings studied by XRD, XPS, XANES and EXAFS.

    PubMed

    Krause, Bärbel; Darma, Susan; Kaufholz, Marthe; Mangold, Stefan; Doyle, Stephen; Ulrich, Sven; Leiste, Harald; Stüber, Michael; Baumbach, Tilo

    2013-08-01

    V-Al-C-N hard coatings with high carbon content were deposited by reactive radio-frequency magnetron sputtering using an experimental combinatorial approach, deposition from a segmented sputter target. The composition-dependent coexisting phases within the coating were analysed using the complementary methods of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure spectroscopy (EXAFS). For the analysis of the X-ray absorption near-edge spectra, a new approach for evaluation of the pre-edge peak was developed, taking into account the self-absorption effects in thin films. Within the studied composition range, a mixed face-centred cubic (V,Al)(C,N) phase coexisting with a C-C-containing phase was observed. No indication of hexagonal (V,Al)(N,C) was found. The example of V-Al-C-N demonstrates how important a combination of complementary methods is for the detection of coexisting phases in complex multi-element coatings. PMID:24046506

  11. Composition-dependent structure of polycrystalline magnetron-sputtered V–Al–C–N hard coatings studied by XRD, XPS, XANES and EXAFS

    PubMed Central

    Krause, Bärbel; Darma, Susan; Kaufholz, Marthe; Mangold, Stefan; Doyle, Stephen; Ulrich, Sven; Leiste, Harald; Stüber, Michael; Baumbach, Tilo

    2013-01-01

    V–Al–C–N hard coatings with high carbon content were deposited by reactive radio-frequency magnetron sputtering using an experimental combinatorial approach, deposition from a segmented sputter target. The composition-dependent coexisting phases within the coating were analysed using the complementary methods of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure spectroscopy (EXAFS). For the analysis of the X-ray absorption near-edge spectra, a new approach for evaluation of the pre-edge peak was developed, taking into account the self-absorption effects in thin films. Within the studied composition range, a mixed face-centred cubic (V,Al)(C,N) phase coexisting with a C–C-containing phase was observed. No indication of hexagonal (V,Al)(N,C) was found. The example of V–Al–C–N demonstrates how important a combination of complementary methods is for the detection of coexisting phases in complex multi-element coatings. PMID:24046506

  12. Uptake of Np(IV) by C-S-H phases and cement paste: an EXAFS study.

    PubMed

    Gaona, Xavier; Dähn, Rainer; Tits, Jan; Scheinost, Andreas C; Wieland, Erich

    2011-10-15

    Nuclear waste disposal concepts developed worldwide foresee the use of cementitious materials for the immobilization of long-lived intermediate level waste (ILW). This waste form may contain significant amounts of neptunium-237, which is expected to be present as Np(IV) under the reducing conditions encountered after the closure of the repository. Predicting the release of Np(IV) from the cementitious near field of an ILW repository requires a sufficiently detailed understanding of its interaction with the main sorbing components of hardened cement paste (HCP). In this study, the uptake of Np(IV) by calcium silicate hydrates (C-S-H) and HCP has been investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy. The EXAFS studies on Np(IV)-doped C-S-H and HCP samples reveal that Np(IV) is predominantly incorporated in the structure of C-S-H phases having different Ca:Si ratios. The two main species identified correspond to Np(IV) in C-S-H with a Ca:Si mol ratio of 1.65 as in fresh cement and with a Ca:Si mol ratio of 0.75 as in highly degraded cement. The local structure of Np(IV) changes with the Ca:Si mol ratio and does not depend on pH. Furthermore, Np(IV) shows the same coordination environment in C-S-H and HCP samples. This study shows that C-S-H phases are responsible for the Np(IV) uptake by cementitious materials and further that incorporation in the interlayer of the C-S-H structure is the dominant uptake mechanism. PMID:21879756

  13. Structural characterization by EXAFS spectroscopy of the binuclear iron center in protein A of methane monooxygenase from methylococcus capsulatus (bath)

    SciTech Connect

    Ericson, A.; Hedman, B.; Hodgson, K.O.; Green, J.; Dalton, H.; Bentsen, J.G.; Beer, R.H.; Lippard, S.J.

    1988-03-30

    Soluble methane monooxygenase (MMO) from Methylococcus capsulatus (Bath) activates dioxygen for incorporation into a remarkable variety of substrates including methane, which is required for bacterial growth (eq 1). MMO is a three component CH/sub 4/ + NADH + H/sup +/ + O/sub 2/ /sup MMO/ ..-->.. CH/sub 3/OH + NAD/sup +/ + H/sub 2/O (1) enzyme. Protein A (M/sub r/ 210,000), believed to be the oxygenase component, contains two iron atoms. Protein B (M/sub r/ 15,700) serves a regulatory function and lacks prosthetic groups, while protein C, the reductase component of the enzyme, is an iron-sulfur flavoprotein (M/sub r/ 42,000) responsible for electron transfer from NADH to protein A. Recently, a binuclear iron center was postulated to occur in protein A based on the finding that one-electron reduction gives rise to electron spin resonance (ESR) signals (g 1.95, 1.88, 1.78) very similar to those observed for the binuclear mixed-valence Fe/sub 2/(III,II) centers in semimet hemerythrin (Hr) and purple acid phosphatase (PAP). In conjunction with model studies, extended X-ray absorption fine structure (EXAFS) spectroscopy has proven to be a powerful method for identifying bridged binuclear iron centers in Hr, ribonucleotide reductase (RR), and PAP. Here the authors report iron K-edge EXAFS results on semireduced protein A of MMO which support the occurrence of a binuclear iron center (Fe-Fe distance, 3.41 A), with no short ..mu..-oxo bridge.

  14. The effect of zirconia content on the structure of zirconia-silica xerogels as determined by x-ray and neutron diffraction and Zr K-edge EXAFS and XANES

    NASA Astrophysics Data System (ADS)

    Mountjoy, G.; Anderson, R.; Newport, R. J.; Smith, M. E.

    2000-04-01

    We present combined x-ray and neutron diffraction, and extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results on a single set of (ZrO2 )x (SiO2 )1-x xerogel samples. In these samples, there is improved homogeneity of Zr compared to our previous study, due to greater dilution of the precursor Zr n-propoxide in propan-1-ol. Structural parameters obtained from model fitting of the diffraction and EXAFS data are compared with those in reference compounds. A qualitative comparison of XANES spectra is also made. The results show that for xicons/Journals/Common/geq" ALT="geq" ALIGN="TOP"/> 0.3 there is phase separation of ZrO2 and the Zr environment is similar to that in monoclinic ZrO2 and Zr hydroxide. For xicons/Journals/Common/leq" ALT="leq" ALIGN="TOP"/> 0.2 there is no phase separation, the SiO2 network is distorted and the Zr coordination is similar to that in Zr n-propoxide, with some Zr-Zr clustering.

  15. SEISMOLOGY OF STANDING KINK OSCILLATIONS OF SOLAR PROMINENCE FINE STRUCTURES

    SciTech Connect

    Soler, R.; Arregui, I.; Oliver, R.; Ballester, J. L.

    2010-10-20

    We investigate standing kink magnetohydrodynamic (MHD) oscillations in a prominence fine structure modeled as a straight and cylindrical magnetic tube only partially filled with the prominence material and with its ends fixed at two rigid walls representing the solar photosphere. The prominence plasma is partially ionized and a transverse inhomogeneous transitional layer is included between the prominence thread and the coronal medium. Thus, ion-neutral collisions and resonant absorption are the damping mechanisms considered. Approximate analytical expressions of the period, the damping time, and their ratio are derived for the fundamental mode in the thin tube and thin boundary approximations. We find that the dominant damping mechanism is resonant absorption, which provides damping ratios in agreement with the observations, whereas ion-neutral collisions are irrelevant for damping. The values of the damping ratio are independent of both the prominence thread length and its position within the magnetic tube, and coincide with the values for a tube fully filled with the prominence plasma. The implications of our results in the context of the MHD seismology technique are discussed, pointing out that the reported short-period (2-10 minutes) and short-wavelength (700-8000 km) thread oscillations may not be consistent with a standing mode interpretation and could be related to propagating waves. Finally, we show that the inversion of some prominence physical parameters, e.g., Alfven speed, magnetic field strength, transverse inhomogeneity length scale, etc., is possible using observationally determined values of the period and damping time of the oscillations along with the analytical approximations of these quantities.

  16. Triosmium clusters on a support: determination of structure by X-ray absorption spectroscopy and high-resolution microscopy.

    PubMed

    Mehraeen, Shareghe; Kulkarni, Apoorva; Chi, Miaofang; Reed, Bryan W; Okamoto, Norihiko L; Browning, Nigel D; Gates, Bruce C

    2011-01-17

    The structures of small, robust metal clusters on a solid support were determined by a combination of spectroscopic and microscopic methods: extended X-ray absorption fine structure (EXAFS) spectroscopy, scanning transmission electron microscopy (STEM), and aberration-corrected STEM. The samples were synthesized from [Os(3) (CO)(12) ] on MgO powder to provide supported clusters intended to be triosmium. The results demonstrate that the supported clusters are robust in the absence of oxidants. Conventional high-angle annular dark-field (HAADF) STEM images demonstrate a high degree of uniformity of the clusters, with root-mean-square (rms) radii of 2.03±0.06 Å. The EXAFS OsOs coordination number of 2.1±0.4 confirms the presence of triosmium clusters on average and correspondingly determines an average rms cluster radius of 2.02±0.04 Å. The high-resolution STEM images show the individual Os atoms in the clusters, confirming the triangular structures of their frames and determining OsOs distances of 2.80±0.14 Å, matching the EXAFS value of 2.89±0.06 Å. IR and EXAFS spectra demonstrate the presence of CO ligands on the clusters. This set of techniques is recommended as optimal for detailed and reliable structural characterization of supported clusters. PMID:21226118

  17. Triosmium Clusters on a Support: Determination of Structure by X-Ray Absorption Spectroscopy and High-Resolution Microscopy

    SciTech Connect

    Shareghe, Mehraeen; Chi, Miaofang; Browning, Nigel D.

    2011-01-01

    The structures of small, robust metal clusters on a solid support were determined by a combination of spectroscopic and microscopic methods: extended X-ray absorption fine structure (EXAFS) spectroscopy, scanning transmission electron microscopy (STEM), and aberration-corrected STEM. The samples were synthesized from [Os{sub 3}(CO){sub 12}] on MgO powder to provide supported clusters intended to be triosmium. The results demonstrate that the supported clusters are robust in the absence of oxidants. Conventional high-angle annular dark-field (HAADF) STEM images demonstrate a high degree of uniformity of the clusters, with root-mean-square (rms) radii of 2.03 {+-} 0.06 {angstrom}. The EXAFS OsOs coordination number of 2.1 {+-} 0.4 confirms the presence of triosmium clusters on average and correspondingly determines an average rms cluster radius of 2.02 {+-} 0.04 {angstrom}. The high-resolution STEM images show the individual Os atoms in the clusters, confirming the triangular structures of their frames and determining OsOs distances of 2.80 {+-} 0.14 {angstrom}, matching the EXAFS value of 2.89 {+-} 0.06 {angstrom}. IR and EXAFS spectra demonstrate the presence of CO ligands on the clusters. This set of techniques is recommended as optimal for detailed and reliable structural characterization of supported clusters.

  18. EXAFS, XANES, and DFT study of the mixed-valence compound YMn2O5 : Site-selective substitution of Fe for Mn

    NASA Astrophysics Data System (ADS)

    Wunderlich, F.; Leisegang, T.; Weißbach, T.; Zschornak, M.; Stöcker, H.; Dshemuchadse, J.; Lubk, A.; Führlich, T.; Welter, E.; Souptel, D.; Gemming, S.; Seifert, G.; Meyer, D. C.

    2010-07-01

    In YMn2O5 , the Mn atoms occupy two nonequivalent Wyckoff sites within the unit cell exhibiting different oxygen coordinations, i.e., the system can be characterized as a mixed-valence compound. For the formation of the orthorhombic crystal structure, Jahn-Teller distortions are assumed to play an important role. In this study, we aimed at the investigation of the crystal structure changes upon the substitution of Mn by the non-Jahn-Teller cation Fe3+ . Therefore, we synthesized a series of YMn2-xFexO5 powder samples with x=0 , 0.5, and 1 by a citrate technique. We utilized extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) analysis as well as density-functional theory (DFT) to investigate the two nonequivalent Wyckoff sites within the orthorhombic crystal structure (confirmed for all compositions) occupied by transition-metal atoms. For quantitative determination of structural short-range order, all plausible options of substitution of Fe for Mn are discussed. On the basis of these evaluations, the EXAFS and XANES behavior is analyzed and appropriate crystallographic weights are assigned to the subset of structural models in accordance with the experimental data. From EXAFS analysis, using multiple-scattering theory, we conclude only the 4h Wyckoff site to be occupied by Fe [occupancy refined is (100±3)% in case of x=1 ]. Furthermore, taking the XANES spectra into account, we are able to verify the EXAFS results and additionally explain the differences in the MnK XANES spectra in dependence on x to be caused by changes in the dipole transitions to 4p final states. From quantitative pre-edge analysis an oxidation number of +4 for the Mn atom for x=1 is determined whereas the Fe valence is shown to be unchanged. Since the substitution process only involves one Wyckoff site, the experimentally observed limit to a maximum amount of x=1 is explained. Additionally, a possible disorder, discussed in the literature, is not

  19. 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.

  20. 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.

  1. Markov Chain Monte Carlo methods applied to measuring the fine structure constant from quasar spectroscopy .

    NASA Astrophysics Data System (ADS)

    King, J. A.; Mortlock, D. J.; Webb, J. K.; Murphy, M. T.

    Recent attempts to constrain cosmological variation in the fine structure constant, alpha , using quasar absorption lines have yielded two statistical samples which initially appear to be inconsistent. One of these samples was subsequently demonstrated to not pass consistency tests; it appears that the optimisation algorithm used to fit the model to the spectra failed. Nevertheless, the results of the other hinge on the robustness of the spectral fitting program VPFIT, which has been tested through simulation but not through direct exploration of the likelihood function. We present the application of Markov Chain Monte Carlo (MCMC) methods to this problem, and demonstrate that VPFIT produces similar values and uncertainties for Delta alpha /alpha , the fractional change in the fine structure constant, as our MCMC algorithm, and thus that VPFIT is reliable.

  2. Markov Chain Monte Carlo methods applied to measuring the fine structure constant from quasar spectroscopy

    NASA Astrophysics Data System (ADS)

    King, Julian; Mortlock, Daniel; Webb, John; Murphy, Michael

    2010-11-01

    Recent attempts to constrain cosmological variation in the fine structure constant, α, using quasar absorption lines have yielded two statistical samples which initially appear to be inconsistent. One of these samples was subsequently demonstrated to not pass consistency tests; it appears that the optimisation algorithm used to fit the model to the spectra failed. Nevertheless, the results of the other hinge on the robustness of the spectral fitting program VPFIT, which has been tested through simulation but not through direct exploration of the likelihood function. We present the application of Markov Chain Monte Carlo (MCMC) methods to this problem, and demonstrate that VPFIT produces similar values and uncertainties for Δα/α, the fractional change in the fine structure constant, as our MCMC algorithm, and thus that VPFIT is reliable.

  3. Constraints on field theoretical models for variation of the fine structure constant

    NASA Astrophysics Data System (ADS)

    Steinhardt, Charles L.

    2005-02-01

    Recent theoretical ideas and observational claims suggest that the fine structure constant α may be variable. We examine a spectrum of models in which α is a function of a scalar field. Specifically, we consider three scenarios: oscillating α, monotonic time variation of α, and time-independent α that is spatially varying. We examine the constraints imposed upon these theories by cosmological observations, particle detector experiments, and “fifth force” experiments. These constraints are very strong on models involving oscillation but cannot compete with bounds from the Oklo subnuclear reactor on models with monotonic timelike variation of α. One particular model with spatial variation is consistent with all current experimental and observational measurements, including those from two seemingly conflicting measurements of the fine structure constant using the many multiplet method on absorption lines.

  4. Characterization of Na+- beta-Zeolite Supported Pd and Pd Ag Bimetallic Catalysts using EXAFS, TEM and Flow Reactor

    SciTech Connect

    Huang,W.; Lobo, R.; Chen, J.

    2008-01-01

    Flow reactor studies of the selective hydrogenation of acetylene in the presence of ethylene have been performed on Na+ exchanged {beta}-zeolite supported Pd, Ag and PdAg catalysts, as an extension of our previous batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. Results from flow reactor studies show that the PdAg/Na+-{beta}-zeolite bimetallic catalyst has lower activity than Pd/Na+-{beta}-zeolite monometallic catalyst, while Ag/Na+-{beta}-zeolite does not show any activity for acetylene hydrogenation. However, the selectivity for the PdAg bimetallic catalyst is much higher than that for either the Pd catalyst or Ag catalyst. The selectivity to byproduct (ethane) is greatly inhibited on the PdAg bimetallic catalyst as well. The results from the current flow reactor studies confirmed the pervious results from batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. In addition, we used transmission electron microscope (TEM), extended X-ray absorption fine structure (EXAFS), and FTIR of CO adsorption to confirm the formation of Pd-Ag bimetallic alloy in the PdAg/Na+-{beta}-zeolite catalyst.

  5. Effect of Organic Matter on Sorption of Zn on Soil: Elucidation by Wien Effect Measurements and EXAFS Spectroscopy.

    PubMed

    Fan, Ting-Ting; Wang, Yu-Jun; Li, Cheng-Bao; He, Jian-Zhou; Gao, Juan; Zhou, Dong-Mei; Friedman, Shmulik P; Sparks, Donald L

    2016-03-15

    Soil organic matter (SOM) is the major factor affecting sequestration of heavy metals in soil. The mean free binding energy and the mean free adsorption energy and speciation of Zn in soil, as affected by SOM, were determined by employing Wien effect measurements. The presence of SOM markedly decreased the Zn binding energy in soils in the following order: Top (5.86 kJ mol(-1)) < Bottom (8.66 kJ mol(-1)) < Top OM-free (9.44 kJ mol(-1)) ≈ Bottom OM-free (9.50 kJ mol(-1)). The SOM also significantly decreased the adsorption energy of Zn on black soil particles by reducing nonspecific adsorption of Zn on their surfaces. The speciation of Zn in soils was elucidated by extended X-ray absorption fine structure spectroscopy and microfocus X-ray fluorescence. The results obtained by linear combination fitting of EXAFS spectra revealed that the main forms of Zn in soil were outer-sphere Zn, Zn-illite, Zn-kaolinite, and HA-Zn. As the SOM content increased, the proportion of HA-Zn among the total immobilized Zn increased, and the proportion of nonspecific adsorbed Zn decreased. The present results implied that SOM is an important controlling factor for the environmental behavior of Zn in soils. PMID:26894796

  6. Combined EXAFS and DFT Structure Calculations Provide Structural Insights into the 1:1 Multi-Histidine Complexes of CuII, CuI and ZnII with the Tandem Octarepeats of the Mammalian Prion Protein

    PubMed Central

    Pushie, M. Jake; Nienaber, Kurt H.; McDonald, Alex; Millhauser, Glenn L.; George, Graham N.

    2014-01-01

    The metal coordinating properties of the prion protein (PrP) have been the subject of intense focus and debate since the first reports of copper interaction with PrP just before the turn of the century. The picture of metal coordination to PrP has been improved and refined over the past decade, and yet the structural details of the various metal coordination modes have not been fully elucidated in some cases. Herein we employ X-ray absorption near edge spectroscopy as well as extended X-ray absorption fine structure (EXAFS) spectroscopy to structurally characterize the dominant 1:1 coordination modes for CuII, CuI and ZnII with an N-terminal fragment of PrP. The PrP fragment constitutes four tandem repeats representative of the mammalian octarepeat domain, designated OR4, which is also the most studied PrP fragment for metal interactions, making our findings applicable to a large body of previous work. Density functional theory (DFT) calculations provide additional structural and thermodynamic data, and candidate structures are used to inform EXAFS data analysis. The optimized geometries from DFT calculations are used to identify potential coordination complexes for multi-histidine coordination of CuII, CuI and ZnII in an aqueous medium, modeled using 4-methylimidazole to represent the histidine side chain. Through a combination of in silico coordination chemistry as well as rigorous EXAFS curve fitting, using full multiple scattering on candidate structures from DFT calculations, we have characterized the predominant coordination modes for the 1:1 complexes of CuII, CuI and ZnII with the OR4 peptide at pH 7.4 at atomic resolution, which are best represented as a square planar [CuII(His)4]2+, digonal [CuI(His)2]+ and tetrahedral [ZnII(His)3(OH2)]2+, respectively. PMID:25042361

  7. EXAFS Study of N- And P-Type Ba(8)Ga(16)Ge(30)

    SciTech Connect

    Jiang, Y.; Bridges, F.; Avila, M.A.; Takabatake, T.; Guzman, J.; Kurczveil, G.

    2009-05-18

    We report extended x-ray absorption fine-structure (EXAFS) studies of n- and p-type Ba{sub 8}Ga{sub 16}Ge{sub 30} samples (type-I clathrate) at the Ga, Ge, and Ba K edges, to probe the local structure, particularly around the Ba atoms located inside 20- and 24-atom cages (Ba1 and Ba2 sites, respectively) composed of Ga/Ge atoms. In agreement with diffraction analysis, we find Ba2 is off center, with a component in the bc plane (0.15 {angstrom}) comparable to that found in diffraction. However, under the assumption of a stiff cage, we also require a significant a component. This suggests a coupling or attraction between the Ba2 atoms and the hexagonal rings at the top or bottom of the cage that encloses the Ba2 site. Further, changing the a component can change the number of shortest Ba2-Ga/Ge neighbors and hence the coupling of Ba2 to the surrounding cage. Within the cage structures which enclose both Ba sites, the Ga-Ga/Ge distances are slightly longer, while the Ge-Ga/Ge distances are slightly shorter than the average distance reported from diffraction. The longer Ga-Ga/Ge distances indicate that the Ba1 and Ba2 cages may be dimpled or distorted. At the second Ga/Ge distance, the local distortions in the Ba clathrate are smaller than those observed in the Eu clathrate, which likely plays a role in understanding the higher thermal conductivity of Ba clathrates compared to that of Eu clathrates. However, there is no clear difference in the EXAFS between the n- and p-type materials for either the Ba, Ga, or Ge K-edge data, which would explain the difference in thermal conductivity between n- and p-type materials. Finally, an average Einstein temperature for the shortest Ba2-Ga/Ge bonds is comparable to that for Ba1-Ga/Ge. This indicates a large effective spring constant for the closest Ga/Ge atoms to Ba2. We also develop a simple vibrational model to show explicitly the three types of vibration for Ba2 within the type-2 cage.

  8. Geological and anthropogenic factors influencing mercury speciation in mine wastes: An EXAFS spectroscopy study

    USGS Publications Warehouse

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

    2004-01-01

    The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600??C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345??C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500-2000 ??m and <45 ??m size fractions (e.g., from 97-810 mg/kg Hg in calcines from the Sulphur Bank Mine, CA). The proportion of Hg-sulfides present also increased by 8-18% as particle size decreased over the same size range. This finding suggests that insoluble yet soft Hg-sulfides are subject to preferential mechanical weathering and become enriched in the fine-grained fraction, while soluble Hg phases are leached out more readily as particle size decreases

  9. EXAFS and XANES investigation of (Li, Ni) codoped ZnO thin films grown by pulsed laser deposition.

    PubMed

    Mino, Lorenzo; Gianolio, Diego; Bardelli, Fabrizio; Prestipino, Carmelo; Senthil Kumar, E; Bellarmine, F; Ramanjaneyulu, M; Lamberti, Carlo; Ramachandra Rao, M S

    2013-09-25

    Ni doped, Li doped and (Li, Ni) codoped ZnO thin films were successfully grown using a pulsed laser deposition technique. Undoped and doped ZnO thin films were investigated using extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES). Preliminary investigations on the Zn K-edge of the undoped and doped ZnO thin films revealed that doping has not influenced the average Zn-Zn bond length and Debye-Waller factor. This shows that both Ni and Li doping do not appreciably affect the average local environment of Zn. All the doped ZnO thin films exhibited more than 50% of substitutional Ni, with a maximum of 77% for 2% Ni and 2% Li doped ZnO thin film. The contribution of Ni metal to the EXAFS signal clearly reveals the presence of Ni clusters. The Ni-Ni distance in the Ni(0) nanoclusters, which are formed in the film, is shorter with respect to the reference Ni metal foil and the Debye-Waller factor is higher. Both facts perfectly reflect what is expected for metal nanoparticles. At the highest doping concentration (5%), the presence of Li favors the growth of a secondary NiO phase. Indeed, 2% Ni and 5% Li doped ZnO thin film shows %Nisub = 75 ± 11, %Nimet = 10 ± 8, %NiO = 15 ± 8. XANES studies further confirm that the substitutional Ni is more than 50% in all the samples. These results explain the observed magnetic properties. PMID:23988792

  10. Examining Mechanisms of Groundwater Hg(II) Treatment by Reactive Materials: An EXAFS Study

    SciTech Connect

    Gibson, Blair D.; Ptacek, Carol J.; Lindsay, Matthew B.J.; Blowes, David W.

    2012-02-07

    Laboratory batch experiments were conducted to examine mechanisms of Hg(II) removal by reactive materials proposed for groundwater treatment. These materials included granular iron filings (GIF), 1:1 (w/w) mixtures of metallurgical granular Fe powder + elemental S (MGI+S) and elemental Cu + elemental S (Cu+S), granular activated carbon (GAC), attapulgite clay (ATP), ATP treated with 2-amino-5-thiol-1,3,4-thiadiazole (ATP-a), and ATP treated with 2,5-dimercapto-1,3,4-thiadiazole (ATP-d). Following treatment of simulated groundwater containing 4 mg L{sup -1} Hg for 8 or 16 days, the solution pH values ranged from 6.8 to 8.8 and Eh values ranged from +400 to -400 mV. Large decreases in aqueous Hg concentrations were observed for ATP-d (>99%), GIF (95%), MGI+S (94%), and Cu+S (90%). Treatment of Hg was less effective using ATP (29%), ATP-a (69%), and GAC (78%). Extended X-ray absorption fine structure (EXAFS) spectra of Hg on GIF, MGI+S, and GAC indicated the presence of an Hg-O bond at 2.04-2.07 {angstrom}, suggesting that Hg was bound to GIF corrosion products or to oxygen complexes associated with water sorbed to activated carbon. In contrast, bond lengths ranging from 2.35 to 2.48 {angstrom} were observed for Hg in Cu+S, ATP-a, and ATP-d treatments, suggesting the formation of Hg-S bonds.

  11. Structures of Plutonium(IV) and Uranium(VI) with N,N-Dialkyl Amides from Crystallography, X-ray Absorption Spectra, and Theoretical Calculations.

    PubMed

    Acher, Eléonor; Hacene Cherkaski, Yanis; Dumas, Thomas; Tamain, Christelle; Guillaumont, Dominique; Boubals, Nathalie; Javierre, Guilhem; Hennig, Christoph; Solari, Pier Lorenzo; Charbonnel, Marie-Christine

    2016-06-01

    The structures of plutonium(IV) and uranium(VI) ions with a series of N,N-dialkyl amides ligands with linear and branched alkyl chains were elucidated from single-crystal X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), and theoretical calculations. In the field of nuclear fuel reprocessing, N,N-dialkyl amides are alternative organic ligands to achieve the separation of uranium(VI) and plutonium(IV) from highly concentrated nitric acid solution. EXAFS analysis combined with XRD shows that the coordination structure of U(VI) is identical in the solution and in the solid state and is independent of the alkyl chain: two amide ligands and four bidentate nitrate ions coordinate the uranyl ion. With linear alkyl chain amides, Pu(IV) also adopt identical structures in the solid state and in solution with two amides and four bidentate nitrate ions. With branched alkyl chain amides, the coordination structure of Pu(IV) was more difficult to establish unambiguously from EXAFS. Density functional theory (DFT) calculations were consequently performed on a series of structures with different coordination modes. Structural parameters and Debye-Waller factors derived from the DFT calculations were used to compute EXAFS spectra without using fitting parameters. By using this methodology, it was possible to show that the branched alkyl chain amides form partly outer-sphere complexes with protonated ligands hydrogen bonded to nitrate ions. PMID:27171842

  12. An EXAFS study on the effects of natural organic matter and the expandability of clay minerals on cesium adsorption and mobility

    NASA Astrophysics Data System (ADS)

    Fan, Q. H.; Tanaka, M.; Tanaka, K.; Sakaguchi, A.; Takahashi, Y.

    2014-06-01

    The relationship between cesium (Cs) adsorption on clay minerals with various expandabilities and Cs mobility in environment was investigated using sequential extraction, batch adsorption, X-ray diffraction (XRD), generalized adsorption model (GAM), and Cs LIII-edge extended X-ray absorption fine structure (EXAFS) analyses with molecular simulations using the density functional theory (DFT). In particular, the difference between the affinities of illite (non-expansion) and vermiculite (intermediate expansion) for Cs and the effect of humic acid (HA) addition on the Cs/clay mineral system were highlighted in this study. These two factors affect Cs mobility and bioavailability in surface soil and sediments. The batch adsorption results showed that Cs adsorption was inhibited to some extent in the ternary clay + HA + Cs system because of (i) the blocked access of Cs to the frayed edge site (FES) and type II site [inner-sphere (IS) complex in GAM] by HA, and (ii) the reduced availability of the interlayer site in vermiculite. EXAFS analysis further confirmed that the adsorbed Cs in clay minerals was drastically changed by the sequential addition of HA. In addition, the dominant IS complex in the illite + Cs and illite + Cs + HA systems (in which HA was added after Cs adsorption on illite) can be converted to the outer-sphere (OS) complex largely in the illite + HA + Cs system (in which HA was added prior to Cs adsorption). These results are consistent with the sequential extraction and GAM results. The IS complex of dehydrated Cs+ mainly formed at the FES and interlayer site on illite (non-expansion) without resulting in any illite structural changes. However, on vermiculite (intermediate expansion), the dehydrated Cs+ can be adsorbed as an IS complex associated with the siloxane group of the di-trigonal cavity in the tetrahedral SiO4 sheet. This adsorption is accompanied by collapse of the layer, which can be easily coated by HA molecules to prevent Cs fixation

  13. 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.

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

    PubMed

    Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

    2015-11-01

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

  15. EDA: EXAFS data analysis software package

    NASA Astrophysics Data System (ADS)

    Kuzmin, A.

    1995-02-01

    The present paper describes the EXAFS data analysis software package, called EDA, originally developed by the author for IBM PC compatible computers. It consists of a set of interactive programs which allow to carry out all steps of the EXAFS data analysis procedure. There are two main differences from known packages. First, a significantly improved algorithm is used for atomic-like background removal in the EXAFS extraction procedure. Second, a model independent derivation of the radial distribution function from EXAFS, based on a maximum-entropy-like algorithm, is available.

  16. 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.

  17. 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.

  18. Temporal Fine Structure and Applications to Cochlear Implants

    ERIC Educational Resources Information Center

    Li, Xing

    2013-01-01

    Complex broadband sounds are decomposed by the auditory filters into a series of relatively narrowband signals, each of which conveys information about the sound by time-varying features. The slow changes in the overall amplitude constitute envelope, while the more rapid events, such as zero crossings, constitute temporal fine structure (TFS).…

  19. EXAFS structure and electrical properties of lithium niobium phosphate

    SciTech Connect

    Bruque, S.; Martinez Lara, M.; Moreno, L.

    1995-02-01

    The acidic character of the hydration water in NbOPO{sub 4} {center_dot} 2H{sub 2}O permits the exchange of protons for Li{sup +} ions. The lithium phase annealed at 773 K presents a slightly distorted lattice with respect to the niobium phosphate network, allowing high mobility of the lithium ion. The structural modifications due to Li insertion have been studied by extended X-ray absorption spectroscopy (EXAFS) at the Nb K-edge. The analysis of the EXAFS spectra indicates the presence of an additional oxygen atom close to Nb which is probably not bonded to the framework. The ionic conductivity of the LiNb(OH)OPO{sub 4} phase is high and increases up to 880 K. At higher temperatures, the Li{sup +} ion migrates to a permanent position in the network and the ionic conductivity is then stopped.

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

    NASA Astrophysics Data System (ADS)

    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 (UO2+2) in uranium L3-edge extended x-ray-absorption fine structure (EXAFS), and L1- and L3-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 [UO2(CH3CO2)2.2H2O], 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 ab initio multiple-scattering (MS) code FEFF 6. Theoretical XANES spectra for uranyl fluoride (UO2F2) 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 L1-edge XANES is obtained. MS paths within the uranyl cation have a notable influence upon the XANES. The measured L3-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 L1-edge XANES calculations, in which overlapping was required for the best agreement with experiment.

  2. High-resolution analysis of Zn2+ coordination in the alkaline phosphatase superfamily by EXAFS and x-ray crystallography

    PubMed Central

    Bobyr, Elena; Lassila, Jonathan K.; Wiersma-Koch, Helen I.; Fenn, Timothy D.; Lee, Jason J.; Nikolic-Hughes, Ivana; Hodgson, Keith O.; Rees, Douglas C.; Hedman, Britt; Herschlag, Daniel

    2011-01-01

    Comparisons among evolutionarily related enzymes offer opportunities to reveal how structural differences produce different catalytic activities. Two structurally-related enzymes, E. coli alkaline phosphatase (AP) and X. axonopodis nucleotide pyrophosphatase/phosphodiesterase (NPP) have nearly identical binuclear Zn2+ catalytic centers, but show tremendous differential specificity for hydrolysis of phosphate monoesters or phosphate diesters. To determine if there are differences in Zn2+ coordination in the two enzymes that might contribute to catalytic specificity, we analyzed both x-ray absorption spectroscopic and x-ray crystallographic data. We report a 1.29 Å crystal structure of alkaline phosphatase with bound phosphate, allowing evaluation of interactions at the AP metal site with high resolution. To make systematic comparisons between AP and NPP, we measured zinc extended x-ray absorption fine structure (EXAFS) for AP and NPP in the free enzyme forms, with AMP and inorganic phosphate ground-state analogs, and with vanadate transition state analogs. These studies yielded average zinc-ligand distances in AP and NPP free-enzyme forms and ground-state analog forms that were identical within error, suggesting little difference in metal ion coordination among these forms. Upon binding of vanadate to both enzymes, small increases in average metal-ligand distances were observed, consistent with an increased coordination number. Slightly longer increases were observed in NPP relative to AP, which could arise from subtle rearrangements of the active site or differences in the geometry of the bound vanadyl species. Overall, the results suggest that the binuclear Zn2+ catalytic site remains very similar between AP and NPP during the course of a reaction cycle. PMID:22056344

  3. Assigning {gamma} deformation from fine structure in exotic nuclei

    SciTech Connect

    Ferreira, L. S.; Maglione, E.; Arumugam, P.

    2011-10-28

    The nonadiabatic quasiparticle model for triaxial shapes is used to perform calculations for decay of {sup 141}Ho, the only known odd-Z even-N deformed nucleus for which fine structure in proton emission from both ground and isomeric states has been observed. All experimental data corresponding to this unique case namely, the rotational spectra of parent and daughter nuclei, decay widths and branching ratios for ground and isomeric states, could be well explained with a strong triaxial deformation {gamma}{approx}20. The recent experimental observation of fine structure decay from the isomeric state, can be explained only with an assignment of I{sup {pi}} = 3/2{sup +} as the decaying state, in contradiction with the previous assignment, of I{sup {pi}} 1/2{sup +}, based on adiabatic calculations. This study reveals that proton emission measurements could be a precise tool to probe triaxial deformations and other structural properties of exotic nuclei beyond the proton dripline.

  4. Analysis of fine structure in the nuclear continuum

    SciTech Connect

    Shevchenko, A.; Kalmykov, Y.; Neumann-Cosel, P. von; Ponomarev, V. Yu.; Richter, A.; Wambach, J.; Carter, J.; Usman, I.; Cooper, G. R. J.; Fearick, R. W.

    2008-02-15

    Fine structure has been shown to be a general phenomenon of nuclear giant resonances of different multipolarities over a wide mass range. In this article we assess various techniques that have been proposed to extract quantitative information from the fine structure in terms of characteristic scales. These include the so-called local scaling dimension, the entropy index method, Fourier analysis, and continuous and discrete wavelet transforms. As an example, results on the isoscalar giant quadrupole resonance in {sup 208}Pb from high-energy-resolution inelastic proton scattering and calculations with the quasiparticle-phonon model are analyzed. Wavelet analysis, both continuous and discrete, of the spectra is shown to be a powerful tool to extract the magnitude and localization of characteristic scales.

  5. Fine Structure of Dark Energy and New Physics

    DOE PAGESBeta

    Jejjala, Vishnu; Kavic, Michael; Minic, Djordje

    2007-01-01

    Following our recent work on the cosmological constant problem, in this letter we make a specific proposal regarding the fine structure (i.e., the spectrum) of dark energy. The proposal is motivated by a deep analogy between the blackbody radiation problem, which led to the development of quantum theory, and the cosmological constant problem, for which we have recently argued calls for a conceptual extension of the quantum theory. We argue that the fine structure of dark energy is governed by a Wien distribution, indicating its dual quantum and classical nature. We discuss observational consequences of such a picture of darkmore » energy and constrain the distribution function.« less

  6. Relative fine-structure intensities in two-photon excitation

    NASA Technical Reports Server (NTRS)

    Crosley, D. R.; Bischel, W. K.

    1984-01-01

    A discrepancy is pointed out between experimental determinations of the relative intensities for different fine-structure components of the two-photon transitions 2p3P 3p3P in oxygen and 2p3 4S0 - 2p2 3p4D0 in nitrogen, which agreed well with calculations involving a single virtual intermediate level, and a two-photon selection rule dJ not equal to one, derived in a purely theoretical and erroneous treatment of these transitions. Five other experiments are also briefly examined, with the conclusion that relative fine-structure intensities in two-photon transitions are well understood as straightforward extensions of angular momentum coupling in single-photon cases, in accordance with allowed dJ = 0, + or -1, and + or -2 transitions.

  7. Surface Arsenic Speciation of a Drinking-Water Treatment Residual Using X-Ray Absorption Spectroscopy

    SciTech Connect

    Makris, K.C.; Sarkar, D.; Parsons, J.G.; Datta, R.; Gardea-Torresdey, J.L.

    2009-06-03

    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{sup -1}) after 48 h of reaction. Subsequent desorption experiments with a high P load (7500 mg kg{sup -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.

  8. 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.

  9. 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.

  10. Efferent Modulation of Stimulus Frequency Otoacoustic Emission Fine Structure

    PubMed Central

    Zhao, Wei; Dewey, James B.; Boothalingam, Sriram; Dhar, Sumitrajit

    2015-01-01

    Otoacoustic emissions, sounds generated in the inner ear, have become a convenient non-invasive tool to examine the efferent modulation of cochlear mechanics. Activation of the medial olivocochlear (MOC) efferents has been shown to alter the magnitude of these emissions. When the effects of efferent activation on the detailed spectral structures of these emissions have been examined, a shift of the spectral patterns toward higher frequencies has been reported for distortion product and spontaneous otoacoustic emissions. Stimulus frequency otoacoustic emissions (SFOAEs) have been proposed as the preferred emission type in the study of efferent modulation due to the simplicity of their production leading to the possibility of clearer interpretation of results. The effects of efferent activation on the complex spectral patterns of SFOAEs have not been examined to the best of our knowledge. We have examined the effects of activating the MOC efferents using broadband noise in normal-hearing humans. The detailed spectral structure of SFOAEs, known as fine structure, was recorded with and without contralateral acoustic stimulation. Results indicate that SFOAEs are reduced in magnitude and their fine structure pushed to higher frequencies by contralateral acoustic stimulation. These changes are similar to those observed in distortion product or spontaneous otoacoustic emissions and behavioral hearing thresholds. Taken together with observations made about magnitude and phase changes in otoacoustic emissions and hearing thresholds upon contralateral acoustic stimulation, all changes in otoacoustic emission and hearing threshold fine structure appear to be driven by a common set of mechanisms. Specifically, frequency shifts in fine structure patterns appear to be linked to changes in SFOAE phase due to contralateral acoustic stimulation. PMID:26696843

  11. Interpretation of unexpected behavior of infrared absorption spectra of ScF3 beyond the quasiharmonic approximation

    NASA Astrophysics Data System (ADS)

    Piskunov, Sergei; Žguns, Pjotrs A.; Bocharov, Dmitry; Kuzmin, Alexei; Purans, Juris; Kalinko, Aleksandr; Evarestov, Robert A.; Ali, Shehab E.; Rocca, Francesco

    2016-06-01

    Scandium fluoride (ScF3), having cubic ReO3-type structure, has attracted much scientific attention due to its rather strong negative thermal expansion (NTE) in the broad temperature range from 10 to 1100 K. Here we use the results of diffraction and extended x-ray absorption fine-structure (EXAFS) spectroscopy to interpret the influence of NTE on the temperature dependence of infrared absorption spectra of ScF3. Original infrared absorption and EXAFS experiments in a large temperature range are presented and interpreted using ab initio lattice dynamics simulations within and beyond quasiharmonic approximations. We demonstrate that ab initio electronic structure calculations, based on the linear combination of atomic orbitals method with hybrid functionals, are able to reproduce well the experimental values of lattice parameter a0, band gap Eg, and lattice dynamics in ScF3. However, the simulations performed within quasiharmonic approximation fail to reproduce the temperature dependence of two infrared active bands due to the F-Sc-F bending (at 220 cm-1) and Sc-F stretching (at 520 cm-1) modes present in the infrared absorption spectra. To overcome this problem, an approach beyond the quasiharmonic approximation is proposed: It accounts for the negative thermal expansion of the lattice and for fluorine atom displacements due to strong F vibrational motion perpendicular to the cubic axes and allows us to explain qualitatively the temperature behavior of infrared spectra of ScF3.

  12. 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.

  13. X-Ray Absorption Spectroscopy of Dense, Shock Compressed, Laser Plasma

    NASA Astrophysics Data System (ADS)

    Goodman, D. A.

    1992-01-01

    Available from UMI in association with The British Library. Requires signed TDF. The central theme of this work involves the diagnosis of shock compressed highly correlated laser plasmas, by observation of the Extended X-ray Absorption Fine Structure (EXAFS) in the absorption spectrum. Measurements have been made using a plane crystal mini-spectrometer and a spectrometer purpose built for EXAFS measurement which employed an elliptically curved x-ray dispersing crystal. Chapter 1 serves as a very brief introduction to the plasma state, and describes how the strongly coupled plasmas which are of interest to this work are created, through laser interaction, and theoretically modelled. Chapters 2, 3 and 4 concern the development and the testing of the elliptical spectrometer. Chapter 2 introduces the theoretical models and concepts which have been developed to predict the behaviour of the spectrometer, and demonstrates how these predictions have influenced the spectrometer design. Chapter 3 charts the development of the EXAFS spectrometer from the early plane crystal geometry to the successful elliptical crystal arrangement. Also described is the process by which the x-ray dispersing crystals are bent to the correct elliptical contour. Chapter 4 describes the testing of the elliptical spectrometer prior to EXAFS measurement, in order to assess the viability of the spectrometer alignment procedure and the general viability of the spectrometer as a diagnostic device. Chapter 5 is concerned with the experimental details of the plasma EXAFS studies. The use of both planar and elliptical crystal spectrometers, in the VULCAN glass laser environment is described. Chapter 6 is concerned with the analysis of the experimental results. The models by which the density, temperature and ion correlation are calculated are introduced, and applied to EXAFS measurements from both spectrometers. The results are presented in tabular and graphical form and discussed at length. Chapter 7

  14. EXAFS studies of local thermal expansion

    SciTech Connect

    Beccara, S.; Dalba, G.; Fornasini, P.; Grisenti, R.; Sanson, A.; Rocca, F.; Purans, J.; Diop, D.

    2003-01-24

    Original information on local thermal expansion can be obtained through a cumulant analysis of EXAFS. The difference between first and third EXAFS cumulants, and the comparison with Bragg diffraction results, can help in disentangling the contributions to thermal expansion of potential anharmonicity and geometrical effects. In germanium, the perpendicular Mean Square Relative Displacement has been obtained from EXAFS. In Ag2O, whose framework structure exhibits negative thermal expansion, a positive expansion of the Ag-O bond has been measured and the deformation of the Ag4O structural units monitored.

  15. EXAFS Energy Shift and Structural Parameters

    NASA Astrophysics Data System (ADS)

    Kelly, Shelly D.; Ravel, Bruce

    2007-02-01

    In EXAFS analysis, the energy shift parameter is used to align the theoretical calculated spectrum to the energy grid of the measured spectrum. Unrealistically large energy shift values, sometimes in excess of 20 eV, are at times published in research articles. We therefore see the need for a concise discussion of the EXAFS energy shift parameter. This paper is intended as a learning tool for the proper alignment of theory to measured EXAFS spectra and proper interpretation of the energy shift parameter.

  16. EXAFS studies on the structure of photoexcited cyclopentadienylnickelnitrosyl(C{sub 5}H{sub 5}NiNO)

    SciTech Connect

    Chen, L.X.; Bowman, M.K.; Montano, A.; Norris, J.R. |

    1993-05-01

    The structures of C{sub 5}H{sub 5}NiNO in a reversible photochemical reaction were studied via EXAFS, FTIR, and optical absorption spectroscopies. A photoexcited intermediate with distinctively different EXAFS, IR, and optical absorption spectra from those of the ground state molecules was generated upon irradiation using 365 mn light at 20K in a 3-methylpentane solution. The reverse reaction was induced by irradiation with 310 mn light. The EXAFS data analysis has shown a 0.12 {Angstrom} elongation of the Ni-N bond and the bending, of Ni-N-0 in the photoexcited intermediate. Several ZINDO calculations were conducted based on the structures obtained from the EXAFS spectroscopy. These calculations reproduced the changes in the optical spectra and the intramolecular electron transfer in C{sub 5}H{sub 5}NiNO.

  17. EXAFS studies on the structure of photoexcited cyclopentadienylnickelnitrosyl(C[sub 5]H[sub 5]NiNO)

    SciTech Connect

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

    1993-01-01

    The structures of C[sub 5]H[sub 5]NiNO in a reversible photochemical reaction were studied via EXAFS, FTIR, and optical absorption spectroscopies. A photoexcited intermediate with distinctively different EXAFS, IR, and optical absorption spectra from those of the ground state molecules was generated upon irradiation using 365 mn light at 20K in a 3-methylpentane solution. The reverse reaction was induced by irradiation with 310 mn light. The EXAFS data analysis has shown a 0.12 [Angstrom] elongation of the Ni-N bond and the bending, of Ni-N-0 in the photoexcited intermediate. Several ZINDO calculations were conducted based on the structures obtained from the EXAFS spectroscopy. These calculations reproduced the changes in the optical spectra and the intramolecular electron transfer in C[sub 5]H[sub 5]NiNO.

  18. COLLISIONAL EXCITATION OF THE [C II] FINE STRUCTURE TRANSITION IN INTERSTELLAR CLOUDS

    SciTech Connect

    Goldsmith, Paul F.; Langer, William D.; Pineda, Jorge L.; Velusamy, T.

    2012-11-15

    We analyze the collisional excitation of the 158 {mu}m (1900.5 GHz) fine structure transition of ionized carbon in terms of line intensities produced by simple cloud models. The single C{sup +} fine structure transition is a very important coolant of the atomic interstellar medium (ISM) and of photon-dominated regions in which carbon is partially or completely in ionized form. The [C II] line is widely used as a tracer of star formation in the Milky Way and other galaxies. Excitation of the [C II] fine structure transition can be via collisions with hydrogen molecules, atoms, and electrons. Analysis of [C II] observations is complicated by the fact that it is difficult to determine the optical depth of the line. We discuss the excitation of the [C II] line, deriving analytic results for several limiting cases and carry out numerical solutions using a large velocity gradient model for a more inclusive analysis. For antenna temperatures up to 1/3 of the brightness temperature of the gas kinetic temperature, the antenna temperature is linearly proportional to the column density of C{sup +} irrespective of the optical depth of the transition. This is appropriately referred to as the effectively optically thin approximation. We review the critical densities for excitation of the [C II] line by various collision partners, briefly analyze C{sup +} absorption, and conclude with a discussion of C{sup +} cooling and how the considerations for line intensities affect the behavior of this important coolant of the ISM.

  19. 3D Whole-prominence Fine Structure Modeling. II. Prominence Evolution

    NASA Astrophysics Data System (ADS)

    Gunár, Stanislav; Mackay, Duncan H.

    2015-10-01

    We use the new three-dimensional (3D) whole-prominence fine structure model to study the evolution of prominences and their fine structures in response to changes in the underlying photospheric magnetic flux distribution. The applied model combines a detailed 3D prominence magnetic field configuration with a realistic description of the prominence plasma distributed along multiple fine structures. In addition, we utilize an approximate Hα visualization technique to study the evolution of the visible cool prominence plasma both in emission (prominence) and absorption (filament). We show that the initial magnetic field configuration of the modeled prominence is significantly disturbed by the changing position of a single polarity of a magnetic bipole as the bipole is advected toward the main body of the filament. This leads to the creation of a barb, which becomes the dominant feature visible in the synthetic Hα images of both the prominence and filament views. The evolution of the bipole also creates conditions that lead to the disappearance and reappearance of large portions of the main body. We also show that an arch-like region containing a dark void (a bubble) can be naturally produced in the synthetic prominence Hα images. While not visible in terms of the magnetic field lines, it is due to a lack of Hα emission from low-pressure, low-density plasma located in shallow magnetic dips lying along the lines of sight intersecting the dark void. In addition, a quasi-vertical small-scale feature consisting of short and deep dips, piled one above the other, is produced.

  20. Silver Valence and Local Environments in Borosilicate and Calcium Aluminoborate Waste Glasses as determined from X-ray Absorption Spectroscopy

    SciTech Connect

    McKeown,D.; Gan, H.; Pegg, I.

    2005-01-01

    Silver K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data were collected and analyzed to characterize silver (Ag) environments in borosilicate and Ca-aluminoborate glass formulations developed as potential candidates for the immobilization of certain nuclear wastes. Silver is found in some nuclear waste streams and must be encapsulated in glass during waste vitrification processes. A related concern deals with phase separation within these glasses and whether colloidal silver would be present in the glass melt, which could present processing issues, or in the waste glass product. Characterization of the silver environments provides useful information for optimizing the silver incorporation ability of such glasses. Data were also gathered on four crystalline standards: Ag-foil, Ag{sub 2}O, argentojarosite (AgFe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6}), and AgO. XANES data indicate Ag{sup +} as the dominant species in the glasses. XANES and EXAFS data show that the average Ag environment in the Ca-aluminoborate glass is different compared with those in the two borosilicate glasses investigated. EXAFS analyses show that Ag in the borosilicate glasses is coordinated by two oxygens in a similar environment to that in crystalline Ag{sub 2}O, except that the associated Ag-O distances are approximately 0.10 Angstroms longer in the glass. Silver in the Ca-aluminoborate glass may be within one highly disordered site, or possibly, several different sites, where the average Ag-O distance, coordination number, and Debye-Waller factor are larger than those determined for the borosilicate glasses. Despite their relatively high silver contents, there is no evidence from XANES or EXAFS of colloidal silver in the glasses investigated.

  1. Nearly Uniform Decaosmium Clusters Supported on MgO: Characterization by X-ray Absorption Spectroscopy and Scanning Transmission Electron Microscopy

    SciTech Connect

    Kulkarni, A.; Mehraeen, S; Reed, B; Okamoto, N; Browning, N; Gates, B

    2009-01-01

    Samples containing small, nearly uniform clusters of a heavy metal, Os, were prepared on a high-area porous support consisting of light atoms, MgO, to provide an opportunity for a critical assessment of estimates of cluster size determined by extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM). Supported carbonyl clusters approximated as decaosmium were prepared by reductive carbonylation of adsorbed Os3(CO)12 at 548 K and 1 bar. Infrared (IR) spectra of the clusters resemble those attributed in earlier work to supported clusters similar to [Os10C(CO)24]2-, consistent with the EXAFS data. The spectra indicate a molar yield of decaosmium carbonyl clusters of about 65-70%. As these clusters were treated in flowing H2, they were partially decarbonylated, as shown by IR and EXAFS spectra. The rms (root-mean-square) radii of the undecarbonylated and partially decarbonylated clusters were found by HAADF-STEM to be 3.11 {+-} 0.09 and 3.06 {+-} 0.05 A, respectively, and the close agreement between these values is consistent with the inference that the cluster frame was essentially the same in each. The average rms radius of the undecarbonylated clusters, estimated on the basis of EXAFS data, was 2.94 {+-} 0.07 A, calculated on the basis of the assumption that the osmium frame matched that of [Os10C(CO)24]2-. EXAFS analysis of the data characterizing the partially decarbonylated sample, aided by the STEM results, showed, consistent with the STEM results, that the partial decarbonylation did not lead to a significant change in the rms radius of the metal frame.

  2. The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

    NASA Astrophysics Data System (ADS)

    Panfili, Frédéric; Manceau, Alain; Sarret, Géraldine; Spadini, Lorenzo; Kirpichtchikova, Tatiana; Bert, Valérie; Laboudigue, Agnès; Marcus, Matthew A.; Ahamdach, Noureddine; Libert, Marie-Françoise

    2005-05-01

    The maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies such as phytoremediation. In the present work, the mineralogical transformations of Zn-containing phases induced by two graminaceous plants (A grostis tenuis and Festuca rubra) in a contaminated sediment ([Zn] = 4700 mg kg -1, [P 2O 5] = 7000 mg kg -1, pH = 7.8), untreated or amended with hydroxylapatite (AP) or Thomas basic slag (TS), were investigated after two yr of pot experiment by scanning electron microscopy coupled with energy-dispersive spectrometry (SEM-EDS), synchrotron-based X-ray microfluorescence (μ-SXRF), and powder and laterally resolved extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. The number and nature of Zn species were evaluated by principal component (PCA) and least-squares fitting (LSF) analysis of the entire set of μ-EXAFS spectra, which included up to 32 individual spectra from regions of interest varying in chemical composition. Seven Zn species were identified at the micrometer scale: sphalerite, gahnite, franklinite, Zn-containing ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted kerolite-like trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra. In the untreated and unvegetated sediment, Zn was distributed as ˜50% (mole ratio of total Zn) sphalerite, ˜40% Zn-ferrihydrite, and ˜10 to 20% (Zn-Al)-hydrotalcite plus Zn-phyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20% and were replaced by Zn-phosphate (˜30˜40%). In the presence of plants, ZnS was almost completely

  3. Evidence for the Presence of Colloidal Metacinnabar in Mercury-DOM-Sulfide Systems as Determined by a Chromatographic-EXAFS Method

    NASA Astrophysics Data System (ADS)

    Gerbig, C. A.; Kim, C. S.; Moreau, J. W.; Aiken, G. R.; Krabbenhoft, D. P.; Nagy, K. L.; Ryan, J. N.

    2008-12-01

    Mercury speciation and bioavailability is frequently thought to be controlled by the presence of dissolved organic matter (DOM) and sulfide. However, the speciation of mercury in these systems is poorly understood due to the complex interactions of mercury, DOM, and sulfide. We have developed a combined chromatographic-extended x-ray absorption fine structure (EXAFS) spectroscopy approach to determine the speciation of the hydrophobic fraction of mercury species in both sulfide-free and sulfide-rich (100 μM) experimental systems that also contain dissolved organic matter isolated from several locations, including the Florida Everglades. Chromatographic experiments were carried out with and without sulfide at varied mercury concentrations ranging from 0.1 nM to 1 μM in the presence of 10 mg L-1 DOM. The method consists of equilibrating the mercury-DOM with or without sulfide for 20 h (pH 6.5, I 0.1M) followed by chromatographic fractionation and concentration on a small column of C18 resin. Greater than 80% of the mercury in all solutions was found to be hydrophobic with respect to the resin when the mercury was interacting with the strong-binding DOM sites. The chromatographic behavior of solutions with and without sulfide was distinctly different. Sulfide-free mercury-DOM systems exhibited typical chromatographic behavior exemplified by resin saturation and subsequent breakthrough of mercury species. The sulfide-rich system exhibited very high resin affinity for almost all mercury species in solution and no apparent breakthrough, regardless of the ratio of mercury to DOM. Similar chromatographic experiments were carried out with and without sulfide at mercury concentrations as low as 250 nM and a DOM concentration of 50 mg L-1. EXAFS spectroscopy at the mercury LIII edge clearly showed spectra consistent with metacinnabar (HgS) as the dominant form of mercury adsorbed to the resin under sulfidic conditions despite the fact that no bulk precipitation was observed

  4. Hydration of Lanthanoid(III) Ions in Aqueous Solution And Crystalline Hydrates Studied By EXAFS Spectroscopy And Crystallography: the Myth of the 'Gadolinium Break'

    SciTech Connect

    Persson, I.; D'Angelo, P.; Panfilis, S.De; Sandstrom, M.; Eriksson, L.

    2009-05-21

    The structures of the hydrated lanthanoid(III) ions including lanthanum(III) have been characterized in aqueous solution and in the solid trifluoromethanesulfonate salts by extended X-ray absorption fine structure (EXAFS) spectroscopy. At ambient temperature the water oxygen atoms appear as a tricapped trigonal prism around the lanthanoid(III) ions in the solid nonaaqualanthanoid(III) trifluoromethanesulfonates. Water deficiency in the capping positions for the smallest ions starts at Ho and increases with increasing atomic number in the [Ln(H(2)O)(9-x)](CF(3)SO(3))(3) compounds with x=0.8 at Lu. The crystal structures of [Ho(H(2)O)(8.91)](CF(3)SO(3))(3) and [Lu(H(2)O)(8.2)](CF(3)SO(3))(3) were re-determined by X-ray crystallography at room temperature, and the latter also at 100 K after a phase-transition at about 190 K. The very similar Ln K- and L(3)-edge EXAFS spectra of each solid compound and its aqueous solution indicate indistinguishable structures of the hydrated lanthanoid(III) ions in aqueous solution and in the hydrated trifluoromethanesulfonate salt. The mean Ln--O bond lengths obtained from the EXAFS spectra for the largest ions, La-Nd, agree with estimates from the tabulated ionic radii for ninefold coordination but become shorter than expected starting at samarium. The deviation increases gradually with increasing atomic number, reaches the mean Ln-O bond length expected for eightfold coordination at Ho, and increases further for the smallest lanthanoid(III) ions, Er-Lu, which have an increasing water deficit. The low-temperature crystal structure of [Lu(H(2)O)(8.2)](CF(3)SO(3))(3) shows one strongly bound capping water molecule (Lu-O 2.395(4) A) and two more distant capping sites corresponding to Lu-O at 2.56(1) A, with occupancy factors of 0.58(1) and 0.59(1). There is no indication of a sudden change in hydration number, as proposed in the 'gadolinium break' hypothesis.

  5. Nucleocapsid zinc fingers detected in retroviruses: EXAFS studies of intact viruses and the solution-state structure of the nucleocapsid protein from HIV-1.

    PubMed Central

    Summers, M. F.; Henderson, L. E.; Chance, M. R.; Bess, J. W.; South, T. L.; Blake, P. R.; Sagi, I.; Perez-Alvarado, G.; Sowder, R. C.; Hare, D. R.

    1992-01-01

    All retroviral nucleocapsid (NC) proteins contain one or two copies of an invariant 3Cys-1His array (CCHC = C-X2-C-X4-H-X4-C; C = Cys, H = His, X = variable amino acid) that are essential for RNA genome packaging and infectivity and have been proposed to function as zinc-binding domains. Although the arrays are capable of binding zinc in vitro, the physiological relevance of zinc coordination has not been firmly established. We have obtained zinc-edge extended X-ray absorption fine structure (EXAFS) spectra for intact retroviruses in order to determine if virus-bound zinc, which is present in quantities nearly stoichiometric with the CCHC arrays (Bess, J.W., Jr., Powell, P.J., Issaq, H.J., Schumack, L.J., Grimes, M.K., Henderson, L.E., & Arthur, L.O., 1992, J. Virol. 66, 840-847), exists in a unique coordination environment. The viral EXAFS spectra obtained are remarkably similar to the spectrum of a model CCHC zinc finger peptide with known 3Cys-1His zinc coordination structure. This finding, combined with other biochemical results, indicates that the majority of the viral zinc is coordinated to the NC CCHC arrays in mature retroviruses. Based on these findings, we have extended our NMR studies of the HIV-1 NC protein and have determined its three-dimensional solution-state structure. The CCHC arrays of HIV-1 NC exist as independently folded, noninteracting domains on a flexible polypeptide chain, with conservatively substituted aromatic residues forming hydrophobic patches on the zinc finger surfaces. These residues are essential for RNA genome recognition, and fluorescence measurements indicate that at least one residue (Trp37) participates directly in binding to nucleic acids in vitro. The NC is only the third HIV-1 protein to be structurally characterized, and the combined EXAFS, structural, and nucleic acid-binding results provide a basis for the rational design of new NC-targeted antiviral agents and vaccines for the control of AIDS. PMID:1304355

  6. As(III) immobilization on gibbsite: Investigation of the complexation mechanism by combining EXAFS analyses and DFT calculations

    NASA Astrophysics Data System (ADS)

    Duarte, Graziele; Ciminelli, Virginia S. T.; Dantas, Maria S. S.; Duarte, Helio A.; Vasconcelos, Igor F.; Oliveira, Augusto F.; Osseo-Asare, Kwadwo

    2012-04-01

    The complexation of aqueous As(III) species on gibbsite was investigated as a function of pH. Theoretical calculations and X-ray absorption fine structure spectroscopy (XAFS) were combined to elucidate the structure of arsenite surface complexes on synthetic gibbsite. Several adsorption sites were evaluated using the self-consistent charge corrected density-functional based tight-binding (SCC-DFTB) method. The formation of bidentate-binuclear, bidentate-mononuclear, monodentate-mononuclear, and monodentate-binuclear complexes by means of both acid-base and non-dissociative mechanisms was studied in detail. The SCC-DFTB calculations showed the bidentate-binuclear/acid-base complex as the most thermodynamically stable geometry for As(III) bonding to gibbsite surface, estimating As-O and As-Al distances of 1.75 and 3.24 Å, respectively. EXAFS results also demonstrated As(III) complexation to three oxygen atoms in the first shell, at a distance of 1.77 Å, and to aluminum in the second shell at a distance of 3.21 Å, characteristic of bidentate-binuclear configuration, at pH 5.0, 7.0 and 9.0. Another As-Al interaction, attributed to the monodentate-binuclear complex due to its distance of 3.49 Å, was shown from EXAFS results to provide a minor contribution to As(III) sorption on gibbsite. Therefore, results from theoretical calculations and experimental measurements confirmed the occurrence of inner-sphere complexation during the As(III) adsorption on gibbsite, in a pH range of 5-9. Hence, the higher As(III) mobility in the environment, when compared to As(V), was suggested to be related to the protonation of the As(III) adsorbed complexes. This protonation would restore the neutral H3AsO3 molecule, which could be then released from the mineral surface. These results might be useful to predict and control arsenic mobility in aqueous environments, particularly where Al oxy-hydroxides are often found.

  7. EXAFS study of copper-hafnium multilayers

    SciTech Connect

    Heald, S.M.; Tranquada, J.M.; Clemens, B.M.; Stec, J.P.

    1986-01-01

    EXAFS measurements have been made on a number of Cu-Hf multilayers with modulation wavelengths of 1/2 to 20 close-packed monolayers. Clear indications are found for an amorphous interfacial compound. Fitting of the EXAFS spectra indicate that the interfacial regions are about 8 to 10 layers thick, and contain nearly equal numbers of layers of Hf and Cu. Results are compared to x-ray diffraction studies of the same samples.

  8. Processing of temporal fine structure as a function of age

    PubMed Central

    Grose, John H.; Mamo, Sara K.

    2010-01-01

    Objectives The purpose of this study was to determine whether the processing of temporal fine structure diminishes with age, even in the presence of relatively normal audiometric hearing. Temporal fine structure processing was assessed by measuring the discrimination of inter-aural phase differences (IPDs). The hypothesis was that IPD discrimination is more acute in middle-aged observers than in older observers but that acuity in middle-aged observers is nevertheless poorer than in young adults. Design Two experiments were undertaken. The first measured discrimination of 0-and π-radian inter-aural phases as a function of carrier frequency. The stimulus was a 5-Hz sinusoidally amplitude modulated tone where, in the signal waveform, the inter-aural phase of the carrier was inverted during alternate modulation periods. The second experiment measured IPD discrimination at fixed frequencies. The stimulus was a pair of tone pulses where, in the signal, the trailing pulse contained an IPD. A total of 39 adults with normal audiograms below 2000 Hz participated: 15 younger, 12 middle-aged, and 12 older. Results Experiment 1 showed that the highest carrier frequency at which a π-radian IPD could be discriminated from the diotic, 0-radian standard was significantly lower in middle-aged listeners than young adults, and lower still in older listeners. Experiment 2 indicated that middle-aged listeners were less sensitive to IPDs than young adults at all but the lowest frequencies tested. Older listeners, as a group, had the poorest thresholds. Conclusions These results suggest that deficits in temporal fine structure processing are evident in the pre-senescent auditory system. This adds to the accumulating evidence that deficiencies in some aspects of auditory temporal processing emerge relatively early in the aging process. It is possible that early-emerging temporal processing deficits manifest themselves in challenging speech-in-noise environments. PMID:20592614

  9. Fine structure of a resonantly excited p -shell exciton in a CdTe quantum dot

    NASA Astrophysics Data System (ADS)

    Smoleński, T.; Kazimierczuk, T.; Goryca, M.; Wojnar, P.; Kossacki, P.

    2016-05-01

    We present a polarization-resolved photoluminescence excitation study of the absorption spectrum of a p -shell neutral exciton in a single CdTe/ZnTe quantum dot. We find that the fine structure of the p -shell exciton is completely analogous to the fine structure of the s -shell exciton, including the selection rules and the effects of a magnetic field applied in Faraday and Voigt configurations. The energy spectrum of the p -shell exciton is found to be well described by introducing respective isotropic and anisotropic constants of the exchange interaction between a p -shell electron and a p -shell hole. The typical values of these exchange constants averaged over several randomly selected quantum dots yield δ0p p=(0.92 ±0.16 ) meV and δ1p p=(0.58 ±0.25 ) meV. Additionally, we demonstrate that the nonresonant relaxation of the p -shell exciton conserves the exciton spin to a very high degree for both bright and dark exciton configurations.

  10. XANES, EXAFS and Kbeta spectroscopic studies of the oxygen-evolving complex in Photosystem II

    SciTech Connect

    Robblee, John H.

    2000-12-01

    A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S{sub 3} {r_arrow} [S{sub 4}] {r_arrow} S{sub 0} transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn K{beta} X-ray emission spectroscopy (Kb XES) to this problem for the first time. The K{beta} XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S{sub 2} {r_arrow} S{sub 3} transition, in contrast to the S{sub 0} {r_arrow} S{sub 1} and S{sub 1} {r_arrow} S{sub 2} transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese {mu}-oxo bridge radical formation during the S{sub 2} {r_arrow} S{sub 3} transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S{sub 0} state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-{mu}-oxo-bridged Mn-Mn moieties increases from 2.7 {angstrom} in the S{sub 1} state to 2.85 {angstrom} in the S{sub 0} state. Furthermore, evidence is presented that shows three di-{mu}-oxo binuclear Mn{sub 2} clusters may be present in the OEC, which is contrary to the widely held theory that two such clusters are present in the OEC. The EPR properties of the S{sub 0} state have been investigated and a characteristic ''multiline'' signal in the S{sub 0} state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S{sub 0} state is paramagnetic. In addition, this signal was simulated using parameters derived from three possible oxidation states of Mn in the S{sub 0

  11. Fischer-Tropsch synthesis: study of the promotion of Pt on the reduction property of Co/Al2O3 catalysts by in situ EXAFS of Co K and Pt LIII edges and XPS.

    PubMed

    Jacobs, Gary; Chaney, John A; Patterson, Patricia M; Das, Tapan K; Maillot, Julie C; Davis, Burtron H

    2004-09-01

    The addition of platinum metal to cobalt/alumina-based Fischer-Tropsch synthesis (FTS) catalysts increases both the reduction rate and, consequently, the density of active cobalt sites. Platinum also lowers the temperature of the two-step conversion of cobalt oxide to cobalt metal observed in temperature programmed reduction (TPR) as Co3O4 to CoO and CoO to Co0. The interaction of the alumina support with cobalt oxide ultimately determines the active site density of the catalyst surface. This interaction can be controlled by varying the cobalt loading and dispersion, selecting supports with differing surface areas or pore sizes, or changing the noble metal promoter. However, the active site density is observed to depend primarily on the cluster size and extent of reduction, and there is a direct relationship between site density and FTS rate. In this work, in situ extended X-ray absorption fine structure (EXAFS) at the LIII edge of Pt was used to show that isolated Pt atoms interact with supported cobalt clusters without forming observable Pt--Pt bonds. K-edge EXAFS was also used to verify that the cobalt cluster size increases slightly for those systems with Pt promotion. X-ray absorption near-edge spectroscopy (XANES) was used to examine the remaining cobalt clusters after the first stage of TPR, and it revealed that the species were almost entirely cobalt (II) oxide. After the second stage of TPR to form cobalt metal, a residual oxide persists in the sample, and this oxide has been identified as cobalt (II) aluminate using X-ray photoelectron spectroscopy (XPS). Sequential in situ reduction of promoted and unpromoted systems was also monitored through XPS, and Pt was seen to increase the extent of cobalt reduction by a factor of two. PMID:15310958

  12. New Tests for Variations of the Fine Structure Constant

    NASA Technical Reports Server (NTRS)

    Prestage, John D.

    1995-01-01

    We describe a new test for possible variations of the fine structure constant, by comparisons of rates between clocks based on hyperfine transitions in alkali atomos with different atomic number Z. H- maser, Cs and Hg+ clocks have a different dependence on ia relativistic contributions of order (Z. Recent H-maser vs Hg+ clock comparison data improves laboratory limits on a time variation by 100-fold to giveFuture laser cooled clocks (Be+, Rb, Cs, Hg+, etc.), when compared, will yield the most senstive of all tests for.

  13. Fine Structure and Optical Depth in the Solar Transition Region

    NASA Astrophysics Data System (ADS)

    Plovanic, Jacob; Kankelborg, C. C.; Williamson, K.

    2011-05-01

    Unresolved fine structure in the solar transition region (TR) has long been inferred from measurements of density-sensitive line pairs showing low filling factor (< 0.01). Low filling factor models for the structure of the He II source region, however, have not been well studied. We propose a highly structured model of the lower atmosphere in which He II is formed at low filling factors, leading to high emission measure and an optically thin He II line. This transparent TR material is juxtaposed with absorbing chromospheric structures, leading to the nearly uniform center to limb behavior of the He II line as observed.

  14. Topological Quantization in Units of the Fine Structure Constant

    SciTech Connect

    Maciejko, Joseph; Qi, Xiao-Liang; Drew, H.Dennis; Zhang, Shou-Cheng; /Stanford U., Phys. Dept. /Stanford U., Materials Sci. Dept. /SLAC

    2011-11-11

    Fundamental topological phenomena in condensed matter physics are associated with a quantized electromagnetic response in units of fundamental constants. Recently, it has been predicted theoretically that the time-reversal invariant topological insulator in three dimensions exhibits a topological magnetoelectric effect quantized in units of the fine structure constant {alpha} = e{sup 2}/{h_bar}c. In this Letter, we propose an optical experiment to directly measure this topological quantization phenomenon, independent of material details. Our proposal also provides a way to measure the half-quantized Hall conductances on the two surfaces of the topological insulator independently of each other.

  15. Fine structure of the solar transition region - Observations and interpretation

    NASA Technical Reports Server (NTRS)

    Cook, J. W.; Brueckner, G. E.

    1991-01-01

    An evaluation is conducted of recent high spatial resolution observations of the solar transition region and temperature minimum, in the form of UV spectra and spectroheliographs from both sounding rockets and the Spacelab 2 flights of the High Resolution Telescope and Spectrograph (HRTS). Attention is given to the solar atmosphere structure implications of the HRST's observational results. The inclusion of fine structure in conjectures concerning the transition region affects the plausibility of 1D average models of the solar atmosphere, as well as the determination of temperature gradients, possible nonradiative-heating mechanisms, and the comparison of transition region structures with corresponding observations of the photosphere and corona.

  16. A simple cosmology with a varying fine structure constant.

    PubMed

    Sandvik, Håvard Bunes; Barrow, John D; Magueijo, João

    2002-01-21

    We investigate the cosmological consequences of a theory in which the electric charge e can vary. In this theory the fine structure "constant," alpha, remains almost constant in the radiation era, undergoes a small increase in the matter era, but approaches a constant value when the universe starts accelerating because of a positive cosmological constant. This model satisfies geonuclear, nucleosynthesis, and cosmic microwave background constraints on time variation in alpha, while fitting the observed accelerating Universe and evidence for small alpha variations in quasar spectra. It also places specific restrictions on the nature of the dark matter. Further tests, involving stellar spectra and Eötvös experiments, are proposed. PMID:11801051

  17. Complexation of Mercury(II) in Soil Organic Matter: EXAFS Evidence for Linear Two-Coordination with Reduced Sulfur Groups

    SciTech Connect

    Skyllberg,U.; Bloom, P.; Qian, J.; Lin, C.; Bleam, W.

    2006-01-01

    The chemical speciation of inorganic mercury (Hg) is to a great extent controlling biologically mediated processes, such as mercury methylation, in soils, sediments, and surface waters. Of utmost importance are complexation reactions with functional groups of natural organic matter (NOM), indirectly determining concentrations of bioavailable, inorganic Hg species. Two previous extended X-ray absorption fine structure (EXAFS) spectroscopic studies have revealed that reduced organic sulfur (S) and oxygen/nitrogen (O/N) groups are involved in the complexation of Hg(II) to humic substances extracted from organic soils. In this work, covering intact organic soils and extending to much lower concentrations of Hg than before, we show that Hg is complexed by two reduced organic S groups (likely thiols) at a distance of 2.33 Angstroms in a linear configuration. Furthermore, a third reduced S (likely an organic sulfide) was indicated to contribute with a weaker second shell attraction at a distance of 2.92-3.08 Angstroms. When all high-affinity S sites, corresponding to 20-30% of total reduced organic S, were saturated, a structure involving one carbonyl-O or amino-N at 2.07 Angstroms and one carboxyl-O at 2.84 Angstroms in the first shell, and two second shell C atoms at an average distance of 3.14 Angstroms, gave the best fit to data. Similar results were obtained for humic acid extracted from an organic wetland soil. We conclude that models that are in current use to describe the biogeochemistry of mercury and to calculate thermodynamic processes need to include a two-coordinated complexation of Hg(II) to reduced organic sulfur groups in NOM in soils and waters.

  18. CTR diffraction and grazing-incidence EXAFS study of U(VI) adsorption onto α-Al 2O 3 and α-Fe 2O 3 (11¯02) surfaces

    NASA Astrophysics Data System (ADS)

    Catalano, Jeffrey G.; Trainor, Thomas P.; Eng, Peter J.; Waychunas, Glenn A.; Brown, Gordon E.

    2005-07-01

    Evaluation of the long-term health risks of uranium contamination in soils, sediments, and groundwater requires a fundamental understanding of the various processes affecting subsurface transport of uranium, including adsorption processes at mineral/water interfaces. In this study, the sites of binding and surface complexation of U(VI) adsorbed on the (11¯02) surfaces of α-Al 2O 3 and α-Fe 2O 3 have been determined using crystal truncation rod (CTR) diffraction and grazing incidence extended X-ray absorption fine structure (GI-EXAFS) spectroscopy. The available binding sites on the (11¯02) surfaces were constrained through bond valence and steric analyses. On both surfaces, U(VI) forms uranyl-carbonato ternary complexes to surface oxygens that are singly coordinated to aluminum or iron. On the α-Al 2O 3 (11¯02) surface, a monodentate complex results, whereas on the α-Fe 2O 3 (11¯02) surface, the binding is bidentate to adjacent singly coordinated oxygen sites (i.e., binuclear). Differences in protonation of the singly coordinated oxygen atoms, surface charging, U(VI) aqueous speciation, substrate structure, or the electronic structure of surface functional groups may be the cause of these differences in adsorption geometry. Both XPS and CTR diffraction reveal higher U(VI) surface coverages on the α-Fe 2O 3 (11¯02) surface than on the α-Al 2O 3 (11¯02) surface. This difference cannot be the result of differences in defect concentration alone as CTR diffraction is not sensitive to U(VI) sorbed to defect sites, implying that the α-Fe 2O 3 (11¯02) surface has an intrinsically higher affinity for U(VI). The surface complexes observed in this study are different from the bidentate, mononuclear complexes typically derived for U(VI) on powdered aluminum- and iron-(oxyhydr)oxides and clay minerals using U L III-edge EXAFS spectroscopy. However, the presence of monodentate, mononuclear and bidentate, binuclear complexes may have been overlooked in past EXAFS

  19. Combined in Situ X-ray absorption and diffuse reflectance infraredspectroscopy: An attractive tool for catalytic investigations

    SciTech Connect

    Marinkovic, N.S.; Ehrlich, S.; Wang, Q.; Barrio, L.; Khalid, S.; et.al.

    2010-11-24

    Catalysis investigations are often followed in a range of spectroscopic techniques. While diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) can be done on a bench-top instrument, X-ray absorption spectroscopy (XAS) techniques, such as extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) require synchrotron light. In order to ensure the same conditions during in situ catalysis for each method, a combined XAS/DRIFTS has been developed at beamline X18A at the National Synchrotron Light Source, Brookhaven National Laboratory. A rapid-scan FTIR spectrometer capable of both mid- and far-infrared measurements is equipped with an arm to redirect the IR beam outside the spectrometer. An in situ reaction chamber, equipped with glassy carbon windows for X-ray light and a KBr window for IR light passage is installed firmly on the arm. The reaction cell can be heated to 600 C and allows passage of gases through the catalyst so that both XAS and DRIFTS techniques can be done simultaneously in controlled environment conditions. Together with a fast-moving monochromator for quick-EXAFS and mass-spectrometric residual gas analysis, this new tool is a powerful method for testing catalytic reactions in real time.

  20. X-ray-absorption-spectroscopy study of manganese-containing compounds and photosynthetic spinach chloroplasts

    SciTech Connect

    Kirby, J.A.

    1981-05-01

    The manganese sites in chloroplasts, long thought to be involved in photosynthetic oxygen evolution have been examined and partially characterized by x-ray Absorption Spectroscopy (XAS) using synchrotron radiation. The local environment about the manganese atoms is estimated from an analysis of the extended X-ray Absorption Fine Structure (EXAFS). Comparisons with and simulations of the manganese EXAFS for several reference compounds leads to a model in which the chloroplast manganese atoms are contained in a binuclear complex similar to di-u-oxo-tetrakis-(2,2'-bipyridine) dimanganese. It is suggested that the partner metal is another manganese. The bridging ligands are most probably oxygen. The remaining manganese ligands are carbon, oxygen, or nitrogen. A roughly linear correlation between the X-ray K edge onset energy and the coordination charge of a large number of manganese coordination complexes and compounds has been developed. Entry of the chloroplast manganese edge energy onto this correlation diagram establishes that the active pool of manganese is in an oxidation state greater than +2.

  1. An x-ray absorption study of the iron site in bacterial photosynthetic reaction centers.

    PubMed Central

    Bunker, G; Stern, E A; Blankenship, R E; Parson, W W

    1982-01-01

    Measurements were made of the extended x-ray absorption fine structure (EXAFS) of the iron site in photosynthetic reaction centers from the bacterium Rhodopseudomonas sphaeroides. Forms with two quinones, two quinones with added o-phenanthroline, and one quinone were studied. Only the two forms containing two quinones maintained their integrity and were analyzed. The spectra show directly that the added o-phenanthroline does not chelate the iron atom. Further analysis indicates that the iron is octahedrally coordinated by nitrogen and/or oxygen atoms located at various distances, with the average value of about 2.14 A. The analysis suggests that most of the ligands are nitrogens and that three of the nitrogen ligands belong to histidine rings. This interpretation accounts for several unusual features of the EXAFS spectrum. We speculate that the quinones are bound to the histidine rings in some manner. Qualitative features of the absorption edge spectra also are discussed and are related to the Fe-ligand distance. PMID:6977382

  2. Numerical models of sunspot formation and fine structure.

    PubMed

    Rempel, Matthias

    2012-07-13

    Sunspots are central to our understanding of solar (and stellar) magnetism in many respects. On the large scale, they link the magnetic field observable in the photosphere to the dynamo processes operating in the solar interior. Properly interpreting the constraints that sunspots impose on the dynamo process requires a detailed understanding of the processes involved in their formation, dynamical evolution and decay. On the small scale, they give an insight into how convective energy transport interacts with the magnetic field over a wide range of field strengths and inclination angles, leading to sunspot fine structure observed in the form of umbral dots and penumbral filaments. Over the past decade, substantial progress has been made on both observational and theoretical sides. Advanced ground- and space-based observations have resolved, for the first time, the details of umbral dots and penumbral filaments and discovered similarities in their substructures. Numerical models have advanced to the degree that simulations of entire sunspots with sufficient resolution to resolve sunspot fine structure are feasible. A combination of improved helioseismic inversion techniques with seismic forward modelling provides new views on the subsurface structure of sunspots. In this review, we summarize recent progress, with particular focus on numerical modelling. PMID:22665895

  3. SOLAR RADIO BURSTS WITH SPECTRAL FINE STRUCTURES IN PREFLARES

    SciTech Connect

    Zhang, Yin; Tan, Baolin; Huang, Jing; Tan, Chengming; Karlický, Marian; Mészárosová, Hana; Simões, Paulo J.A.

    2015-01-20

    Good observations of preflare activities are important for us to understand the origin and triggering mechanism of solar flares, and to predict the occurrence of solar flares. This work presents the characteristics of microwave spectral fine structures as preflare activities of four solar flares observed by the Ondřejov radio spectrograph in the frequency range of 0.8-2.0 GHz. We found that these microwave bursts which occurred 1-4 minutes before the onset of flares have spectral fine structures with relatively weak intensities and very short timescales. They include microwave quasi-periodic pulsations with very short periods of 0.1-0.3 s and dot bursts with millisecond timescales and narrow frequency bandwidths. Accompanying these microwave bursts are filament motions, plasma ejection or loop brightening in the EUV imaging observations, and non-thermal hard X-ray emission enhancements observed by RHESSI. These facts may reveal certain independent, non-thermal energy releasing processes and particle acceleration before the onset of solar flares. They may help us to understand the nature of solar flares and to predict their occurrence.

  4. Fine-structure studies of experimental skeletal muscle trauma.

    PubMed Central

    Paddle, B. M.; Freeman, S. E.; Mawson, I.; Graham, H.

    1981-01-01

    A study was made of damage to skeletal muscle caused by a high-velocity rifle bullet. Such damage extends peripherally from the permanent wound cavity and is focal in nature. A fine-structure investigation of this region suggests that some components of the muscle are more susceptible to the wounding process than others. The sarcoplasmic reticulum appeared most sensitive and areas as far as 3 cm from the wound cavity frequently showed gross vacuolization. Mitochrondrial damage was seen, but only in areas where there was also damage to myofibrils and the microvasculature. Focal capillary leakage up to 3 cm from the wound cavity was demonstrated in an earlier study by the use of a fluorescein-labelled dextran (Paddle and Freeman, 1979). This finding was confirmed. A possible correlate at the fine structural level was swelling of te capillary endothelial cells, which occurred in the absence of other signs of microvascular damage. Damage to the endothelial junctions was not observed, even in severely damaged tissue. Intravascular colloidal carbon escaped into the extravascular space only when the microvasculature was fractured. The relationship of these findings to macroscopic damage is discussed. Images Fig. 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 6 Fig. 7 Fig. 8 Fig. 9 PMID:7326215

  5. Characterization by X-Ray Absorption, X-Ray Powder Diffraction, and Magnetic Susceptibility of Cu Zn Co Al Containing Hydroxycarbonates, Oxycarbonates, Oxides, and Their Products of Reduction

    NASA Astrophysics Data System (ADS)

    Porta, Piero; Morpurgo, Simone; Pettiti, Ida

    1996-02-01

    Copper-zinc-cobalt-aluminium-containing crystalline hydroxycarbonates having hydrotalcite structure have been prepared by coprecipitation. X-ray powder diffraction (XRPD), magnetic susceptibility, and extended X-ray absorption fine structure (EXAFS) indicate that Cu2+, Zn2+, and Co2+are present in an octahedral environment. Calcination of the hydroxycarbonates at 723 K produces quasi-amorphous oxycarbonates where Cu2+and Co2+still retain octahedral coordination and cobalt is almost completely oxidized to Co3+. The coordination of Zn2+, at this stage, is intermediate between the octahedral one of the precursors and the tetrahedral one of ZnO and Zn-based spinels. Further calcination at 973 K produces a mixture of crystalline oxides such as CuO, ZnO, CuAl2O4, ZnAl2O4, and ZnCo2O4. EXAFS analysis of these samples indicates that copper is mainly in a fourfold coordination (although two longer Cu-O distances are also detected), zinc is tetrahedral, and cobalt (as Co3+) is essentially octahedral. EXAFS and XANES investigations performed afterin situreduction (10% H2/N2, at 523 and 623 K) on the oxycarbonates and oxides reveal that the total Cu2+→ Cu0reduction occurs only at 623 K in both series of samples, Co3+is reduced to Co2+only at 623 K in the oxycarbonates, and Zn2+is never reduced.

  6. 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.

  7. Wide angle X-ray scattering (WAXS) study of "two-line" ferrihydrite structure: Effect of arsenate sorption and counterion variation and comparison with EXAFS results

    USGS Publications Warehouse

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

    1996-01-01

    Wide angle X-ray scattering (WAXS) measurements have been made on a suite of "two-line" ferrihydrite (FHY2) samples containing varying amounts of coprecipitated arsenate. Samples prepared at pH 8 with counter ions chloride, nitrate, and a mixture of both also were examined. The raw WAXS scattering functions show that "two-line" ferrihydrite actually has a large number of non-Bragg (i.e., diffuse scattering) maxima up to our observation limit of 16 A??-1. The type of counter ion used during synthesis produces no significant change in this function. In unarsenated samples, Radial Distribution Functions (RDFs) produced from the scattering functions show a well-defined Fe-O peak at 2.02 A?? in excellent agreement with the mean distance of 2.01 A?? from extended X-ray absorption fine structure (EXAFS) analysis. The area under the Fe-O peak is consistent with only octahedral oxygen coordination about iron, and an iron coordination about oxygen of 2.2, in agreement with the EXAFS results, the sample composition, and XANES measurements. The second peak observed in the RDFs is clearly divided into two populations of correlations, at 3.07 and 3.52 A??, respectively. These distances are close to the EXAFS-derived Fe-Fe subshell distances of 3.02-3.05 and 3.43-3.46 A??, respectively, though this is misleading as the RDF peaks also include contributions from O-Fe and O-O correlations. Simulated RDFs of the FeOOH polymorphs indicate how the observed RDF structure relates to the EXAFS pair-correlation function, and allow comparisons with an ordered ferrihydrite structure. The effect of increasing arsenate content is dramatic, as the RDF peaks are progressively smeared out, indicating a wider range of interatomic distances even at moderate surface coverages, and a loss of longer range correlations. At an As/Fe ratio of 0.68, the surface saturation level of arsenate, the RDF shows little order beyond what would be expected from small pieces of dioctahedral Fe oxyhydroxyl chains or

  8. Astronomical constraints on the cosmic evolution of the fine structure constant and possible quantum dimensions.

    PubMed

    Carilli, C L; Menten, K M; Stocke, J T; Perlman, E; Vermeulen, R; Briggs, F; de Bruyn, A G; Conway, J; Moore, C P

    2000-12-25

    We present measurements of absorption by the 21 cm hyperfine transition of neutral hydrogen toward radio sources at substantial look-back times. These data are used in combination with observations of rotational transitions of common interstellar molecules to set limits on the evolution of the fine structure constant: alpha/ alpha<3.5x10(-15) yr(-1), to a look-back time of 4.8 Gyr. In the context of string theory, the limit on the secular evolution of the scale factor of the compact dimensions, R, is &Rdot/ R<10(-15) yr(-1). Including terrestrial and other astronomical measurements places 2sigma limits on slow oscillations of R from the present to the epoch of cosmic nucleosynthesis, just seconds after the big bang, of DeltaR /R<10(-5). PMID:11136034

  9. `Fingerprint' Fine Structure in the Solar Decametric Radio Spectrum Solar Physics

    NASA Astrophysics Data System (ADS)

    Zlotnik, E. Y.; Zaitsev, V. V.; Melnik, V. N.; Konovalenko, A. A.; Dorovskyy, V. V.

    2015-07-01

    We study a unique fine structure in the dynamic spectrum of the solar radio emission discovered by the UTR-2 radio telescope (Kharkiv, Ukraine) in the frequency band of 20 - 30 MHz. The structure was observed against the background of a broadband type IV radio burst and consisted of parallel drifting narrow bands of enhanced emission and absorption on the background emission. The observed structure differs from the widely known zebra pattern at meter and decimeter wavelengths by the opposite directions of the frequency drift within a single stripe at a given time. We show that the observed properties can be understood in the framework of the radiation mechanism by virtue of the double plasma resonance effect in a nonuniform coronal magnetic trap. We propose a source model providing the observed frequency drift of the stripes.

  10. Constraints on a possible variation of the fine structure constant from galaxy cluster data

    NASA Astrophysics Data System (ADS)

    Holanda, R. F. L.; Landau, S. J.; Alcaniz, J. S.; Sánchez G., I. E.; Busti, V. C.

    2016-05-01

    We propose a new method to probe a possible time evolution of the fine structure constant α from X-ray and Sunyaev-Zel'dovich measurements of the gas mass fraction (fgas) in galaxy clusters. Taking into account a direct relation between variations of α and violations of the distance-duality relation, we discuss constraints on α for a class of dilaton runaway models. Although not yet competitive with bounds from high-z quasar absorption systems, our constraints, considering a sample of 29 measurements of fgas, in the redshift interval 0.14 < z < 0.89, provide an independent estimate of α variation at low and intermediate redshifts. Furthermore, current and planned surveys will provide a larger amount of data and thus allow to improve the limits on α variation obtained in the present analysis.

  11. Novel Preparation Methods for the Fabrication of Thin-Film EXAFS Samples

    SciTech Connect

    Ridgway, M. C.; Glover, C. J.; Kluth, P.; Johannessen, B.; Foran, G. J.

    2007-02-02

    Thin-film EXAFS samples have been fabricated using semiconductor-processing and wet-chemical etching techniques to eliminate artifacts associated with transmission and fluorescence measurements. Examples include crystalline GexSi1-x alloys, amorphous GaAs and Cu and Au nanocrystals in SiO2. In general, thin films of several microns thickness were first formed on bulk substrates then EXAFS samples were fabricated by separating the thin film and substrate. For transmission measurements, thin films were stacked together to yield the optimum absorption while sample inhomogeneity, non-uniformity and non-continuity were readily eliminated. For fluorescence measurements, scattering/diffraction from the substrate was eliminated and stacking the thin films together increased the areal concentration of the absorber. The use of such techniques to fabricate EXAFS samples yielded a significant increase in accessible photo-electron wave number range and hence more accurate structural parameter determinations.

  12. Spin Equilibria in Monomeric Manganocenes: Solid State Magnetic and EXAFS Studies

    SciTech Connect

    Walter, M. D.; Sofield, C. D.; Booth, C. H.; Andersen, R. A.

    2009-02-09

    Magnetic susceptibility measurements and X-ray data confirm that tert-butyl-substituted manganocenes [(Me{sub 3}C){sub n}C{sub 5}H{sub 5?n}]{sub 2}Mn (n = 1, 2) follow the trend previously observed with the methylated manganocenes; that is, electron-donating groups attached to the Cp ring stabilize the low-spin (LS) electronic ground state relative to Cp{sub 2}Mn and exhibit higher spin-crossover (SCO) temperatures. However, introducing three CMe{sub 3} groups on each ring gives a temperature-invariant high-spin (HS) state manganocene. The origin of the high-spin state in [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sub 2}Mn is due to the significant bulk of the [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sup -} ligand, which is sufficient to generate severe inter-ring steric strain that prevents the realization of the low-spin state. Interestingly, the spin transition in [1,3-(Me{sub 3}C){sub 2}C{sub 5}H{sub 3}]{sub 2}Mn is accompanied by a phase transition resulting in a significant irreversible hysteresis ({Delta}T{sub c} = 16 K). This structural transition was also observed by extended X-ray absorption fine-structure (EXAFS) measurements. Magnetic susceptibility studies and X-ray diffraction data on SiMe{sub 3}-substituted manganocenes [(Me{sub 3}Si){sub n}C{sub 5}H{sub 5-n}]{sub 2}Mn (n = 1, 2, 3) show high-spin configurations in these cases. Although tetra- and hexasubstituted manganocenes are high-spin at all accessible temperatures, the disubstituted manganocenes exhibit a small low-spin admixture at low temperature. In this respect it behaves similarly to [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn, which has a constant low-spin admixture up to 90 K and then gradually converts to high-spin. Thermal spin-trapping can be observed for [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn on rapid cooling.

  13. Investigations on local structures in new Bi2-2xLa2xUO6 (x = 0-0.05) solid solutions: a combined XRD, EXAFS, PL and EPR study.

    PubMed

    Sanyal, Kaushik; Pathak, Nimai; Yadav, Ashok Kumar; Kanrar, Buddhadev; Kadam, Ramakant Mahadeo; Jha, Shambhu Nath; Bhattacharya, Dibyendu; Misra, N L

    2016-05-01

    La doped Bi2UO6 solid solutions of the general formula Bi2-2xLa2xUO6 (x = 0-0.05) were prepared by the solid state reaction of Bi2O3, La(OH)3 and U3O8 in a stoichiometric ratio. These solid solutions were characterized by X-ray diffraction, Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Spectroscopy (XANES) studies. It was found that La goes to the Bi sites of the Bi2UO6 lattice during the formation of these solid solutions. For further confirmation, a photoluminescence (PL) study on an iso-structural Bi1.96Eu0.04UO6 was performed, and this supports the above observation. The solid solutions were also probed by EPR studies. The PL and EPR studies suggest that there are doping induced oxygen vacancies in these solid solutions. PMID:27052597

  14. Atomic Clocks and Variations of the FIne Structure Constant

    NASA Technical Reports Server (NTRS)

    Prestage, John D.; Tjoelker, Robert L.; Maleki, Lute

    1995-01-01

    We describe a new test for possible variations of the fine structure constant alpha by comparisons of rates between clocks based on hyperfine transitions in alkali atoms with different atomic number Z. H-maser, Cs, and Hg(+) clocks have a different dependence on alpha via relativistic contributions of order (Z-alpha)(sup 2). Recent H-maser vs Hg(+) clock comparison data improve laboratory limits on a time variation by 100-fold to give dot-alpha less than or equal to 3.7 x 10(exp -14)/yr. Future laser cooled clocks (Be(+), Rb, Cs, Hg(+), etc.), when compared, will yield the most sensitive of all tests for dot-alpha/alpha.

  15. Fine structure of track-plated Au-Cu alloy

    SciTech Connect

    Johnson, K.A.; Staudhammer, K.P.

    1982-01-01

    The burnishing process, i.e., mechanical rubbing of the deposit during electrodeposition, produces continuous nucleation of new grains during deposition which effectively prevents large columnar grains and macroporosity. In addition, track plating produces a uniform subgrain and substructure. By the use of STEM and TEM we were able to define a number of structural features of this material. Evident from the micrographs is the non-uniform polishing of the layers resulting from the chemical variation in the plating process. Microstructural features of the Au rich regions are shown. The unit size of this structure is about 22 nm. The fine-grained structure does not have well defined boundaries but does contain a slight amount of preferred alignment. Each equivalent unit has periodic fine structure measurable to approx. 2 nm.

  16. FOURIER ANALYSIS OF EXTENDED FINE STRUCTURE WITH AUTOREGRESSIVE PREDICTION

    SciTech Connect

    Barton, J.; Shirley, D.A.

    1985-01-01

    Autoregressive prediction is adapted to double the resolution of Angle-Resolved Photoemission Extended Fine Structure (ARPEFS) Fourier transforms. Even with the optimal taper (weighting function), the commonly used taper-and-transform Fourier method has limited resolution: it assumes the signal is zero beyond the limits of the measurement. By seeking the Fourier spectrum of an infinite extent oscillation consistent with the measurements but otherwise having maximum entropy, the errors caused by finite data range can be reduced. Our procedure developed to implement this concept applies autoregressive prediction to extrapolate the signal to an extent controlled by a taper width. Difficulties encountered when processing actual ARPEFS data are discussed. A key feature of this approach is the ability to convert improved measurements (signal-to-noise or point density) into improved Fourier resolution.

  17. The Beta Environmental Fine Structure (BEFS): The XAFS Nuclear Analogue

    SciTech Connect

    Monfardini, A.; Benedek, G.; Cremonesi, O.; Nucciotti, A.; Sisti, M.; Filipponi, A.

    2007-02-02

    The Beta Environmental Fine Structure (BEFS) effect is an oscillatory modulation on the otherwise smooth spectrum of electrons emitted by beta-decaying nuclei. The existence of this effect was theoretically proposed in 1991, for condensed emitters, in analogy with XAFS. In BEFS the electron, playing the role of the XAFS photoelectron, originates directly from the nucleus and an anti-neutrino is emitted at the same time. We present evidence for BEFS oscillations observed in Silver Perrhenate (AgReO4) low-temperature (0.1K) microbolometers, together with a XAFS-like analysis that allowed for the first time a direct measurement of the anti-neutrino angular momentum. We discuss the physical analogies and differences between BEFS and XAFS and the implications for the next generation experiments aimed at measuring the neutrino mass on purely kinematic grounds. Moreover, we briefly discuss the potential and the limits of BEFS-based techniques with respect to the classical XAFS.

  18. Fine structure of the magnetic field in active regions

    NASA Astrophysics Data System (ADS)

    Pustilnik, Lev; Beskrovnaya, Nina; Ikhsanov, Nazar

    High-resolution observations with SOHO, SDO, TRACE, HINODE suggest that the solar magnetic field in active regions has a complicated fine structure. There is a large number of thin magnetic arcs extended from the photosphere to corona with almost constant cross-section. We explore a possibility to model the complex of interacting arcs in terms of a dynamical percolating network. A transition of the system into flaring can be triggered by the flute instability of prominences and/or coronal condensations. We speculate around an assumption that the energy release in active regions is governed by the same scenario as dynamical current percolation through a random resistors network in which the saltatory conduction is controlled by a local current level.

  19. Oscillator Strengths for Fine-Structure Transitions in S III

    NASA Technical Reports Server (NTRS)

    Tayal, S. S.

    1997-01-01

    Oscillator strengths and transition probabilities for transitions among the fine-structure levels of the terms belonging to the 3s(sup 2)3p(sup 2), 3s3p(sup 3), 3s(sup 2)3p3d, 3s(sup 2)3p4s, 3s(sup 2)3p4p, and 3s(sup 2)3p4d configurations of S III are calculated using extensive configuration-interaction wave functions. The relativistic effects in intermediate coupling are incorporated by means of the Breit-Pauli Hamiltonian. Small adjustments to the diagonal elements of the Hamiltonian matrices have been made so that the energy splittings are as close as possible to the experimental values. The present results are compared with other available calculations and experiments.

  20. The fine structure of capillaries and small arteries.

    PubMed

    MOORE, D H; RUSKA, H

    1957-05-25

    Details of capillary endothelia of the mammalian heart are described and compared with capillaries of other organs and tissues. Continuous invagination and pinching off of the plasma membrane to form small vesicles which move across the cytoplasm are suggested as constituting a means of active and selective transmission through capillary walls (12). This might be designated as cytopempsis (transmission by cell). The fine structure of the different layers in the walls of small heart arteries is demonstrated. Endothelial protrusions extend through windows of the elestica interna to make direct contact with smooth muscle plasma membranes. The elastica interna appears to vary greatly in both thickness and density, and probably restricts filtration, diffusion, and osmosis to such an extent that windows and the transport mechanisms described (cytopempsis) are necessary for the functional integrity of the smooth muscle layer. The contractile material consists of very fine, poorly oriented filaments. PMID:13438930

  1. Exciton Fine Structure in Single CdSe Nanorods

    NASA Astrophysics Data System (ADS)

    Le Thomas, N.; Herz, E.; Schöps, O.; Woggon, U.; Artemyev, M. V.

    2005-01-01

    We study the optical properties of excitons in one-dimensional (1D) nanostructures at low temperatures. In single CdSe/ZnS core-shell nanorods we observe a fine structure splitting and explain it by exchange interaction. Two peaks are observed with different degrees of linear polarization of DLP<0.85 and DLP>0.95. For small nanorod radii R≤aB/2, an increase in the photoluminescence decay time is found when the temperature increases from 10 to 80K. The observations are explained by a radius-dependent change in the symmetry of the 1D-exciton ground state which transforms from a dark state into bright states below a critical radius of Rcrit≈3.7 nm.

  2. Vertical fine structure observations in the eastern equatorial Pacific

    SciTech Connect

    Hayes, S.P.

    1981-11-20

    Measurements of vertical displacement and horizontal velocity finestructure near the equator at 110/sup 0/W in the eastern Pacific Ocean are reported. Profiles were scaled to a constant Bruent-Vaeisaelae frequency ocean (N/sub 0/ = 1 cph) in accordance with a WKBJ approximation. A total of 57 CTD casts between 3/sup 0/N and 3/sup 0/S taken during five cruises in 1979 were analyzed. Results show an equatorial enhancement of vertical displacement is similar variance for vertical wavelengths longer than 50 sdbar (stretched decibars). This enhancement is similar to that which has been reported at 125/sup 0/W and 179/sup 0/E. Difference between locations can be accounted for by the observed temporal variability at 110/sup 0/W. Coherence between vertical displacement profiles separated in time by dealys of 2 hours to 120 hour indicate that the high wave number structures were largely associated with time scales of 4 days and less. Meridionally, vertical structures longer than 300 sdbar were coherent within 50 km of the equator. We interpret this vertical displacement fine structure enhancement as high wave number equatorially trapped inertial-gravity waves. The velocity fine structure measurements in July 1979 also indicate equatorially enhanced horizontal kinetic energy for vertical wave lengths longer than 100 sdbar. The velocity structures persisted over the 56 hour of measurement and appeared to have longer time scales than the vertical displacements. Meridional energy measurement and appeared to have longer time scales than the vertical displacements. Meridional energy exceeded zonal energy; however, the two components were coherent. We interpret these velocity structures as inertial-gravity waves which were produced off the equator and are propagating through the equatorial region.

  3. Effect of heat treatment on the far-infrared emission spectra and fine structures of black tourmaline.

    PubMed

    Meng, Junping; Liang, Jinsheng; Liu, Jie; Ding, Yan; Gan, Kun

    2014-05-01

    Mineral black tourmaline powders were heat-treated at different temperatures. Their crystal structure was studied by X-ray diffractometer. Their infrared absorption and emission spectra before and after the heat treatment were analyzed by the Fourier transform infrared spectrometer. The corresponding fine structures were discussed in detail. The results showed that the powders possessed higher infrared emissivity at the band where they showed stronger infrared absorption. However, there is no certain correlation between the peak intensity of infrared absorption and emissivity values at the same frequency. Because of the crystal shrinkage of c-axis, the electronic transitions were stimulated between different energy levels, and the abilities of infrared absorption and emission were enhanced with increasing the temperature of heat treatment. PMID:24734598

  4. Characterization of the particulate methane monooxygenase metal centers in multiple redox states by X-ray absorption spectroscopy.

    PubMed

    Lieberman, Raquel L; Kondapalli, Kalyan C; Shrestha, Deepak B; Hakemian, Amanda S; Smith, Stephen M; Telser, Joshua; Kuzelka, Jane; Gupta, Rajeev; Borovik, A S; Lippard, Stephen J; Hoffman, Brian M; Rosenzweig, Amy C; Stemmler, Timothy L

    2006-10-01

    The integral membrane enzyme particulate methane monooxygenase (pMMO) converts methane, the most inert hydrocarbon, to methanol under ambient conditions. The 2.8-A resolution pMMO crystal structure revealed three metal sites: a mononuclear copper center, a dinuclear copper center, and a nonphysiological mononuclear zinc center. Although not found in the crystal structure, solution samples of pMMO also contain iron. We have used X-ray absorption spectroscopy to analyze the oxidation states and coordination environments of the pMMO metal centers in as-isolated (pMMO(iso)), chemically reduced (pMMO(red)), and chemically oxidized (pMMO(ox)) samples. X-ray absorption near-edge spectra (XANES) indicate that pMMO(iso) contains both Cu(I) and Cu(II) and that the pMMO Cu centers can undergo redox chemistry. Extended X-ray absorption fine structure (EXAFS) analysis reveals a Cu-Cu interaction in all redox forms of the enzyme. The Cu-Cu distance increases from 2.51 to 2.65 A upon reduction, concomitant with an increase in the average Cu-O/N bond lengths. Appropriate Cu2 model complexes were used to refine and validate the EXAFS fitting protocols for pMMO(iso). Analysis of Fe EXAFS data combined with electron paramagnetic resonance (EPR) spectra indicates that Fe, present as Fe(III), is consistent with heme impurities. These findings are complementary to the crystallographic data and provide new insight into the oxidation states and possible electronic structures of the pMMO Cu ions. PMID:16999437

  5. X-ray absorption spectroscopy of xanthine oxidase. The molybdenum centres of the functional and the desulpho forms.

    PubMed Central

    Bordas, J; Bray, R C; Garner, C D; Gutteridge, S; Hasnain, S S

    1980-01-01

    X-ray absorption spectra have been recorded for the molybdenum K-edge region of xanthine oxidase. Both the absorption edge and the extended fine structure (e.x.a.f.s.) regions were investigated. Spectra were obtained for samples of the desulpho enzyme as well as for mixtures of this with the active enzyme. The spectrum of the pure active form was then obtained by difference. The desulpho enzyme shows a pronounced step in the absorption edge, of a type previously associated terminal oxygen ligands. In the active enzyme this step has decreased markedly. Satisfactory simulations of the e.x.a.f.s. spectrum of the desulpho enzyme could be obtained by assuming the molybdenum to be bonded to two terminal oxygen atoms (Mo = O about .175 nm), two sulphur atoms (presumably from cysteine residues, Mo-S about .0250 nm) and one sulphur atom (presumably from a methionine residue, Mo-S about 0.290 nm). E.x.a.f.s. of the active enzyme differed appreciably from this. In keeping with earlier proposals [Gutteridge, Tanner & Bray (1978) Biochem. J. 175, 887-897], the spectrum of the active enzyme could be simulated if a sulphur atom at about 0.225 nm (i.e. presumably a terminal sulphur atom) replaced one of the terminal oxygen atoms of the desulpho from, with small changes in the other bond distances. Validity of the interpretative procedures, which involved phase shift and amplitude calculations ab initio, was demonstrated by using low molecular weight compounds of known structure. PMID:6894537

  6. Reconstruction of the fine structure of an acoustic scatterer against the distorting influence of its large-scale inhomogeneities

    NASA Astrophysics Data System (ADS)

    Burov, V. A.; Grishina, I. M.; Lapshenkina, O. I.; Morozov, S. A.; Rumyantseva, O. D.; Sukhov, E. G.

    2003-11-01

    In the ultrasonic diagnostics of small-size neoplasms of biological tissues at the earliest stage of their development, an efficient way to eliminate the distorting influence of high-contrast or large inhomogeneities of the biological medium is to apply the iterative technique. A simple approach is proposed, which makes it possible with only two iteration steps to achieve an efficient focusing of the tomograph array. At the first step, the unknown distribution of the large-scale inhomogeneities of sound velocity and absorption over the scatterer is reconstructed, where the large-scale inhomogeneities are those whose size exceeds several wavelengths. At the second step, the fine structure of the scatterer is reconstructed against the large-scale background, which can be performed with a high accuracy owing to the evaluation of the background at the first step. The possibility of simultaneous reconstruction of the large-scale and fine structures by the noniterative Grinevich-Novikov algorithm is considered as an alternative. This algorithm reconstructs in an explicit form two-dimensional refractive-absorbing acoustic scatterers of almost arbitrary shape and strength. Taking into account the effects of multiple scattering, this algorithm provides resolution of the fine structure almost as good as that achieved in reconstructing the same structure against an undistorting homogeneous background. The results of numerical simulations of both algorithms are presented.

  7. Validation of EXAFS Analysis of Iridium Compounds

    NASA Astrophysics Data System (ADS)

    Feiters, M. C.; Longo, A.; Banerjee, D.; van der Ham, C. J. M.; Hetterscheid, D. G. H.

    2016-05-01

    Results of iridium L3 edge EXAFS measurements of compounds relevant for water oxidation catalysis are compared to those of other structural techniques. The structural results from EXAFS for the Ir compounds investigated here compare well to those of other structural techniques. Multiple scattering contributions are important in the coordinated Cp* and NHC ligands as well as in the IrCl6 unit and the IrO2 rutile structure. NHC is relatively weak compared to Ir, Cl, and even Cp* and O, and often out of phase with the other contributions.

  8. On the molecular basis of the activity of the antimalarial drug chloroquine: EXAFS-assisted DFT evidence of a direct Fe-N bond with free heme in solution

    NASA Astrophysics Data System (ADS)

    Macetti, Giovanni; Rizzato, Silvia; Beghi, Fabio; Silvestrini, Lucia; Lo Presti, Leonardo

    2016-02-01

    4-aminoquinoline antiplasmodials interfere with the biocrystallization of the malaria pigment, a key step of the malaria parasite metabolism. It is commonly believed that these drugs set stacking π···π interactions with the Fe-protoporphyrin scaffold of the free heme, even though the details of the heme:drug recognition process remain elusive. In this work, the local coordination of Fe(III) ions in acidic solutions of hematin at room temperature was investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy in the 4.0-5.5 pH range, both in the presence and in the absence of the antimalarial drug chloroquine. EXAFS results were complemented by DFT simulations in polarizable continuum media to model solvent effects. We found evidence that a complex where the drug quinoline nitrogen is coordinated with the iron center might coexist with formerly proposed adduct geometries, based on stacking interactions. Charge-assisted hydrogen bonds among lateral chains of the two molecules play a crucial role in stabilizing this complex, whose formation is favored by the presence of lipid micelles. The direct Fe-N bond could reversibly block the axial position in the Fe 1st coordination shell in free heme, acting as an inhibitor for the crystallization of the malaria pigment without permanently hampering the catalytic activity of the redox center. These findings are discussed in the light of possible implications on the engineering of drugs able to thwart the adaptability of the malaria parasite against classical aminoquinoline-based therapies.

  9. EXAFS studies of battery materials

    SciTech Connect

    McBreen, J.

    1991-12-31

    X-ray absorption spectroscopy (XAS) has been used at extensively at Brookhaven National Laboratory (BNL) to study materials and electrodes of several battery systems. The power and the general applicability of the technique is illustrated by studies of several battery materials such as PEO-salt complexes, PbO{sub 2}, and in situ studies of mossy zinc deposition in alkaline electrolyte.

  10. EXAFS studies of battery materials

    SciTech Connect

    McBreen, J.

    1991-01-01

    X-ray absorption spectroscopy (XAS) has been used at extensively at Brookhaven National Laboratory (BNL) to study materials and electrodes of several battery systems. The power and the general applicability of the technique is illustrated by studies of several battery materials such as PEO-salt complexes, PbO{sub 2}, and in situ studies of mossy zinc deposition in alkaline electrolyte.

  11. Studies of Element-Specific Local Structures in Compound Materials Using X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Soo, Yun-Liang

    1995-01-01

    The x-ray absorption spectroscopy techniques have been used to study a variety of semiconductor and superconductor materials. In such experiments, synchrotron radiation harnessed by a delicate beamline electronic and control system are used to obtain data with analyzable quality in a reasonable time scale. The element-selectivity is achieved by selecting an energy-scan range close to a characteristic "absorption edge" of the selected element. Peak structures below the absorption edge (pre-edge structures) reflect the local unoccupied states of the selected atomic species. The position of absorption edge (part of the near-edge x-ray absorption fine structure, NEXAFS) provides some qualitative information of the effective valency of the selected element. And, most importantly, the modulation in the spectrum some 40 eV above the absorption edge (extended x-ray absorption fine structure, EXAFS) gives quantitative information of the local structure around the selected atomic species. The selected atomic species such as magnetic Mn ions in III-V diluted magnetic semiconductors (DMS) rm In_{1-x}Mn_{x}As, Mn as the luminescent centers in nanocrystals of ZnS, O in the CuO_2 planes which host the carriers in high-T_{rm c} superconductors, and F as the electron reservoir in the n-type high-T_{rm c} superconductors rm Nd_2CuO _{4-x}F_{x} all play an important role in the novel mechanism of these new materials. Along with other detailed information, our EXAFS results have revealed (i) III-V DMS can indeed be prepared by substitutional doping of magnetic impurities under proper processing conditions. (ii) Mn ions substitute for the Zn sites in the nanocrystals of ZnS with significant size-dependent local structural changes. (iii) Only ~6% of O in the CuO_2 planes in rm Nd_2CuO_{4 -x}F_{x} are substituted by F. The rest of F atoms substitute for O atoms in the NdO layers and serve as electron reservoirs. The NEXAFS results have shown that the effective valency of Mn in Zn

  12. [Study on the fine structure of K-feldspar of Qichun granite].

    PubMed

    Du, Deng-Wen; Hong, Han-Lie; Fan, Kan; Wang, Chao-Wen; Yin, Ke

    2013-03-01

    Fine structure of K-feldspar from the Qichun granite was investigated using X-ray diffraction (XRD), Fourier infrared absorption spectroscopy (FTIR), and inductively coupled plasma mass spectrometry methods to understand the evolution of the granitic magmatism and its correlation to molybdenite mineralization. The XRD results showed that K-feldspar of the potassic alteration veins has higher ordering index and triclinicity and is namely microcline with triclinic symmetry. K-feldspar of the early cretaceous granite has relatively lower ordering index and has widening [131] peak and is locally triclinic ordering. K-feldspar of the late cretaceous granite has lowest ordering index and sharp [131] peak and is honiogeneously monoclinic. The FTIR results showed that the IR spectra of the Qichun K-feldspar are similar to that of orthoclase reported by Farmer (1974). The 640 cm-1 absorption band increases while the 540 cm-' absorption band decreases with increase in K-feldspar ordering index, also, the 1,010 cm-1 absorption band separates into 1,010 and 1,046 cm-1 absorption bands, with a change in the band shape from widening to sharp outline. The ICP-MS results suggested that K-feldspar of the early cretaceous granite has relatively higher metal elements and rare earth elements, and the granite exhibits better mineralization background, K-feldspar of the potassic alteration veins has markedly lower Sr and Ba, indicating that the alteration fluid originated from the granitic magmatism, and hence, potassic alteration is a good indicator for molybdenite exploration. PMID:23705418

  13. Fine structure and optical properties of biological polarizers in crustaceans and cephalopods

    NASA Astrophysics Data System (ADS)

    Chiou, Tsyr-Huei; Caldwell, Roy L.; Hanlon, Roger T.; Cronin, Thomas W.

    2008-04-01

    The lighting of the underwater environment is constantly changing due to attenuation by water, scattering by suspended particles, as well as the refraction and reflection caused by the surface waves. These factors pose a great challenge for marine animals which communicate through visual signals, especially those based on color. To escape this problem, certain cephalopod mollusks and stomatopod crustaceans utilize the polarization properties of light. While the mechanisms behind the polarization vision of these two animal groups are similar, several distinctive types of polarizers (i.e. the structure producing the signal) have been found in these animals. To gain a better knowledge of how these polarizers function, we studied the relationships between fine structures and optical properties of four types of polarizers found in cephalopods and stomatopods. Although all the polarizers share a somewhat similar spectral range, around 450- 550 nm, the reflectance properties of the signals and the mechanisms used to produce them have dramatic differences. In cephalopods, stack-plates polarizers produce the polarization patterns found on the arms and around their eyes. In stomatopods, we have found one type of beam-splitting polarizer based on photonic structures and two absorptive polarizer types based on dichroic molecules. These stomatopod polarizers may be found on various appendages, and on the cuticle covering dorsal or lateral sides of the animal. Since the efficiencies of all these polarizer types are somewhat sensitive to the change of illumination and viewing angle, how these animals compensate with different behaviors or fine structural features of the polarizer also varies.

  14. Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

    NASA Astrophysics Data System (ADS)

    Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

    2015-06-01

    The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2- (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2- species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2-, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples.

  15. Fine-structure infrared lines from the Cassiopeia A knots

    NASA Astrophysics Data System (ADS)

    Docenko, D.; Sunyaev, R. A.

    2010-01-01

    Aims: Archival observations of infrared fine-structure lines of the young Galactic supernova remnant Cassiopeia A allow us to test existing models and determine the physical parameters of various regions of the fast-moving knots, which are metal-dominated clouds of material ejected by the supernova explosion. Methods: The fluxes of far-infrared [O i] and [O iii] lines are extracted from previously unpublished archival ISO data. The archival Spitzer data are used to determine the fluxes of the O, Ne, Si, S, Ar, and Fe ion fine-structure lines originating in the fast-moving knots. The ratios of these line fluxes are used as plasma diagnostics. We also determine the infrared line flux ratios with respect to the optical [O iii] 5007 Å line in the knots with previously measured reddening. Additionally, we analyze several optical and near-infrared observations of the fast-moving knots to obtain clearer insight into the post-shock photoionized region structure. Results: We show that the infrared oxygen line flux predictions of all existing theoretical models are correct only to within a factor of a several. Comparison of the model predictions shows that to reproduce the observations it is essential to include the effects of the electron conductivity and dust. Detailed analysis of the diagnostic line flux ratios of various ions allows us to qualitatively confirm the general model of fast-moving knot emission and determine observationally for the first time the physical conditions in the photoionized region after the shock. We infer from the [O iii] line flux ratios that the pre-shock cloud densities are higher than assumed in existing theoretical models and most probably correspond to several hundred particles per cm3. We also determine the Cas A luminosity in the infrared continuum and lines. We show that accounting for the charge exchange processes in the post-shock photoionized region allows us to reproduce most of the relevant spectral line ratios even in the frame of

  16. Varying fine structure 'constant' and charged black holes

    SciTech Connect

    Bekenstein, Jacob D.; Schiffer, Marcelo

    2009-12-15

    Speculation that the fine-structure constant {alpha} varies in spacetime has a long history. We derive, in 4-D general relativity and in isotropic coordinates, the solution for a charged spherical black hole according to the framework for dynamical {alpha} J. D. Bekenstein, Phys. Rev. D 25, 1527 (1982).. This solution coincides with a previously known one-parameter extension of the dilatonic black hole family. Among the notable properties of varying-{alpha} charged black holes are adherence to a 'no hair' principle, the absence of the inner (Cauchy) horizon of the Reissner-Nordstroem black holes, the nonexistence of precisely extremal black holes, and the appearance of naked singularities in an analytic extension of the relevant metric. The exteriors of almost extremal electrically (magnetically) charged black holes have simple structures which makes their influence on applied magnetic (electric) fields transparent. We rederive the thermodynamic functions of the modified black holes; the otherwise difficult calculation of the electric potential is done by a shortcut. We confirm that variability of {alpha} in the wake of expansion of the universe does not threaten the generalized second law.

  17. FINE STRUCTURE OF THE EYE OF A CHAETOGNATH.

    PubMed

    EAKIN, R M; WESTFALL, J A

    1964-04-01

    Electron microscopy reveals a star-like pigment cell at the center of the eye of the arrow-worm, Sagitta scrippsae. Between the arms of the pigment cell are clusters of photoreceptor cell processes, each process consisting of: (1) a tubular segment containing longitudinally arranged microtubules about 500 A in diameter and 20 micro in length; (2) a remarkable conical body, composed of cords and large granules, situated at the base of the tubular segment; and (3) a connecting piece which, like that of rods and cones, connects the process with the sensory cell proper and through which runs a fibrillar apparatus consisting of nine peripheral double tubules. Beneath the connecting piece lies a typical centriole with a striated rootlet. The receptor cell process is deeply recessed into the sensory cell which may possess a corona of microvilli at its inner surface. A nerve fiber arises from the outer end of the cell and passes into the optic nerve. Additional features are some supporting cells, an external layer of flattened epithelial cells, and an over-all investment of basement membrane and thick fibrous capsule. The fine structure and function of these elements of the eye are discussed in relation to earlier studies with the light microscope. The ciliary nature of the photoreceptor cell process in S. scrippsae points to a probable evolutionary relationship of chaetognaths to echinoderms and chordates. PMID:14154485

  18. Bumblebee Homing: The Fine Structure of Head Turning Movements

    PubMed Central

    Boeddeker, Norbert; Mertes, Marcel; Dittmar, Laura; Egelhaaf, Martin

    2015-01-01

    Changes in flight direction in flying insects are largely due to roll, yaw and pitch rotations of their body. Head orientation is stabilized for most of the time by counter rotation. Here, we use high-speed video to analyse head- and body-movements of the bumblebee Bombus terrestris while approaching and departing from a food source located between three landmarks in an indoor flight-arena. The flight paths consist of almost straight flight segments that are interspersed with rapid turns. These short and fast yaw turns (“saccades”) are usually accompanied by even faster head yaw turns that change gaze direction. Since a large part of image rotation is thereby reduced to brief instants of time, this behavioural pattern facilitates depth perception from visual motion parallax during the intersaccadic intervals. The detailed analysis of the fine structure of the bees’ head turning movements shows that the time course of single head saccades is very stereotypical. We find a consistent relationship between the duration, peak velocity and amplitude of saccadic head movements, which in its main characteristics resembles the so-called "saccadic main sequence" in humans. The fact that bumblebee head saccades are highly stereotyped as in humans, may hint at a common principle, where fast and precise motor control is used to reliably reduce the time during which the retinal images moves. PMID:26352836

  19. Fine structure of the Mn acceptor in GaAs

    NASA Astrophysics Data System (ADS)

    Krainov, I. V.; Debus, J.; Averkiev, N. S.; Dimitriev, G. S.; Sapega, V. F.; Lähderanta, E.

    2016-06-01

    We reveal the electronic level structure of the Mn acceptor, which consists of a valence-band hole bound to an Mn2 + ion, in presence of applied uniaxial stress and an external magnetic field in bulk GaAs. Resonant spin-flip Raman scattering is used to measure the g factor of the AMn0 center in the ground and excited states with the total angular momenta F =1 and F =2 and characterize the optical selection rules of the spin-flip transitions between these Mn-acceptor states. We determine the random stress fields near the Mn acceptor, the constant of the antiferromagnetic exchange interaction between the valence-band holes and the electrons of the inner Mn2 + shell as well as the deformation potential for the exchange energy. The p -d exchange energy, in particular, decreases significantly with increasing compressive stress. By combining the experimental Raman study with the developed theoretical model on the scattering efficiency, in which also the random local and external uniaxial stresses and magnetic field are considered, the fine structure of the Mn acceptor is determined in full detail.

  20. Consonant identification using temporal fine structure and recovered envelope cuesa)

    PubMed Central

    Swaminathan, Jayaganesh; Reed, Charlotte M.; Desloge, Joseph G.; Braida, Louis D.; Delhorne, Lorraine A.

    2014-01-01

    The contribution of recovered envelopes (RENVs) to the utilization of temporal-fine structure (TFS) speech cues was examined in normal-hearing listeners. Consonant identification experiments used speech stimuli processed to present TFS or RENV cues. Experiment 1 examined the effects of exposure and presentation order using 16-band TFS speech and 40-band RENV speech recovered from 16-band TFS speech. Prior exposure to TFS speech aided in the reception of RENV speech. Performance on the two conditions was similar (∼50%-correct) for experienced listeners as was the pattern of consonant confusions. Experiment 2 examined the effect of varying the number of RENV bands recovered from 16-band TFS speech. Mean identification scores decreased as the number of RENV bands decreased from 40 to 8 and were only slightly above chance levels for 16 and 8 bands. Experiment 3 examined the effect of varying the number of bands in the TFS speech from which 40-band RENV speech was constructed. Performance fell from 85%- to 31%-correct as the number of TFS bands increased from 1 to 32. Overall, these results suggest that the interpretation of previous studies that have used TFS speech may have been confounded with the presence of RENVs. PMID:25235005

  1. FINE STRUCTURES AND OVERLYING LOOPS OF CONFINED SOLAR FLARES

    SciTech Connect

    Yang, Shuhong; Zhang, Jun; Xiang, Yongyuan

    2014-10-01

    Using the Hα observations from the New Vacuum Solar Telescope at the Fuxian Solar Observatory, we focus on the fine structures of three confined flares and the issue why all the three flares are confined instead of eruptive. All the three confined flares take place successively at the same location and have similar morphologies, so can be termed homologous confined flares. In the simultaneous images obtained by the Solar Dynamics Observatory, many large-scale coronal loops above the confined flares are clearly observed in multi-wavelengths. At the pre-flare stage, two dipoles emerge near the negative sunspot, and the dipolar patches are connected by small loops appearing as arch-shaped Hα fibrils. There exists a reconnection between the small loops, and thus the Hα fibrils change their configuration. The reconnection also occurs between a set of emerging Hα fibrils and a set of pre-existing large loops, which are rooted in the negative sunspot, a nearby positive patch, and some remote positive faculae, forming a typical three-legged structure. During the flare processes, the overlying loops, some of which are tracked by activated dark materials, do not break out. These direct observations may illustrate the physical mechanism of confined flares, i.e., magnetic reconnection between the emerging loops and the pre-existing loops triggers flares and the overlying loops prevent the flares from being eruptive.

  2. The importance of source positions during radio fine structure observations

    NASA Astrophysics Data System (ADS)

    Chernov, Guennadi P.; Yan, Yi-Hua; Fu, Qi-Jun

    2014-07-01

    The measurement of positions and sizes of radio sources in the observations of the fine structure of solar radio bursts is a determining factor for the selection of the radio emission mechanism. The identical parameters describing the radio sources for zebra structures (ZSs) and fiber bursts confirm there is a common mechanism for both structures. It is very important to measure the size of the source in the corona to determine if it is distributed along the height or if it is point-like. In both models of ZSs (the double plasma resonance (DPR) and the whistler model) the source must be distributed along the height, but by contrast to the stationary source in the DPR model, in the whistler model the source should be moving. Moreover, the direction of the space drift of the radio source must correlate with the frequency drift of stripes in the dynamic spectrum. Some models of ZSs require a local source, for example, the models based on the Bernstein modes, or on explosive instability. The selection of the radio emission mechanism for fast broadband pulsations with millisecond duration also depends on the parameters of their radio sources.

  3. Stochastic quintessence models: Jerk and fine-structure variability constraints

    NASA Astrophysics Data System (ADS)

    Dantas, Christine C.; Ribeiro, André L. B.

    2016-02-01

    We report on constraints to the cosmological jerk parameter (j ) and to possible variability of the fine-structure constant (Δ α /α ) based on stochastic quintessence models of dark energy, discussed by Chongchitnan and Efstathiou [Phys. Rev. D 76, 043508 (2007)]. We confirm the results by these authors in the sense that many viable solutions can be obtained, obeying current observational constraints in low redshifts. We add the observables j and Δ α /α to this conclusion. However, we find peculiarities that may produce, in the nearby universe, potential observational imprints in future cosmological data. We conclude, for redshifts z ≲3 , that (i) j (z ) fluctuates due to the stochasticity of the models, reaching an amplitude of up to 5% relatively to the Λ cold dark matter model value (jΛ CDM=1 ); and (ii) by contrasting two distinct ("extreme") types of solutions, variabilities in α (z ), linked to a linear coupling (ζ ) between the dark energy and electromagnetic sectors, are weakly dependent on redshift, for couplings of the order |ζ |˜1 0-4, even for large variations in the equation of state parameter at relatively low redshifts. Nonlinear couplings produce an earlier and steeper onset of the evolution in Δ α /α (z ), but can still accommodate the data for weak enough couplings.

  4. Bumblebee Homing: The Fine Structure of Head Turning Movements.

    PubMed

    Boeddeker, Norbert; Mertes, Marcel; Dittmar, Laura; Egelhaaf, Martin

    2015-01-01

    Changes in flight direction in flying insects are largely due to roll, yaw and pitch rotations of their body. Head orientation is stabilized for most of the time by counter rotation. Here, we use high-speed video to analyse head- and body-movements of the bumblebee Bombus terrestris while approaching and departing from a food source located between three landmarks in an indoor flight-arena. The flight paths consist of almost straight flight segments that are interspersed with rapid turns. These short and fast yaw turns ("saccades") are usually accompanied by even faster head yaw turns that change gaze direction. Since a large part of image rotation is thereby reduced to brief instants of time, this behavioural pattern facilitates depth perception from visual motion parallax during the intersaccadic intervals. The detailed analysis of the fine structure of the bees' head turning movements shows that the time course of single head saccades is very stereotypical. We find a consistent relationship between the duration, peak velocity and amplitude of saccadic head movements, which in its main characteristics resembles the so-called "saccadic main sequence" in humans. The fact that bumblebee head saccades are highly stereotyped as in humans, may hint at a common principle, where fast and precise motor control is used to reliably reduce the time during which the retinal images moves. PMID:26352836

  5. Sequestration of Sr(II) By Calcium Oxalate - a Batch Uptake Study And EXAFS Analysis of Model Compounds And Reaction Products

    SciTech Connect

    Singer, D.M.; Johnson, S.B.; Catalano, J.G.; Farges, F.; Brown, G.E.; Jr.

    2009-05-26

    Calcium oxalate monohydrate (CaC{sub 2}O{sub 4}{center_dot}H{sub 2}O -- abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II){sub aq} following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4--10, with initial Sr solution concentrations, [Sr]{sub aq}, ranging from 1 x 10{sup -4} to 1 x 10{sup -3} M and ionic strengths ranging of 0.001--0.1 M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sr{sub aq} for two days, the solution Ca concentration, [Ca]{sup aq}, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sr{sub aq} removed from solution was nearly equal to the total [Ca]{sup aq} after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model

  6. Speciation and solubility of heavy metals in contaminated soil using X-ray microfluorescence, EXAFS spectroscopy, chemical extraction, and thermodynamic modeling

    NASA Astrophysics Data System (ADS)

    Kirpichtchikova, Tatiana A.; Manceau, Alain; Spadini, Lorenzo; Panfili, Fré; dé; ric; Marcus, Matthew A.; Jacquet, Thierry

    2006-05-01

    Synchrotron-based X-ray radiation microfluorescence (μ-SXRF) and micro-focused and powder extended X-ray absorption fine structure (EXAFS) spectroscopy measurements, combined with desorption experiments and thermodynamic calculations, were used to evaluate the solubility of metal contaminants (Zn, Cu, Pb) and determine the nature and fractional amount of Zn species in a near-neutral pH (6.5-7.0) truck-farming soil contaminated by sewage irrigation for one hundred years. Zn is the most abundant metal contaminant in the soil (1103 mg/kg), followed by Pb (535 mg/kg) and Cu (290 mg/kg). The extractability of Zn, Pb, and Cu with citrate, S, S-ethylenediaminedisuccinic acid (EDDS), and ethylenediaminetetraacetic acid (EDTA) was measured as a function of time (24 h, 72 h, 144 h), and also as a function of the number of applications of the chelant (5 applications each with 24 h of contact time). Fifty-three percent of the Zn was extracted after 144 h with citrate, 51% with EDDS and 46% with EDTA, compared to 69, 87, and 61% for Cu, and 24, 40, and 34% for Pb. Renewing the extracting solution removed more of the metals. Seventy-nine, 65, and 57% of the Zn was removed after five cycles with citrate, EDDS and EDTA, respectively, compared to 88, 100, and 72% for Cu, and 91, 65, and 47% for Pb. Application to the untreated soil of μ-SXRF, laterally resolved μ-EXAFS combined with principal component analysis, and bulk averaging powder EXAFS with linear least-squares combination fit of the data, identified five Zn species: Zn-sorbed ferrihydrite, Zn phosphate, Zn-containing trioctahedral phyllosilicate (modeled by the Zn kerolite, Si 4(Mg 1.65Zn 1.35)O 10(OH) 2 · nH 2O), willemite (Zn 2SiO 4), and gahnite (ZnAl 2O 4), in proportions of ˜30, 28, 24, 11, and less than 10%, respectively (precision: 10% of total Zn). In contrast to Cu and Pb, the same fractional amount of Zn was extracted after 24 h contact time with the three chelants (40-43% of the initial content), suggesting

  7. A New Physical Meaning of Sommerfeld Fine Structure Constant

    NASA Astrophysics Data System (ADS)

    Sohrab, Siavash

    2015-04-01

    Identifying physical space or Casimir vacuum as a compressible tachyon fluid, Planck compressible ether, leads to stochastic definitions of Planck h = mk <λk > c and Boltzmann k = mk <νk > c constants, finite photon mass mk = (hk/c3)1/2 , amu = mk c2 = (hkc)1/2 , and modified Avogadro-Loschmidt number No = 1/(hkc)1/2 = 6.03766 x1023 mole-1 . Thus, Lorentz-FitzGerald contractions now result from compressibility of physical space and become causal (Pauli) in accordance with Poincaré-Lorentz dynamic theory of relativity as opposed to Einstein kinematic theory of relativity. At thermodynamic equilibrium he = me <λe > ve = hk = mk <λk > c = h, Compton wavelength can be expressed as λc = h/me c = (ve /c)h <λe > /(me <λe > ve) = αλe . Hence, Sommerfeld fine structure constant α is identified as the ratio of electron to photon speeds α = e2/(2ɛo hc) = ve/c = 1/137.036. The mean thermal speed of electron at equilibrium with photon gas is ve = 2.187640x106 m/s and its de Broglie wavelength is λe = 3.3250x10-10 m. Also, electron kinetic energy for oscillations in two directions < x + > and < x- > or ɛe = hνe = me ve2= kTe results in electron temperature Te = 3.15690x105 K.

  8. A X-Ray Absorption Spectroscopy Study of Manganese Containing Compounds and Photosynthetic Spinach Chloroplasts.

    NASA Astrophysics Data System (ADS)

    Kirby, Jon Allan

    The manganese sites in chloroplasts, long thought to be involved in photosynthetic oxygen evolution have been examined and partially characterized by X-ray Absorption Spectroscopy (XAS) using synchrotron radiation. The local environment about the manganese atoms is estimated from an analysis of the extended X-ray Absorption Fine Structure (EXAFS). Comparisons with and simulations of the manganese EXAFS for several reference compounds leads to a model in which the chloroplast manganese atoms are contained in a binuclear complex similar to di-u-oxo -tetrakis-(2,2'-bipyridine) dimanganese. It is suggested that the partner metal is another manganese. The bridging ligands are most probably oxygen. The remaining manganese ligands are carbon, oxygen, or nitrogen. A roughly linear correlation between the X-ray K edge onset energy and the "coordination charge" of a large number of manganese coordination complexes and compounds has been developed. Entry of the chloroplast manganese edge energy onto this correlation diagram establishes that the active pool of manganese is in an oxidation state greater than +2. If the manganese is in a dimeric form the oxidation states are most probably (II,III). Underlying these results is an extensive data analysis methodology. The method developed involves the use of many different background removal techniques, Fourier transforms and ultimately curve fitting to the modulations in the x-ray absorption cross sections. A large number of model compounds were used to evaluate the analysis method. These analyses are used to show that the two major curve fitting models available are essentially equivalent. Due to its greater versatility, the theoretical model of Teo and Lee is preferred (J. Am. Chem. Soc. (1979), 101, 2815). The results are also used to determine the informational limitations of XAS within the limits of the present understanding of X-ray absorption phenomena by inner shell electrons for atoms with atomic number greater than that

  9. X-ray absorption spectroscopy of hemes and hemeproteins in solution: multiple scattering analysis.

    PubMed

    D'Angelo, Paola; Lapi, Andrea; Migliorati, Valentina; Arcovito, Alessandro; Benfatto, Maurizio; Roscioni, Otello Maria; Meyer-Klaucke, Wolfram; Della-Longa, Stefano

    2008-11-01

    A full quantitative analysis of Fe K-edge X-ray absorption spectra has been performed for hemes in two porphynato complexes, that is, iron(III) tetraphenylporphyrin chloride (Fe(III)TPPCl) and iron(III) tetraphenylporphyrin bis(imidazole) (Fe(III)TPP(Imid)2), in two protein complexes whose X-ray structure is known at atomic resolution (1.0 A), that is, ferrous deoxy-myoglobin (Fe(II)Mb) and ferric aquo-myoglobin (Fe(III)MbH2O), and in ferric cyano-myoglobin (Fe(III)MbCN), whose X-ray structure is known at lower resolution (1.4 A). The analysis has been performed via the multiple scattering approach, starting from a muffin tin approximation of the molecular potential. The Fe-heme structure has been obtained by analyzing independently the Extended X-ray Absorption Fine Structure (EXAFS) region and the X-ray Absorption Near Edge Structure (XANES) region. The EXAFS structural results are in full agreement with the crystallographic values of the models, with an accuracy of +/- 0.02 A for Fe-ligand distances, and +/-6 degrees for angular parameters. All the XANES features above the theoretical zero energy (in the lower rising edge) are well accounted for by single-channel calculations, for both Fe(II) and Fe(III) hemes, and the Fe-N p distance is determined with the same accuracy as EXAFS. XANES evaluations of Fe-5th and Fe-6th ligand distances are determined with 0.04-0.07 A accuracy; a small discrepancy with EXAFS (0.01 to 0.05 A beyond the statistical error), is found for protein compounds. Concerns from statistical correlation among parameters and multiple minima in the parameter space are discussed. As expected, the XANES accuracy is slightly lower than what was found for polarized XANES on Fe(III)MbCN single crystal (0.03-0.04 A), and states the actual state-of-the-art of XANES analysis when used to extract heme-normal parameters in a solution spectrum dominated by heme-plane scattering. PMID:18837548

  10. Testing interaction models by using x-ray absorption spectroscopy: solid Pb

    NASA Astrophysics Data System (ADS)

    Di Cicco, Andrea; Minicucci, Marco; Principi, Emiliano; Witkowska, Agnieszka; Rybicki, Jaroslaw; Laskowski, Robert

    2002-04-01

    Structural models obtained using classical molecular dynamics (MD) simulations and realistic interatomic potentials for solid metals are tested using experimental results obtained by x-ray absorption spectroscopy (XAS). Accurate L-edge extended x-ray absorption fine-structure (EXAFS) measurements of Pb grains dispersed in BN and graphite matrices have been collected for temperatures up to the melting point. The thermal expansion of the grains was measured by energy-dispersive x-ray diffraction techniques and found to be coincident with that of pure Pb up to the limit of the present measurements. L3-edge EXAFS measurements of solid Pb at various temperatures have been analysed using advanced data-analysis techniques (GNXAS) based on exact spherical-wave multiple-scattering simulation of the absorption cross-section. Realistic structural models for solid Pb were obtained from MD simulations using an empirical pair potential (Dzugutov, Larsson and Ebbsjo (DLE)), a tight-binding (TB) square-root functional, and an embedded-atom (EA) model potential parametrized by us. The short-range pair distribution function g(r) reconstructed by means of EXAFS is compared with those obtained by MD simulations. The empirical DLE potential, originally designed for the liquid state, is too soft, showing too-large values for the average distance R, variance σ2, and skewness β. The TB and EA potentials are both compatible with XAS data as regards the average distance and skewness of the first neighbours. The distance variance, associated with the thermal vibration amplitudes, is underestimated for the TB potential, while the EA model is found to be in agreement with XAS data. The present results are also compared with those from a previous EXAFS study on solid lead, where the cumulant expansion and a simple one-dimensional anharmonic oscillator model were used. The need for realistic interaction models and appropriate simulation schemes for reliable XAS data analysis is emphasized

  11. Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

    NASA Astrophysics Data System (ADS)

    Isaure, Marie-Pierre; Laboudigue, Agnès; Manceau, Alain; Sarret, Géraldine; Tiffreau, Christophe; Trocellier, Patrick; Lamble, Géraldine; Hazemann, Jean-Louis; Chateigner, Daniel

    2002-05-01

    Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system. The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn 2SiO 4), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn 2SiO 4, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si

  12. X-ray absorption spectroscopy study of H 2S sorption on iron-rich soil: Characterization of iron-sulfur species

    NASA Astrophysics Data System (ADS)

    Ko, Tzu-Hsing; Yu, Lung-Sheng; Hung, Chien-Jen

    2007-08-01

    Iron-rich soil after sorption of H 2S was characterized using X-ray absorption near-edge structural (XANES) and extended X-ray absorption fine structure spectroscopy (EXAFS) for determination the possible products in the present work. EXAFS revealed that the main Fe-S species in the sulfided sample were FeS (troilite) and Fe 1- xS (pyrrohotite). Iron in the sulfided sample was found to possess a Fe-S bond distance of 2.36 Å and a Fe-O bond distance of 1.72 Å in the Fe-K-edge spectra whereas the Fe-S bond distance of 2.25 Å was determined in the sulfur K-edge spectra. In the second shells, the bond distance of Fe-O-Si or Fe-O-Al with 3.28 Å was also observed. No FeS 2 (pyrite) was included in the sulfided sample. The formation of Fe 1- xS was probably attributed to the presence of Fe 3O 4, a type of spinel structure with a lattice deficiency.

  13. X-ray absorption spectroscopic studies of the diiron center in methane monooxygenase in the presence of substrate and the coupling protein of the enzyme system

    SciTech Connect

    DeWitt, J.G.; Rosenzweig, A.C.; Salifoglou, A.

    1995-05-10

    The interaction among the hydroxylase component of methane monooxygenase (MMO) from Methylococcus capsulatus (Bath), the coupling protein of the MMO enzyme system (component B), and substrate has been investigated by using Fe K-edge X-ray absorption spectroscopy (XAS). Fe K-edge extended X-ray absorption fine structure (EXAFS) studies of the semimet form of the hydroxylase in the presence of the coupling protein, 1-bromo-1-propene, and both the coupling protein and 1-bromo-1-propene revealed small differences in the appearance of the EXAFS above k = 8 {Angstrom}{sup {minus}1} as compared to the noncomplexed hydroxylase. No dramatic change in the Fe coordination was seen in fits to the data. The average first shell Fe-O/N distance for the complexed forms of the semimet hydroxylase ranged between 2.06 and 2.08 {Angstrom}, which is comparable to the distance found for the noncomplexed form, 2.06-2.09 {Angstrom}. Although the average first shell coordination was similar for all samples, a difference was seen in the distribution of long vs short distance contributions to the first shell coordination sphere for samples with component B present. This difference was accompanied by a small but consistent decrease in the Fe-Fe distance of the B-complexed hydroxylase samples, from 3.42 to 3.39 {angstrom}.

  14. Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

    PubMed

    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

    2016-06-22

    Copper ferrite, CuFe2O4, 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 CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used 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). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging. PMID:27292604

  15. Density and velocity fine structure enhancement in oceanic eddies

    NASA Astrophysics Data System (ADS)

    Miller, Jerry L.; Evans, David L.

    1985-05-01

    Advection-diffusion models of the oceanic thermocline require a global ocean, mean vertical eddy diffusivity of about 1 cm2 s-1; however, maximum values estimated from microstructure measurements at mid-gyre locations are generally smaller and, occasionally, 1-2 orders of magnitude less, depending on the particular assumptions made by individual analysts. Mesoscale features are high kinetic energy sources, which may fuel vertical mixing mechanisms on fine structure scales, resulting in local enhancements of eddy diffusivity above the canonical value of 1 cm2 s-1. The effects of one such mechanism, the Kelvin-Helmholtz instability, are assessed for a Gulf Stream ring and a mid-thermocline eddy. The necessary Richardson numbers are computed from Yvette profiles obtained in these features and are accurate to within about 10% for Ri = 1, and more accurate at the critical value Ri = 0.25. A plausible extension of the Miles-Howard theorem for a nonparallel shear flow is formulated for a two-dimensional perturbation. The shear appropriate for this Richardson number calculation is well approximated by the total shear for slowly depth-varying direction, as is the case for the vast majority of the data. Upper and lower bounds on the vertical scale for the Richardson number calculation are set by the shear spectra and the Ozmidov scale. Median Richardson number was lower toward the center of the eddy because of a large decrease in Brunt-Vaisala frequency (N2) and was depressed on the fringes by high shear. Lower median Ri is also found at the center of the ring as a result of low N2. Lower bounds on vertical eddy diffusivity are estimated based on the assumptions of a simple, mixing-length model and of complete mixing of each region where Ri is less than 0.25. The spatial distribution of this quantity within the eddy and the ring mirrors that of median Ri. Values range from Az ˜ 1.1 cm2 s-1 near the center of the eddy and 0.90 cm2 s-1 near the center of the ring to zero in

  16. Surface structure of CdSe Nanorods revealed by combined X-rayabsorption fine structure measurements and ab-initio calculations

    SciTech Connect

    Aruguete, Deborah A.; Marcus, Matthew A.; Li, Liang-shi; Williamson, Andrew; Fakra, Sirine; Gygi, Francois; Galli, Giulia; Alivisatos, A. Paul

    2006-01-27

    We report orientation-specific, surface-sensitive structural characterization of colloidal CdSe nanorods with extended X-ray absorption fine structure spectroscopy and ab-initio density functional theory calculations. Our measurements of crystallographically-aligned CdSe nanorods show that they have reconstructed Cd-rich surfaces. They exhibit orientation-dependent changes in interatomic distances which are qualitatively reproduced by our calculations. These calculations reveal that the measured interatomic distance anisotropy originates from the nanorod surface.

  17. Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

    PubMed

    Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

    2013-01-15

    The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination. PMID:23227949

  18. Luminescence and fine structure correlation in ZnO permeated porous silicon nanocomposites.

    PubMed

    Gallach, D; Muñoz-Noval, A; Torres-Costa, V; Manso-Silván, M

    2015-08-28

    Nanocomposites formed by porous silicon (PS) and zinc oxide (ZnO) have potential for applications in optoelectronic devices. However, understanding the distribution of both materials in the nanocomposite, and especially the fine structure of the synthesized ZnO crystals, is key for future device fabrication. This study focuses on the advanced characterization of a range of PS-ZnO nanocomposites by using photon- and ion-based techniques, such as X-ray absorption spectroscopy (XAS) and elastic backscattering spectroscopy (EBS), respectively. PS substrates formed by the electrochemical etching of p(+)-type Si are used as host material for the sol-gel nucleation of ZnO nanoparticles. Different properties are induced by annealing in air at temperatures ranging from 200 °C to 800 °C. Results show that wurtzite ZnO nanoparticles form only at temperatures above 200 °C, coexisting with Si quantum dots (QDs) inside a PS matrix. Increasing the annealing temperature leads to structural and distribution changes that affect the electronic and local structure of the samples changing their luminescence. Temperatures around 800 °C activate the formation of a new zinc silicate phase and transform PS into an amorphous silicon oxide (SiOx, x≈ 2) matrix with a noticeably reduced presence of Si QDs. Thus, these changes affect dramatically the emission from these nanocomposites and their potential applications. PMID:26202423

  19. Emission wavelength tuning of fluorescence by fine structural control of optical metamaterials with Fano resonance.

    PubMed

    Moritake, Y; Kanamori, Y; Hane, K

    2016-01-01

    We demonstrated fine emission wavelength tuning of quantum dot (QD) fluorescence by fine structural control of optical metamaterials with Fano resonance. An asymmetric-double-bar (ADB), which was composed of only two bars with slightly different bar lengths, was used to obtain Fano resonance in the optical region. By changing the short bar length of ADB structures with high dimensional accuracy in the order of 10 nm, resonant wavelengths of Fano resonance were controlled from 1296 to 1416 nm. Fluorescence of QDs embedded in a polymer layer on ADB metamaterials were modified due to coupling to Fano resonance and fine tuning from 1350 to 1376 nm was observed. Wavelength tuning of modified fluorescence was reproduced by analysis using absorption peaks of Fano resonance. Tuning range of modified fluorescence became narrow, which was interpreted by a simple Gaussian model and resulted from comparable FWHM in QD fluorescence and Fano resonant peaks. The results will help the design and fabrication of metamaterial devices with fluorophores such as light sources and biomarkers. PMID:27622503

  20. Impact of instrumental systematic errors on fine-structure constant measurements with quasar spectra

    NASA Astrophysics Data System (ADS)

    Whitmore, Jonathan B.; Murphy, Michael T.

    2015-02-01

    We present a new `supercalibration' technique for measuring systematic distortions in the wavelength scales of high-resolution spectrographs. By comparing spectra of `solar twin' stars or asteroids with a reference laboratory solar spectrum, distortions in the standard thorium-argon calibration can be tracked with ˜10 m s-1 precision over the entire optical wavelength range on scales of both echelle orders (˜50-100 Å) and entire spectrographs arms (˜1000-3000 Å). Using archival spectra from the past 20 yr, we have probed the supercalibration history of the Very Large Telescope-Ultraviolet and Visible Echelle Spectrograph (VLT-UVES) and Keck-High Resolution Echelle Spectrograph (HIRES) spectrographs. We find that systematic errors in their wavelength scales are ubiquitous and substantial, with long-range distortions varying between typically ±200 m s-1 per 1000 Å. We apply a simple model of these distortions to simulated spectra that characterize the large UVES and HIRES quasar samples which previously indicated possible evidence for cosmological variations in the fine-structure constant, α. The spurious deviations in α produced by the model closely match important aspects of the VLT-UVES quasar results at all redshifts and partially explain the HIRES results, though not self-consistently at all redshifts. That is, the apparent ubiquity, size and general characteristics of the distortions are capable of significantly weakening the evidence for variations in α from quasar absorption lines.

  1. Synthesis, fine structural characterization, and CO2 adsorption capacity of metal organic frameworks-74.

    PubMed

    Adhikari, Abhijit Krishna; Lin, Kuen-Song

    2014-04-01

    Two metal organic frameworks of MOF-74 group (zinc and copper-based) were successfully synthesized, characterized, and evaluated for CO2 adsorption. The both samples such as MOF-74(Zn) and MOF-74(Cu) were characterized with FE-SEM for morphology and particle size, XRD patterns for phase structure, FTIR for organic functional groups, nitrogen adsorption for pore textural properties, and X-ray absorption spectroscopy for fine structural parameters and oxidation states of central metal atoms. CO2 adsorption isotherms of MOF-74 samples were measured in a volumetric adsorption unit at 273 K and pressure up to 1.1 bar. The MOF-74(Zn) and MOF-74(Cu) adsorbents have the pore widths of 8.58 and 8.04 angstroms with the BET specific surface areas of 1,474 and 1,345 m2 g(-1), respectively. CO2 adsorption capacities of MOF-74(Zn) and MOF-74(Cu) were 4.10 and 3.38 mmol x g(-1), respectively measured at 273 K and 1.1 bar. The oxidation state of central atoms in MOF-74(Zn) was Zn(II) confirmed by XANES spectra while MOF-74(Cu) was composed of Cu(I) and Cu(II) central atoms. The bond distances of Zn--O and Cu--O were 1.98 and 1.94 angstroms, respectively. PMID:24734683

  2. Fine Structure of Starch-Clay Composites as Biopolymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Midsol 50 wheat starch and 5% Cloisite clay with or without the addition of glycerin were used to prepare biopolymers in a twin-screw extruder. Early trials of sectioning the unembedded biopolymer resulted in the immediate absorption of water and subsequent dissolution of the sample due to the the ...

  3. Relative importance of temporal envelope and fine structure in lexical-tone perception (L)

    NASA Astrophysics Data System (ADS)

    Xu, Li; Pfingst, Bryan E.

    2003-12-01

    The relative importance of temporal envelope and fine structure in speech and music perception was investigated by Smith et al. [Nature (London) 416, 87-90 (2002)] using ``auditory chimera'' in which the envelope from one sound was paired with the fine structure of another. Smith et al. found that, when 4 to 16 frequency bands were used, recognition of English speech was dominated by the envelope, whereas recognition of melody was dominated by the fine structure. In the present study, Mandarin Chinese monosyllables were divided into 4, 8, or 16 frequency bands and the fine structure and envelope of one tone pattern were exchanged with those of another tone pattern of the same monosyllable. Five normal-hearing native Mandarin Chinese speakers completed a four-alternative forced-choice tone-identification task. In the vast majority of trials, subjects based their identification of the monosyllables on the fine structure rather than the envelope. Thus, the relative importance of envelope and fine structure for lexical-tone perception resembled that for melody recognition rather than that for English speech recognition. Delivering fine-structure information in cochlear implant stimulation could be particularly beneficial for lexical-tone perception.

  4. Fine-structure enhancement — assessment of a simple method to resolve overlapping bands in spectra

    NASA Astrophysics Data System (ADS)

    Barth, Andreas

    2000-05-01

    A simple mathematical procedure — fine-structure enhancement — has been assessed on its ability to resolve overlapping bands in spectra. Its advantages and limitations have been explored using synthetic and experimental spectra. Fine-structure enhancement involves smoothing the original spectrum, multiplying the smoothed spectrum with a weighting factor and subtracting this spectrum from the original spectrum. As a result, the fine-structure of the original spectrum is enhanced in the processed spectrum and bands that overlap in the original spectrum appear as distinct bands in the processed spectrum. To be resolved by fine-structure enhancement, Lorentzian lines have to be separated by more than their quarter width at half maximum, Gaussian lines by more than their half width at half maximum. A comparison of fine-structure enhancement and Fourier self-deconvolution shows that Fourier self-deconvolution has in theory a higher potential to resolve overlapping bands. However, this depends crucially on the correct choice of the parameters. In practice, when parameters commonly used are chosen for Fourier self-deconvolution, fine-structure enhancement leads to similar results. This is demonstrated at the example of the infrared absorbance spectrum of the protein papain, where the amide I band components could be resolved similarly with both methods. Thus, fine-structure enhancement seems to be a simple alternative to Fourier self-deconvolution that does not require specialised software.

  5. EXAFS and principal component analysis : a new shell game.

    SciTech Connect

    Wasserman, S.

    1998-10-28

    The use of principal component (factor) analysis in the analysis EXAFS spectra is described. The components derived from EXAFS spectra share mathematical properties with the original spectra. As a result, the abstract components can be analyzed using standard EXAFS methodology to yield the bond distances and other coordination parameters. The number of components that must be analyzed is usually less than the number of original spectra. The method is demonstrated using a series of spectra from aqueous solutions of uranyl ions.

  6. Fine structure of the amide i band in acetanilide

    NASA Astrophysics Data System (ADS)

    Careri, G.; Gratton, E.; Shyamsunder, E.

    1988-05-01

    Their absorption spectrum of both single crystals and powdered samples of acetanilide (a model system for proteins) has been studied in the amide i region, where a narrow band has been identified as a highly trapped soliton state. The powder-sample spectra have been decomposed using four Lorentzian bands. A strong temperature dependence has been found for the intensity of two of the subbands, which also show a complementary behavior. Polarization studies performed on thin crystals have shown that the subbands have the same polarization. Low-temperature spectra of partially deuterated samples show the presence of the subbands at the same absorption frequencies found using the fitting procedure in the spectra of nondeuterated samples. The soliton model currently proposed to explain the origin of the anomalous amide i component at 1650 cm-1 still holds, but some modification of the model is required to account for the new features revealed by this study.

  7. Calcium EXAFS establishes the Mn-Ca cluster in the oxygen-evolving complex of Photosystem II

    SciTech Connect

    Cinco, Roehl M.; McFarlane Holman, Karen L.; Robblee, John H.; Yano, Junko; Pizarro, Shelly A.; Bellacchio, Emanuele; Sauer, Kenneth; Yachandra, Vittal K.

    2002-08-02

    The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared subsequent to Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 angstroms, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is {approx}; 3.5 angstroms distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster.

  8. EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides - II. Effects of chloride and sulfate

    USGS Publications Warehouse

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

    2004-01-01

    Common complexing ligands such as chloride and sulfate can significantly impact the sorption of Hg(II) to particle surfaces in aqueous environmental systems. To examine the effects of these ligands on Hg(II) sorption to mineral sorbents, macroscopic Hg(II) uptake measurements were conducted at pH 6 and [Hg]i=0.5 mM on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) in the presence of chloride or sulfate, and the sorption products were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of chloride resulted in reduced uptake of Hg(II) on all three substrates over the Cl- concentration ([Cl-]) range 10-5 to 10-2 M, lowering Hg surface coverages on goethite, ??-alumina, and bayerite from 0.42 to 0.07 ??mol/m2, 0.06 to 0.006 ??mol/m2, and 0.55 to 0.39 ??mol/m2 ([Cl -]=10-5 to 10-3 M only), respectively. This reduction in Hg(II) uptake is primarily a result of the formation of stable, nonsorbing aqueous HgCl2 complexes in solution, limiting the amount of free Hg(II) available to sorb. At higher [Cl-] beam reduction of Hg(II) to Hg(I) was observed, resulting in the possible formation of aqueous Hg2Cl2 species and the precipitation of calomel, Hg 2Cl2(s). The presence of sulfate caused enhanced Hg(II) uptake over the sulfate concentration ([SO42-]) range 10-5 to 0.9 M, increasing Hg surface coverages on goethite, ??-alumina, and bayerite from 0.39 to 0.45 ??mol/m2, 0.11 to 0.38 ??mol/m2, and 0.36 to 3.33 ??mol/m2, respectively. This effect is likely due to the direct sorption or accumulation of sulfate ions at the substrate interface, effectively reducing the positive surface charge that electrostatically inhibits Hg(II) sorption. Spectroscopic evidence for ternary surface complexation was observed in isolated cases, specifically in the Hg-goethite-sulfate system at high [SO42-] and in the Hg-goethite-chloride system. ?? 2003 Elsevier Inc. All rights reserved.

  9. An Elliptical Crystal Spectrometer Suitable for EXAFS Studies of Laser Compressed Materials and for High Resolution X-Ray Spectroscopy.

    PubMed

    Ridgeley, A; Goodman, D; Hall, T A

    1995-01-01

    Using an x-ray spectrometer with an elliptically curved crystal it is possible to study absorption spectra from a target placed at one focus of the ellipse using a backlighting source placed at the other focus. This principle has been used to develop a spectrometer for EXAFS studies of laser compressed materials. The backlighting source is placed at one focus of the ellipse and the laser compressed EXAFS sample at the other. Using this technique a small area of the EXAFS target can be probed, thereby minimizing any spatial variations in the compressed plasma due to nonuniformities in the laser beams. Also, the dispersive nature of the crystal ensures that it acts as a bandpass filter, so that the EXAFS sample is not probed by other x-ray wavelengths which may cause unwanted heating. Another advantage is that compressed and uncompressed EXAFS spectra can be compared on a single shot. The optical properties of the spectrometer are discussed analytically and using a computer ray-tracing program. The development and alignment of the elliptical spectrometer are discussed, and its performance using both x-ray film and a CCD detector is evaluated. The use of the elliptical spectrometer as a high-resolution x-ray instrument is presented. PMID:21307480

  10. 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.

  11. 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.

  12. 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. PMID:27182829

  13. Sulphur speciation in bitumens and asphaltenes by X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Kasrai, Masoud; Bancroft, G. Michael; Brunner, Roger W.; Jonasson, Ralph G.; Brown, James R.; Tan, Kim H.; Feng, Xinghong

    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 -8 torr). Thus XANES represents a rapid, nondestructive mean of characterizing specific classes of compounds in complex matrices, such as bitumen.

  14. 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.

  15. A new detector for sub-millisecond EXAFS spectroscopy at the European Synchrotron Radiation Facility

    PubMed Central

    Kantor, Innokenty; Labiche, Jean-Claude; Collet, Emmanuel; Siron, Laurent; Thevenin, Jean-Jacques; Ponchut, Cyril; Borrel, Jacques; Mairs, Trevor; Marini, Carlo; Strohm, Cornelius; Mathon, Olivier; Pascarelli, Sakura

    2014-01-01

    A new FReLoN (Fast-Readout Low-Noise) high-frame-rate detector adopted for the fast continuous collection of X-ray absorption spectra is presented. The detector is installed on the energy-dispersive X-ray absorption beamline ID24 at the ESRF and is capable of full time-resolved EXAFS spectra collection with over 4 kHz repetition rate and 0.2 ms exposure time. An example of the in situ kinetic study of the high-temperature oxidation of metallic iron is presented. PMID:25343790

  16. Hydride phase formation in carbon supported palladium hydride nanoparticles by in situ EXAFS and XRD

    NASA Astrophysics Data System (ADS)

    Bugaev, A. L.; Guda, A. A.; Lomachenko, K. A.; Lazzarini, A.; Srabionyan, V. V.; Vitillo, J. G.; Piovano, A.; Groppo, E.; Bugaev, L. A.; Soldatov, A. V.; Dmitriev, V. P.; Pellegrini, R.; van Bokhoven, J. A.; Lamberti, C.

    2016-05-01

    In the current work we present a detailed analysis of the hydride phase formation in industrial Pd/C nanocatalysts by means of combined in situ X-ray absorption spectroscopy (EXAFS), X-ray diffraction (XRD) and volumetric measurements for the temperatures from - 10 to 50 °C in the hydrogen pressure range from 0 to 1000 mbar. α- and β- hydride phases are clearly distinguished in XRD. For the first time, H/Pd atomic ratio were obtained by theoretical fitting of the near-edge region of the absorption spectra (XANES) and compared with volumetric measurements.

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

    SciTech Connect

    Cinco, Roehl M.

    1999-12-16

    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 NH{sub 2}OH-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 [Mn{sub 4}O{sub 3}X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn{sub 4}O{sub 3}Cl 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 glutathione show distinct

  18. Nickel Sorption to Bacteriogenic Manganese Oxides: Insights from X-ray Absorption Spectroscopy and Density Functional Theory

    NASA Astrophysics Data System (ADS)

    Pena, J.; Kwon, K.; Refson, K.; Bargar, J. R.; Sposito, G.

    2008-12-01

    Bacteriogenic Mn oxides are ubiquitous, highly reactive minerals with a remarkable capacity to scavenge metals due to their nanoparticulate dimensions and abundant structural defects. These minerals are commonly deposited in a matrix of bacterial cells and extracellular polymeric substances, forming geosymbiotic systems whose reactivity with contaminant metals is not fully characterized. In the current study, a synergistic experimental-computational approach was used to study the mechanism of Ni adsorption at varying loadings and at pH 6-8 using the Mn oxide produced by Pseudomonas putida GB-1. Extended X-ray absorption fine structure (EXAFS) spectra showed two dominant coordination environments: Ni bound as a triple corner sharing (TCS) complex at octahedral vacancy sites and Ni incorporated into the octahedral sheet. The proportion of adsorbed and incorporated Ni varied as a function of surface coverage and pH, with the latter form of Ni being favored at higher loadings and decreased proton activity. These two coordination environments, although consistent with data published for Ni sorbed by synthetic MnO2(s), did not describe fully all of our EXAFS spectra, leading us to consider the binding of Ni at particle edges or via a non-specific sorption mechanism. In parallel to the spectral analysis, density functional theory (DFT) calculations were performed to test different adsorbate-adsorbent configurations and the pH dependence of the adsorption mechanism. Geometry optimized structures for Ni sorbed above vacancies (i.e., TCS) or incorporated into the Mn oxide structure were in excellent agreement with corresponding structural parameters obtained from EXAFS analysis. The calculated energy barriers for the transition from adsorbed TCS to incorporated Ni were consistent with the hypothesis that the TCS complex is a precursor for Ni incorporation and that incorporation is favored by decreased proton activity. The combined perspectives obtained from these two

  19. The apparent fine-tuning of the cosmological, gravitational and fine structure constants

    NASA Astrophysics Data System (ADS)

    Eaves, Laurence

    2016-02-01

    A numerical coincidence relating the values of the cosmological, gravitational and electromagnetic fine structure constants is presented and discussed in relation to the apparent anthropic fine-tuning of these three fundamental constants of nature.

  20. New fine structure cooling rate. [electron impact transitions in the ionosphere

    NASA Technical Reports Server (NTRS)

    Hoegy, W. R.

    1976-01-01

    One of the dominant electron cooling processes in the ionosphere is caused by electron impact induced fine structure transitions among the ground state levels of atomic oxygen. This fine structure cooling rate is based on theoretical cross sections. Recent advances in the numerical cross section determinations to include polarization effects and more accurate representations of the atomic target result in new lower values. These cross sections are employed in this paper to derive a new fine structure cooling rate which is between 40% and 60% of the currently used rate. A new generalized formula is presented for the cooling rate (from which the fine structure cooling rate is derived), valid for arbitrary mass and temperature difference of the colliding particles and arbitrary inelastic energy difference.

  1. 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.

  2. Models for molybdenum coordination during the catalytic cycle of periplasmic nitrate reductase from Paracoccus denitrificans derived from EPR and EXAFS spectroscopy.

    PubMed

    Butler, C S; Charnock, J M; Bennett, B; Sears, H J; Reilly, A J; Ferguson, S J; Garner, C D; Lowe, D J; Thomson, A J; Berks, B C; Richardson, D J

    1999-07-13

    The periplasmic nitrate reductase from Paracoccus denitrificans is a soluble two-subunit enzyme which binds two hemes (c-type), a [4Fe-4S] center, and a bis molybdopterin guanine dinucleotide cofactor (bis-MGD). A catalytic cycle for this enzyme is presented based on a study of these redox centers using electron paramagnetic resonance (EPR) and extended X-ray absorption fine structure (EXAFS) spectroscopies. The Mo(V) EPR signal of resting NAP (High g [resting]) has g(av) = 1.9898 is rhombic, exhibits low anisotropy, and is split by two weakly interacting protons which are not solvent-exchangeable. Addition of exogenous ligands to this resting state (e.g., nitrate, nitrite, azide) did not change the form of the signal. A distinct form of the High g Mo(V) signal, which has slightly lower anisotropy and higher rhombicity, was trapped during turnover of nitrate and may represent a catalytically relevant Mo(V) intermediate (High g [nitrate]). Mo K-edge EXAFS analysis was undertaken on the ferricyanide oxidized enzyme, a reduced sample frozen within 10 min of dithionite addition, and a nitrate-reoxidized form of the enzyme. The oxidized enzyme was fitted best as a di-oxo Mo(VI) species with 5 sulfur ligands (4 at 2. 43 A and 1 at 2.82 A), and the reduced form was fitted best as a mono-oxo Mo(IV) species with 3 sulfur ligands at 2.35 A. The addition of nitrate to the reduced enzyme resulted in reoxidation to a di-oxo Mo(VI) species similar to the resting enzyme. Prolonged incubation of NAP with dithionite in the absence of nitrate (i.e., nonturnover conditions) resulted in the formation of a species with a Mo(V) EPR signal that is quite distinct from the High g family and which has a g(av) = 1.973 (Low g [unsplit]). This signal resembles those of the mono-MGD xanthine oxidase family and is proposed to arise from an inactive form of the nitrate reductase in which the Mo(V) form is only coordinated by the dithiolene of one MGD. In samples of NAP that had been reduced with

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

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the species and structures existing in a series of ZnCl2-H2O-NaCl solutions with different chloride/zinc ratios and in a solution of ZnCl2 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 Zn2+ is significantly related to the chloride/zinc ratio, and no inner complex formation between Zn2+ and Cl- ions has been detected for low ZnCl2 concentration (0.1 and 0.2 M). Conversely, in the same concentration range (0.13 M) the ZnCl2 species do not dissociate in EAN and the Zn2+ 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.

  4. Comparison of the manganese oxygen-evolving complex in photosystem II of spinach and Synechococcus sp. with multinuclear manganese model compounds by X-ray absorption spectroscopy

    SciTech Connect

    DeRose, V.J.; Mukerji, I.; Latimer, M.J. ); Yachandra, V.K.; Klein, M.P. ); Sauer, K. Lawrence Berkeley Lab., CA )

    1994-06-15

    The evaluation of Mn X-ray absorption fine structure (EXAFS) studies on the oxygen-evolving complex (OEC) from photosystem II is described for preparations from both spinach and the cyanobacterium Synechococcus sp. poised in the S[sub 1] and S[sub 2] states. In addition to reproducing previous results suggesting the presence of bis([mu]-oxo)-bridged Mn centers in the OEC, a Fourier transform peak due to scatterers at an average distance of > 3 [angstrom] is detected in both types of preparation. In addition, subtle but reproducible changes are found in the relative amplitudes of the Fourier transform peaks due to mainly O ([approximately]1.8 [angstrom]) and Mn ([approximately] 2.7 [angstrom]) neighbors upon cryogenic advance from the S[sub 1] to the S[sub 2] state. Analysis of the peak due to scatterers at [approximately] 3 [angstrom] favors assignment to (per 4 Mn in the OEC) 1-2 heavy atom (Mn, Ca) scatterers at an average distance of 3.3-3.4 [angstrom]. The EXAFS data of several multinuclear Mn model compounds containing such scattering interactions are analyzed and compared with the data for the OEC. Structural models for the OEC are evaluated on the basis of these results. 40 refs., 9 figs., 5 tabs.

  5. New Limit on the Spatial and Temporal Variations of the Fine-Structure Constant Using High Redshifts of Quasar Spectra

    NASA Astrophysics Data System (ADS)

    Le, T. D.

    2015-03-01

    Highly precise measurements on the light from distant quasars can served as a powerful tool to test the possible spatial and temporal variations of the fine-structure constant α = e 2 /c during the evolution of the Universe. Here we set a limit on the possible cosmological space-time variations of α by comparing transitions in the absorption lines of the SiIV doublet observed in the early Universe with those mesured in the laboratory. The weighted mean value of the α-variation derived from our analysis over the redshift range 2.0 ≤ cps≤ 3.7 is Δα/α (-0.53 ± 0.72) ×10-5. This result improves the constraint on Δα/α by a factor of ~ seven compared to the published results in the literature.

  6. ISO-LWS observations of Herbig Ae/Be stars. I. Fine structure lines

    NASA Astrophysics Data System (ADS)

    Lorenzetti, D.; Tommasi, E.; Giannini, T.; Nisini, B.; Benedettini, M.; Pezzuto, S.; Strafella, F.; Barlow, M.; Clegg, P. E.; Cohen, M.; di Giorgio, A. M.; Liseau, R.; Molinari, S.; Palla, F.; Saraceno, P.; Smith, H. A.; Spinoglio, L.; White, G. J.

    1999-06-01

    We present the results of the first spectrophotometric survey of a sample of eleven Herbig Ae/Be stars (HAEBE) obtained with the Long Wavelength Spectrometer (LWS) on board the Infrared Space Observatory (ISO). The [OI] 63mu m and the [CII] 158mu m lines are observed in all the investigated sources, while the [OI] 145mu m transition, due to its relative faintness, sometimes remains undetected. By comparing line intensity ratios with model predictions, photodissociation, due to the UV photons from the central star, results the dominating excitation mechanism although contributions of C-shocks to the [OI] emission cannot be ruled out. A clear example for the presence of a photodissociation region (PDR) illuminated by an HAEBE is shown by LWS spectroscopic mapping of NGC 7129. Some diagnostic probes of the radiation field and density are provided for the objects in our sample: these substantially agree with the known characteristics of both the star and its circumstellar environment, although the observed ratio [OI]63/[OI]145 tends to be smaller than predicted by PDR models. The most likely explanation for this behaviour is self-absorption at 63mu m by cold atomic oxygen. Fine structure lines of the ionised species [OIII], [NII] were detected whenever the star had a spectral type of B0 or earlier; in particular, around the star CoD-42(deg) 11721, besides a compact HII region, evidence is given for an extended low electron density ionised region. Finally, molecular line emission is associated with stars powering a CO outflow, and clumpy PDR models, better than C-shock models, predict for them relative cooling (CO vs OI and CO vs OH) similar to the observed ones. Based on observations with ISO, an ESA project with instruments funded by ESA Member States and with the participation of ISAS and NASA}

  7. 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.

  8. Raman and x-ray absorption spectroscopy characterization of Zr-doped MOCVD YBa2Cu2O6+delta.

    SciTech Connect

    Maroni, V. A.; Kropf, Arthur J; Aytug, Tolga; Paranthaman, Mariappan Parans

    2010-01-01

    Metal organic chemical vapor deposited YBa2Cu3O6+ (YBCO) films (about 0.9 m thick) containing varying amounts of added zirconium were examined by Raman microscopy and synchrotron x-ray absorption spectroscopy. The self-field and in-field (1 T, B c) Jc performance of the YBCO films at 77 K (reported by the group at Oak Ridge National Laboratory that fabricated the samples) exhibited an increase on going from 0 mol% (m/o) Zr-added to 2.5 m/o Zr-added but then decreased sharply with increasing Zr content. Raman measurements on these films showed that the added Zr had little effect on YBCO cation disorder up to about 7.5 m/o Zr-added. Cation disorder increased while Ba Cu O content remained relatively constant for Zr additions 7.5 m/o. In the region of sharpest descent of Jc with increasing Zr content (2.5 7.5 m/o Zr-added) neither the cation disorder nor the Ba Cu O content showed a systematic variation with Jc. Zirconium K edge x-ray absorption near-edge spectroscopy revealed that virtually all of the added Zr in each sample was present as a BaZrO3-like phase (BZO). The Jc performance of the Zr-added films showed a high correlation with the variations in the next-nearest-neighbor Zr M (M = Zr, Y) scattering path amplitude from the extended x-ray absorption fine structure (EXAFS) and the critical temperature over the full range of Zr additions and with cation disorder at the higher Zr-added levels (>7.5 m/o). There was no obvious correlation with the amount of residual barium cuprate or CuO. Approximate ranges for the BZO particle dimensions estimated from the EXAFS data indicated that the mean particle size gets larger with increasing Zr addition.

  9. 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

  10. CONSTRAINTS ON SPATIAL VARIATIONS IN THE FINE-STRUCTURE CONSTANT FROM PLANCK

    SciTech Connect

    O'Bryan, Jon; Smidt, Joseph; De Bernardis, Francesco; Cooray, Asantha

    2015-01-01

    We use the cosmic microwave background (CMB) anisotropy data from Planck to constrain the spatial fluctuations of the fine-structure constant α at a redshift of 1100. We use a quadratic estimator to measure the four-point correlation function of the CMB temperature anisotropies and extract the angular power spectrum fine-structure constant spatial variations projected along the line of sight at the last scattering surface. At tens of degree angular scales and above, we constrain the fractional rms fluctuations of the fine-structure constant to be (δα/α){sub rms} < 3.4 × 10{sup –3} at the 68% confidence level. We find no evidence for a spatially varying α at a redshift of 10{sup 3}.

  11. A simulation for gravity fine structure recovery from high-low GRAVSAT SST data

    NASA Technical Reports Server (NTRS)

    Estes, R. H.; Lancaster, E. R.

    1976-01-01

    Covariance error analysis techniques were applied to investigate estimation strategies for the high-low SST mission for accurate local recovery of gravitational fine structure, considering the aliasing effects of unsolved for parameters. Surface density blocks of 5 deg x 5 deg and 2 1/2 deg x 2 1/2 deg resolution were utilized to represent the high order geopotential with the drag-free GRAVSAT configured in a nearly circular polar orbit at 250 km. altitude. GEOPAUSE and geosynchronous satellites were considered as high relay spacecraft. It is demonstrated that knowledge of gravitational fine structure can be significantly improved at 5 deg x 5 deg resolution using SST data from a high-low configuration with reasonably accurate orbits for the low GRAVSAT. The gravity fine structure recoverability of the high-low SST mission is compared with the low-low configuration and shown to be superior.

  12. Chapter 1 - The Impacts of X-Ray Absorption Spectroscopy on Understanding Soil Processes and Reaction Mechanisms

    SciTech Connect

    Ginder-Vogel, Matthew; Sparks, Donald L.

    2011-11-17

    During the last two decades, X-ray absorption spectroscopy (XAS) has developed into a mature technique for obtaining the speciation (e.g., oxidation state) and short-range structure of elements present in soils and sediments. XAS encompasses both X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. XAS has a number of advantageous qualities for studying soils and sediments, which include elemental specificity, sensitivity to the local chemical and structural state of an element, and the ability to analyze materials in situ. This information allows accurate determination of oxidation state, type of nearest neighbors, coordination number, bond distance, and orbital symmetries of the X-ray absorbing element. In this review, we examine the application of a wide variety of synchrotron X-ray techniques to fundamental issues in environmental soil chemistry. Additionally, we examine the application of microfocused and time-resolved XAS to determine speciation (e.g., oxidation state and/or local coordination environment) and transformation kinetics of contaminants in heterogeneous environmental systems. During the last three decades, XAS has a played a critical role in furthering our understanding of a myriad of environmental systems and will continue to do so into the foreseeable future.

  13. A note on chromospheric fine structure at active region polarity boundaries.

    NASA Technical Reports Server (NTRS)

    Prata, S. W.

    1971-01-01

    High resolution H-alpha filtergrams from Big Bear Solar Observatory reveal that some filamentary features in active regions have fine structure and hence magnetic field transverse to the gross structure and the zero longitudinal field line. These features are distinct from the usual active region filament, in which fine structure, magnetic field, and filament are all parallel to the zero longitudinal field line. The latter occur on boundaries between regions of weaker fields, while the former occur at boundaries between regions of stronger field.

  14. Coupled-channels study of fine structure in the {alpha} decay of platinum isotopes

    SciTech Connect

    Ni Dongdong; Ren Zhongzhou

    2011-09-15

    The fine structure observed in the {alpha} decay of deformed platinum isotopes is investigated using the recently developed five-channel formalism, based on the coupled-channel Schroedinger equation with outgoing wave boundary conditions. The internal effect of daughter states is taken into account in dealing with the interaction matrix and the {alpha}-cluster formation. The available experimental data concerning {alpha}-decay half-lives and fine structures are reproduced. Some predictions are made especially for the {alpha} decay of neutron-rich isotopes, which could guide future experiments.

  15. Progress towards a precision measurement of the n=2 triplet P fine structure of atomic helium

    NASA Astrophysics Data System (ADS)

    Kato, K.; Fitzakerley, D. W.; George, M. C.; Vutha, A. C.; Storry, C. H.; Hessels, E. A.

    2016-05-01

    We report progress on the measurement of the J = 1 to J = 2 23 P fine-structure interval of atomic helium. The measurement uses a liquid-nitrogen-cooled DC discharge source of metastable helium and the atomic beam is laser cooled in the transverse directions. The atoms are excited to 23 P by a 1083-nm diode laser, and the fine-structure transition is driven by microwaves using the frequency-offset separated oscillatory fields technique. The transition is detected by further laser excitation to a Rydberg state, followed by Stark ionization. This work is supported by NSERC, CRC.

  16. Effect of acoustic fine structure cues on the recognition of auditory-only and audiovisual speech.

    PubMed

    Meister, Hartmut; Fuersen, Katrin; Schreitmueller, Stefan; Walger, Martin

    2016-06-01

    This study addressed the hypothesis that an improvement in speech recognition due to combined envelope and fine structure cues is greater in the audiovisual than the auditory modality. Normal hearing listeners were presented with envelope vocoded speech in combination with low-pass filtered speech. The benefit of adding acoustic low-frequency fine structure to acoustic envelope cues was significantly greater for audiovisual than for auditory-only speech. It is suggested that this is due to complementary information of the different acoustic and visual cues. The results have potential implications for the assessment of bimodal cochlear implant fittings or electroacoustic stimulation. PMID:27369134

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

    PubMed

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

    2015-07-21

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

  18. Understanding Structural Properties of Carbonate-Silicate Melts: An EXAFS Study on Y and Sr in the System Na2O-CaO-Al2O3-SiO2-CO2

    NASA Astrophysics Data System (ADS)

    Pohlenz, J.; Pascarelli, S.; Mathon, O.; Belin, S.; Shiryaev, A.; Safonov, O.; Murzin, V.; Shablinskaya, K.; Irifune, T.; Wilke, M.

    2014-12-01

    Carbonatite volcanism generally occurs in intra-plate settings associated with continental rifting. The only active carbonatitic volcano is the Oldoinyo Lengai, Tanzania, which generates sodium-rich carbonatites in close association with phonolites and nephelinites1. The processes of carbonatite genesis are still unresolved, however carbonate-bearing melts evidently play a crucial role during mantle melting, in diamond formation and as metasomatic agents. Carbonate melts show extraordinary properties, especially in regard to their low melt viscosities and densities, high surface tensions and electrical conductivities as well as distinct geochemical affinities to a wide range of trace elements2. Understanding the structural properties of carbonate-bearing melts is fundamental to explaining their chemical and physical behaviour as well as modeling processes operating in the deep Earth. Extended X-ray absorption fine structure (EXAFS) spectroscopy is a versatile tool for element specific investigation of the short to medium range structure of melts and glasses. This study focuses on unraveling the influence of carbonate concentration on the structural incorporation of the geochemically important trace elements Y and Sr in silicate and carbonate melts in the system Na2O-CaO-Al2O3-SiO2-CO2. First, we present structural data of silicate glasses with up to 10 wt% CO2, quenched from melts under high temperature and pressure, which indicate that the local structure of Y and Sr is not or only slightly affected by CO2. Melts with higher CO2 contents could not be quenched to glass, so far. Second, we show results of high pressure, high temperature experiments conducted in the Paris Edinburgh-Press, which provides in-situ insight into carbonate-silicate melts. All EXAFS measurements were performed at the synchrotron facility beamlines SAMBA (SOLEIL) and BM23 (ESRF). Information derived from the trace elements' local structure is used to develop a structural model for carbonate

  19. Investigation of the different binding edge sites for Zn on montmorillonite using P-EXAFS - The strong/weak site concept in the 2SPNE SC/CE sorption model

    NASA Astrophysics Data System (ADS)

    Dähn, Rainer; Baeyens, Bart; Bradbury, Michael H.

    2011-09-01

    The 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) sorption model has been used over the past decade or so to quantitatively describe the uptake of metals with oxidation states from II to VI on 2:1 clay minerals; montmorillonite and illite. One of the main features in this model is that there are two broad categories of amphoteric edge sorption sites; the so called strong ( tbnd S SOH) and weak ( tbnd S W1OH) sites. Because of their different sorption characteristics, it was expected that the coordination environments of the surface complexes on the two site types would be different. Zn isotherm data on two montmorillonites, Milos and STx-1, were measured and modelled using the 2SPNE SC/CE sorption model. The results were used to define the most favourable experimental conditions under which Zn sorption was either dominated by the strong ( tbnd S SOH, ˜2 mmol kg -1) or by the weak sites ( tbnd S W1OH, ˜40 mmol kg -1). Highly oriented self-supporting films were prepared for polarised extended X-ray absorption fine structure (P-EXAFS) investigations. Montmorillonites often contain Zn incorporated in the clay matrix. The Zn bound in this form was quantified and the results from the analysis of the P-EXAFS spectra were taken into account in the interpretation of the spectra measured at low Zn loadings (˜2 mmol kg -1) and medium Zn loadings (˜30 mmol kg -1). The Zn spectra on the "strong sites" exhibited a pronounced angular dependency and formed surface complexes in the continuity of the Al-octahedral sheets at the montmorillonite edges. In contrast, the Zn "weak site" spectra showed only a weak angular dependency. The spectroscopic evidence indicates the existence of two distinct groups of edge surface binding sites which is consistent with a multi-site sorption model and in particular with the strong/weak site concept intrinsic to the 2SPNE S/CE sorption model.

  20. Suppression of fine-structure splitting and oscillator strength of sodium D-line in a Debye plasma

    SciTech Connect

    Basu, Joyee Ray, Debasis

    2014-01-15

    We investigate theoretically the influence of static plasma screening on relativistic spin-orbit interaction-induced fine-structure splitting of the D-line doublet arising from the transitions 3p{sub 1/2}–3s{sub 1/2} and 3p{sub 3/2}–3s{sub 1/2} of the valence electron of a sodium atom embedded in a model plasma environment. The many-electron atomic problem is formulated first as an effective one-electron problem in which the interaction between the optically active valence electron and the atomic ion core is represented by an accurate parametric model potential including core-polarization correction, and then the plasma effect on the atomic system is simulated by the Debye-screening model for the valence-core interaction. It is observed that the magnitude of spin-orbit energy shift reduces for both the upper component 3p{sub 3/2} and the lower component 3p{sub 1/2} with increasing plasma screening strength, thereby reducing the spin-orbit energy separation between these two components as the screening becomes stronger. As a consequence, the magnitude of fine-structure splitting between the D{sub 1} and D{sub 2} line energies of sodium drops significantly with stronger plasma screening. The optical (absorption) oscillator strength for 3s → 3p transition is seen to reduce with stronger screening and this leads to a screening-induced gradual suppression of the 3p → 3s spontaneous decay rate.

  1. Delay between the Circularly Polarized Components in Fine Structures during Solar Type IV Events

    NASA Astrophysics Data System (ADS)

    Chernov, G. P.; Zlobec, P.

    1995-08-01

    We analyzed intermediately polarized (20 80%) fine structures (pulsations, sudden reductions, fiber bursts and zebras) that were recorded in type IV events. The mean polarization degree was practically the same for all the fine structures recorded in an interval lasting a few minutes and it was similar to the polarization of the continuum. A detailed analysis during the evolution of single structures reveals changes in polarization (in particular an ‘undulation’ at flux density minima) even stronger than 20%. They were caused by a delay, up to 0.1 s, between the two circularly polarized components. The weaker polarimetric component was delayed in 2 sets and the stronger one in 1 set. In the event of April 24, 1985 different types of fine structures were sporadically detected in more than one hour long time interval. Short delays of the stronger or of the weaker component were sometimes observed. The events characterized by fine structures are generally totally polarized in the ordinary mode. We assume that this holds also for the phenomena studied here. The observed intermediate polarization therefore requires a depolarization due to propagation effects. We discuss the mode coupling and the reflection of the original radio signal that could also generate the delay of the weaker and the stronger component respectively. The possibility of polarization variation due to the change of the angle between the direction of the propagation and the magnetic field in a quasi-transversal region and in a low intensity magnetic field in a current sheet is also given.

  2. Fine structural characterization of microbodies and Woronin bodies in Trichophyton mentagrophytes.

    PubMed

    Vannini, G L; Mares, D

    1975-08-15

    Microbodies and Woronin bodies, organelles surrounded by a single unit membrane, were identified in the hyphal cells of Trichophyton mentagrophytes by employing a fixative containing TAPO. The fine structure of the organelles is described and their possible significance discussed. PMID:1157867

  3. Compensation of logarithmic corrections in calculating the fine structure of levels in hydrogen-like atoms

    SciTech Connect

    Boikova, N. A. Tyukhtyaev, Yu. N.; Faustov, R. N.

    2011-01-15

    Special features of the quasipotential approach to calculating logarithmic (in the fine-structure constant) contributions to the fine splitting of energy levels in hydrogen-like atoms are analyzed. The boundaries of the region of applicability of the Fell technique are indicated, and the order of corrections beyond this region is estimated.

  4. The impact of cochlear fine structure on hearing thresholds and DPOAE levels

    NASA Astrophysics Data System (ADS)

    Lee, Jungmee; Long, Glenis; Talmadge, Carrick L.

    2001-05-01

    Although otoacoustic emissions (OAE) are used as clinical and research tools, the correlation between OAE behavioral estimates of hearing status is not large. In normal-hearing individuals, the level of OAEs can vary as much as 30 dB when the frequency is changed less than 5%. These pseudoperiodic variations of OAE level with frequency are known as fine structure. Hearing thresholds measured with high-frequency resolution reveals a similar (up to 15 dB) fine structure. We examine the impact of OAE and threshold fine structures on the prediction of auditory thresholds from OAE levels. Distortion product otoacoustic emissions (DPOAEs) were measured with sweeping primary tones. Psychoacoustic detection thresholds were measured using pure tones, sweep tones, FM tones, and narrow-band noise. Sweep DPOAE and narrow-band threshold estimates provide estimates that are less influenced by cochlear fine structure and should lead to a higher correlation between OAE levels and psychoacoustic thresholds. [Research supported by PSC CUNY, NIDCD, National Institute on Disability and Rehabilitation Research in U.S. Department of Education, and The Ministry of Education in Korea.

  5. The role of adiabaticity in alkali atom-fine structure mixing

    NASA Astrophysics Data System (ADS)

    Eshel, Ben; Weeks, David E.; Perram, Glen P.

    2014-02-01

    Fine-structure mixing cross-sections for the alkalis in collisions with the rare gases are reviewed. Included in the review are all the rare gases in collisions with all of the first excited state of the alkalis, the second excited state for K, Rb and Cs and the third excited state for Rb and Cs. The cross-sections are converted to probabilities for energy transfer using a quantum-defect calculated cross-section and are then presented as a function of adiabaticity. The data shows a clear decreasing trend with adiabaticity but secondary factors prevent the probabilities from decreasing as quickly as expected. Polarizability is introduced as a proxy for the secondary influences on the data as it increases with both rare gas partner and alkali excited state. The polarizability is shown to cause the probability of fine structure transition to be higher than expected. An empirical model is introduced and fit to the data. Future work will develop a model using time-independent perturbation theory in order to further develop a physical rational for the dependence of fine structure cross sections on adiabaticity and to further understand the secondary influences on the probability for fine structure transition.

  6. Accuracy of mapping the Earth's gravity field fine structure with a spaceborne gravity gradiometer mission

    NASA Technical Reports Server (NTRS)

    Kahn, W. D.

    1984-01-01

    The spaceborne gravity gradiometer is a potential sensor for mapping the fine structure of the Earth's gravity field. Error analyses were performed to investigate the accuracy of the determination of the Earth's gravity field from a gravity field satellite mission. The orbital height of the spacecraft is the dominating parameter as far as gravity field resolution and accuracies are concerned.

  7. 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.

  8. Comparison of EXAFS Foil Spectra from Around the World

    SciTech Connect

    Kelly, S. D.; Bare, S. R.; Greenlay, N.; Azevedo, G.; Balasubramanian, M.; Barton, D.; Chattopadhyay, S.; Fakra, S.; Johannessen, B.; Newville, M.; Pena, J.; Pokrovski, G. S; Proux, O.; Priolkar, K.; Ravel, B.; Webb, S. M.

    2010-07-16

    The EXAFS spectra of Cu and Pd foil from many different beamlines and synchrotrons are compared to address the dependence of the amplitude reduction factor (S{sub 0}{sup 2}) on beamline specific parameters. Even though S{sub 0}{sup 2} is the same parameter as the EXAFS coordination number, the value for S{sub 0}{sup 2} is given little attention, and is often unreported. The S{sub 0}{sup 2} often differs for the same material due to beamline and sample attributes, such that no importance is given to S{sub 0}{sup 2}-values within a general range of 0.7 to 1.1. EXAFS beamlines have evolved such that it should now be feasible to use standard S{sub 0}{sup 2} values for all EXAFS measurements of a specific elemental environment. This would allow for the determination of the imaginary energy (Ei) to account for broadening of the EXAFS signal rather than folding these errors into an effective S{sub 0}{sup 2}-value. To test this concept, we model 11 Cu-foil and 6 Pd-foil EXAFS spectra from around the world to compare the difference in S{sub 0}{sup 2}- and Ei-values.

  9. A complete sketch for fine-structure contamination by internal waves

    NASA Astrophysics Data System (ADS)

    Gostiaux, L.; van Haren, H.

    2012-04-01

    Oceanic fine structure has been studied since the development of CTD and microstructure profilers allowed to resolve the vertical scales of temperature and salinity in the ocean. In the context of internal waves, it rapidly appeared that the advection of oceanic fine-structure may lead to erroneous interpretations of temperature measurements, and much theoretical work was achieved to distinguish real internal wave signal from the so-called fine-structure contamination. The pioneering work of Phillips (1971) revealed how the vertical advection of temperature steps by internal waves contaminates temperature records at fixed depths. Fine-structure contamination can be recognized in the super-buoyant part of the spectrum as a typical -2 slope, theoretically predicted for sharp stair cases in the temperature profile. However, distinguishing fine-structure contamination from other (turbulent) signals in real datasets is sometimes difficult. We will show how the use of a large number of highly accurate temperature sensors allows to completely resolve the fine-structure contamination sketch. More precisely, the coherence spectrum between vertically separated sensors shows a characteristic π-phase signature above the Brunt-Väisälä frequency N that we can reproduce using a simple kinematic model. The dataset used consists of temperature time series (1Hz during 1.5 year) obtained in the Canary Basin. Over a range of 132.5m, 54 NIOZ High Sampling Rate Thermistors (NIOZ-HST, 1mK relative accuracy) were moored around 1455m. Coherence between individual records shows a weak, but significant peak above N for all vertical separations. Instead of a dominant 0-phase difference over the range of sensors, as observed for internal waves at frequencies f < σ < N, f denoting the inertial frequency, this super-buoyancy coherence shows π-phase difference over a frequency band, that shifts to higher frequencies as the vertical separation between thermistors diminishes. In the time

  10. Dense clumps of ionized gas near Pi Scorpii, as revealed by the fine-structure excitation of N II

    NASA Technical Reports Server (NTRS)

    Bertoldi, Frank; Jenkins, Edward B.

    1992-01-01

    The column density and the emission of the ionized gas along the line of sight toward the B1 V + B2 V binary star Pi Sco are measured on the basis of the fine-structure absorption lines of the ground state N II. It is found that the bulk of this ionized gas must be clumped on a length scale of 0.025 pc, which is far smaller than the observed size of the diffuse H II region surrounding Pi Sco of about 6 pc. The observed column density of S III toward Pi Sco yields an upper limit on the distance of the absorbing, clumped gas from the star of less than about 0.02 pc, assuming that both the N II and S III absorption arise from the same gas. The possibility that the ionized gas originates from a photoevaporating circumstellar disk directly surrounding Pi Sco is excluded, since such a disk would have an unusual size of order 0.025 pc and would have had to survive for the estimated age of Pi Sco of 5-8 Myr. The derived mean density of the clumped gas is of order 40/cu cm, so that the gas is at a pressure that far exceeds the mean pressure in the H II region. It is concluded that the ionized gas could originate from evaporation flows off a cluster of compact neutral objects that evaporate due to the ionizing radiation of Pi Sco.

  11. Searching for space-time variation of the fine structure constant using QSO spectra: overview and future prospects

    NASA Astrophysics Data System (ADS)

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

    Theories unifying gravity with other interactions suggest the possibility of spatial and temporal variation of fundamental ``constants'' in the Universe. Using quasar absorption systems we can probe the value of the fine-structure constant, alpha = e2/hbar c, over the history of the universe. Previous studies of three independent samples of data, containing 143 absorption systems spread from 2 to 10 billion years after big bang, hint that alpha was smaller 7 - 11 billion years ago. However competing studies show no such alpha -variation. The studies can be improved by utilising more atomic transitions that are seen in quasar spectra, however in many cases this is hampered by a lack of accurate laboratory frequency measurements. The aim of this paper is to provide a compilation of transitions of importance to the search for alpha variation. They are E1 transitions from the ground state in several different atoms and ions, with wavelengths ranging from around 900 - 6000 Å, and require an accuracy of better than 10-4 Å. We also discuss isotope shift measurements that are needed in order to resolve systematic effects in the study. Researchers who are interested in performing these measurements should contact the authors directly.

  12. Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

    PubMed Central

    Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

    2015-01-01

    The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

  13. Correlation between Active Center Structure and Enhanced Dioxygen Binding in Co(salen) Nanoparticles: Characterization by In Situ Infrared, Raman, and X-ray Absorption Spectroscopies

    SciTech Connect

    Johnson,C.; Long, B.; Nguyen, J.; Day, V.; Borovik, A.; Subramaniam, B.; Guzman, J.

    2008-01-01

    The structure and ligand environment of Co(salen) nanoparticles and unprocessed Co(salen) have been determined by the combined application of infrared, Raman, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies, and X-ray diffraction (XRD) experiments before and during interaction with O2. The Co(salen) nanoparticles were prepared by the precipitation with compressed antisolvent (PCA) technique using commercially obtained Co(salen) [denoted as unprocessed Co(salen)] as the parent compound. The unprocessed Co(salen) particles exist as dimer species with a square-pyramidal coordination geometry that display no measurable O2 binding at room temperature. In sharp contrast, the Co(salen) nanoparticles show near-stoichiometric O2 adsorption, as demonstrated by microbalance gas binding experiments. The spectroscopy results indicate the presence of CoII centers with distorted tetrahedral geometry in the Co(salen) nanoparticles with no evidence of metallic Co clusters, confirmed by the lack of Co-Co contributions at bonding distances in the EXAFS spectra and the presence of characteristic features of CoII in the XANES spectra. The EXAFS data also indicate that there are on average two Co-N and two Co-O bonds with a distance of 1.81 {+-} 0.02 and 1.90 {+-} 0.02 Angstroms, respectively, consistent with typical metal salen structures. Upon O2 binding on the Co(salen) nanoparticles, the XANES results indicate oxidation of the CoII to CoIII, consistent with the vibrational data showing new bands associated with oxygen species bonded to Co centers and the increase in the oxygen coordination number from 1.8 to 2.9 in the EXAFS data. The results indicate that the enhanced O2 binding properties of Co(salen) nanoparticles are related to the unique distorted tetrahedral geometry, which is not observed in the unprocessed samples that contain mainly dimers with square planar geometry. The results presented here provide a

  14. Ni(II) complexation to amorphous hydrous ferric oxide: an X-ray absorption spectroscopy study.

    PubMed

    Xu, Ying; Axe, Lisa; Boonfueng, Thipnakarin; Tyson, Trevor A; Trivedi, Paras; Pandya, Kaumudi

    2007-10-01

    Ni(II) sorption onto iron oxides and in particular hydrous ferric oxide (HFO) is among the important processes impacting its distribution, mobility, and bioavailability in environment. To develop mechanistic models for Ni, extended X-ray absorption fine structure (EXAFS) analysis has been conducted on Ni(II) sorbed to HFO. Coprecipitation revealed the formation of the metastable alpha-Ni(OH)(2) at a Ni(II) loading of 3.5 x 10(-3) molg(-1). On the other hand, Ni(II) formed inner-sphere mononuclear bidentate complexes along edges of FeO(6) octahedra when sorbed to HFO surfaces with Ni-O distances of 2.05-2.07 A and Ni-Fe distances of 3.07-3.11 A. This surface complex was observed by EXAFS study over 2.8 x 10(-3) to 10(-1) ionic strength, pH from 6 to 7, a Ni(II) loading of 8 x 10(-4) to 8.1 x 10(-3) molg(-1) HFO, and reaction times from 4 hours to 8 months. The short- and long-range structure analyses suggest that the presence of Ni(II) inhibited transformation of the amorphous iron oxide into a more crystalline form. However, Ni(2+) was not observed to substitute for Fe(3+) in the oxide structure. This study systematically addresses Ni(II) adsorption mechanisms to amorphous iron oxide. The experimentally defined surface complexes can be used to constrain surface complexation modeling for improved prediction of metal distribution at the iron oxide/aqueous interface. PMID:17561066

  15. In Situ Investigations of Laser-Generated Ligand-Free Platinum Nanoparticles by X-ray Absorption Spectroscopy: How Does the Immediate Environment Influence the Particle Surface?

    PubMed

    Fischer, Mathias; Hormes, Josef; Marzun, Galina; Wagener, Philipp; Hagemann, Ulrich; Barcikowski, Stephan

    2016-09-01

    Pulsed laser ablation in liquid (PLAL) has proven its usefulness as a nanoparticle (NP) synthesis method alternative to traditional chemical reduction methods, where the absence of any molecular ligands or residual reactants makes laser-generated nanoparticles ideal reference materials for charge-transfer experiments. We synthesized additive-free platinum nanoparticles by PLAL and in-situ characterized their interaction with H2O, sodium phosphate buffer, and sodium citrate as well as a TiO2 support by X-ray absorption fine structure (XAFS), i.e., X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Differences in the white-line intensity among the colloidal particles in the three liquids indicate that the respective NP-solvent interaction varies in strength. The ions added ex situ diffuse through the particles' electric double layer and interact electrostatically with the Stern plane. Consequently, these ions weaken the interaction of the functional OH groups that are bound to the partially oxidized platinum surfaces and cause their partial reduction. Comparing XAFS spectra of laser-generated Pt NPs in citrate with wet-chemically synthesized ones (both ligand-covered) indicates different types of Pt-O bonds: a Pt(IV)O2 type in the case of wet-chemical NPs and a Pt(II)O type in the case of laser-generated NPs. A comparison of unsupported laser-generated platinum NPs in H2O with TiO2-supported ones shows no white-line intensity differences and also an identical number of Pt-O bonds in both cases. This suggests that in the deposition process at least part of the double-layer coating stays intact and that the ligand-free Pt particle properties are preserved in the TiO2-supported Pt particles, relevant for heterogeneous catalysis. PMID:27489980

  16. 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

  17. Influences of different environmental parameters on the sorption of trivalent metal ions on bentonite: batch sorption, fluorescence, EXAFS and EPR studies.

    PubMed

    Verma, P K; Pathak, P N; Mohapatra, P K; Godbole, S V; Kadam, R M; Veligzhanin, A A; Zubavichus, Y V; Kalmykov, S N

    2014-04-01

    The presence of long-lived radionuclides in natural aquatic systems is of great environmental concern in view of their possible migration into biospheres of mankind. Trivalent actinides such as (241/243)Am can contribute a great deal to radioactivity for several thousand years. This migration is significantly influenced by various factors such as pH, complexing ions present in aquatic environments, and the sorption of species involving radionuclides by sediments around water bodies. Clay minerals such as bentonite are known to be highly efficient in radionuclide retention and hence are suitable candidates for backfill materials. This study presents experimental results on the interaction of Eu(iii) and Gd(iii) (chemical analogs of Am(iii) and Cm(iii)) with bentonite clay under varying experimental conditions of contact time, pH, and the presence of complexing anions such as humic acid (HA) and citric acid (cit). The sorption of HA on bentonite decreased with increasing the pH from 2 to 8, which was attributed to electrostatic interactions between HA and the bentonite surfaces. The sorption of Eu(iii) on bentonite colloids showed marginal variation with pH (>95%). However, a decrease in Eu(iii) sorption was observed in the presence of HA beyond pH 5 due to the increased aqueous complexation of Eu(iii) with deprotonated HA in the aqueous phase. The complexation of Eu(iii) with citrate ions was studied using Time Resolved Laser induced Fluorescence Spectroscopy (TRLFS) to explain the sorption data. Extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) investigations were carried out to understand the local chemical environment surrounding Eu(iii) and Gd(iii) (EPR probe) sorbed on bentonite under different experimental conditions. Surface complexation modelling shows the predominant formation of ≡XOEu(+2) (silanol) up to pH < 7, and beyond which ≡YOEu(OH)(+) (aluminol) is responsible for the quantitative sorption of Eu(iii) onto

  18. X-ray absorption studies of the local structure and f-level occupancy in CeIr(1-x)Rh(x)In(5)

    SciTech Connect

    Daniel, M.; Han, S.-W.; Booth, C.H.; Cornelius, A.L.; Pagliuso, P.G.; Sarrao, J.L.; Thompson, J.D.

    2004-04-15

    The CeIr{sub 1-x}Rh{sub x}In{sub 5} series exhibits a range of interesting phenomena, including heavy-fermion superconductivity, non-Fermi liquid behavior, and concomitant antiferromagnetism (AF) and superconductivity (SC). In the low-Rh concentration range (0.1 {ge} x {ge} 0.5), specific heat measurements show a broad anomaly, suggestive of gross phase separation. We have performed x-ray absorption experiments at the Ce L{sub III}, Ir L{sub III}, and Rh K-edges as a function of Rh concentration and temperature. X-ray absorption near-edge structure (XANES) measurements indicate that cerium is close to trivalent in this system, with no measurable change with temperature from 20-300 K, consistent with a heavy-fermion material. Extended x-ray absorption fine structure (EXAFS) measurements as a function of temperature from all measured edges indicate the local crystal structure of all samples is well ordered, with no gross phase separation observed, even for samples with x = 0.125 and x = 0.25. These results therefore suggest that the anomalous specific heat behavior in the 0.1 {ge} x {ge} 0.5 range have some other explanation, and some possibilities are discussed.

  19. Fine structure in plasma waves and radiation near the plasma frequency in Earth's foreshock

    NASA Technical Reports Server (NTRS)

    Cairns, Iver H.

    1994-01-01

    Novel observations are presented of intrunsic fine structure in the frequency spectrum of electomagnetic (EM) radiation and plasma waves near the electron plasma frequency f(sub p) during a period of unusually high interplanetary magnetic field strength. Measured using the wideband receiver on the International Sun-Earth Explorer (ISEE) 1 spacecraft, fine-structured emissions are observed both in the solar wind and the foreshock, The fine structure is shown to correspond to emissions spaced above f(sub p) near half harmonies of the electon cyclotron frequency f(sub ce), i.e., near f(sub p) + nf(sub ce)/2. These appear to be the first space physics observations of emissions spaced by f(sub ce)/2. Indirect but strong arguments are used to discriminate between EM and electrostatic (ES) signals, to identify whether ISEE 1 is in the solar wind or the foreshock, and to determine the relative frequencies of the emissions and the local f(sub p). The data are consistent with generation of the ES and EM emissions in the foreshock, with subsequent propagation of the EM emissions into the solar wind. It remains possible that some emissions currently identified as ES have significant EM character. The ES and EM emisions often merge into one another with minimal changes in frequency, arguing that their source regions and generation mechanisms are related and imposing significant constraints on theories. The f(sub ce)/2 ES and EM fine structures observed may be intrinsic to the emission mechanisms or to superposition of two series of signals with f(sub ce) spacing that differ in starting frequency by f(sub ce)/2. Present theories for nonlinear wave coupling processes, cyclotron maser emission, and other linear instability processes are all unable to explain multiple EM and/or ES components spaced by approximately f(sub ce)/2 above f(sub p) for f(sub p)/f(sub ce) much greater than 1 and typical for shock beams parameters. Suitable avenues for further theoretical research are

  20. Magnetic fields, plasma densities, and plasma beta parameters estimated from high-frequency zebra fine structures

    NASA Astrophysics Data System (ADS)

    Karlický, M.; Jiricka, K.

    2002-10-01

    Using the recent model of the radio zebra fine structures (Ledenev et al. 2001) the magnetic fields, plasma densities, and plasma beta parameters are estimated from high-frequency zebra fine structures. It was found that in the flare radio source of high-frequency (1-2 GHz) zebras the densities and magnetic fields vary in the intervals of (1-4)×1010 cm-3 and 40-230 G, respectively. Assuming then the flare temperature as about of 107K, the plasma beta parameters in the zebra radio sources are in the 0.05-0.81 interval. Thus the plasma pressure effects in such radio sources, especially in those with many zebra lines, are not negligible.

  1. Topological map of the Hofstadter butterfly: Fine structure of Chern numbers and Van Hove singularities

    NASA Astrophysics Data System (ADS)

    Naumis, Gerardo G.

    2016-04-01

    The Hofstadter butterfly is a quantum fractal with a highly complex nested set of gaps, where each gap represents a quantum Hall state whose quantized conductivity is characterized by topological invariants known as the Chern numbers. Here we obtain simple rules to determine the Chern numbers at all scales in the butterfly fractal and lay out a very detailed topological map of the butterfly by using a method used to describe quasicrystals: the cut and projection method. Our study reveals the existence of a set of critical points that separates orderly patterns of both positive and negative Cherns that appear as a fine structure in the butterfly. This fine structure can be understood as a small tilting of the projection subspace in the cut and projection method and by using a Chern meeting formula. Finally, we prove that the critical points are identified with the Van Hove singularities that exist at every band center in the butterfly landscape.

  2. Measuring the fine structure constant with Bragg diffraction and Bloch oscillations

    NASA Astrophysics Data System (ADS)

    Yu, Chenghui; Estey, Brian; Parker, Richard; Dudley, Jordan; Müller, Holger

    2016-05-01

    We have demonstrated a new scheme for atom interferometry based on large-momentum-transfer Bragg beam splitters and Bloch oscillations. In this new scheme, we have achieved a resolution of δα / α =0.25ppb in the fine structure constant measurement, which gives up to 4.4 million radians of phase difference between freely evolving matter waves. We have suppressed many systematic effects known in most atom interferometers with Raman beam splitters such as light shift, Zeeman effect shift as well as vibration. We have also simulated multi-atom Bragg diffraction to understand sub-ppb systematic effects, and implemented spatial filtering to further suppress systematic effects. We present our recent progress toward a measurement of the fine structure constant, which will provide a stringent test of the standard model of particle physics.

  3. Fine structure of alpha decay to rotational states of heavy nuclei

    SciTech Connect

    Wang, Y. Z.; Dong, J. M.; Peng, B. B.; Zhang, H. F.

    2010-06-15

    To gain a better insight into alpha-decay fine structure, we calculate the relative intensities of alpha decay to 2{sup +} and 4{sup +} rotational states in the framework of the generalized liquid drop model (GLDM) and improved Royer's formula. The calculated relative intensities of alpha decay to 2{sup +} states are in good agreement with the experimental data. For the relative intensities of alpha decay to 4{sup +} states, a good agreement with experimental data is achieved for Th and U isotopes. The formula we obtain is useful for the analysis of experimental data of alpha-decay fine structure. In addition, some predicted relative intensities which are still not measured are provided for future experiments.

  4. Relation Between Basophilia and Fine Structure of Cytoplasm in the Fungus Allomyces macrogynus Em

    PubMed Central

    Blondel, Benigna; Turian, Gilbert

    1960-01-01

    In a fungus, Allomyces macrogynus Em., staining tests have revealed changes in the location of cytoplasmic basophilia following different phases of the developmental cycle. These variations in location were used to observe which fine structures correspond to basophile and non-basophile areas of the cytoplasm. Hyphae, gametangia, zygotes, and plants were fixed at various developmental stages in OsO4, pH 6.1, and embedded in vestopal. Sections were examined in the electron microscope. Comparison of basophile and non-basophile cytoplasms leads to the conclusion that cytoplasmic particles of 150 to 200 A in diameter are responsible for basophilia. The possibility of these particles being ribosomes is discussed and confirmed. The present paper also describes some observations on the fine structure of other cellular components of this fungus, such as nuclei, mitochondria, various granules, and flagella. PMID:13801597

  5. Measuring h /mCs and the Fine Structure Constant with Bragg Diffraction and Bloch Oscillations

    NASA Astrophysics Data System (ADS)

    Parker, Richard

    2016-05-01

    We have demonstrated a new scheme for atom interferometry based on large-momentum-transfer Bragg beam splitters and Bloch oscillations. In this new scheme, we have achieved a resolution of δα / α =0.25ppb in the fine structure constant measurement, which gives up to 4.4 million radians of phase difference between freely evolving matter waves. We suppress many systematic effects, e.g., Zeeman shifts and effects from Earth's gravity and vibrations, use Bloch oscillations to increase the signal and reduce the diffraction phase, simulate multi-atom Bragg diffraction to understand sub-ppb systematic effects, and implement spatial filtering to further suppress systematic effects. We present our recent progress toward a measurement of the fine structure constant, which will provide a stringent test of the standard model of particle physics.

  6. Solar Cycle Fine Structure and Surface Rotation from Ca II K-Line Time Series Data

    NASA Technical Reports Server (NTRS)

    Scargle, Jeff; Keil, Steve; Worden, Pete

    2011-01-01

    Analysis of three and a half decades of data from the NSO/AFRL/Sac Peak K-line monitoring program yields evidence for four components to the variation: (a) the solar cycle, with considerable fine structure and a quasi-periodicity of 122.4 days; (b) a stochastic process, faster than (a) and largely independent of it, (c) a quasi-periodic signal due to rotational modulation, and of course (d) observational errors (shown to be quite small). Correlation and power spectrum analyses elucidate periodic and aperiodic variation of these chromospheric parameters. Time-frequency analysis is especially useful for extracting information about differential rotation, and in particular elucidates the connection between its behavior and fine structure of the solar cycle on approximately one-year time scales. These results further suggest that similar analyses will be useful at detecting and characterizing differential rotation in stars from stellar light-curves such as those being produced at NASA's Kepler observatory.

  7. The fine-structure intervals of (N-14)+ by far-infrared laser magnetic resonance

    NASA Technical Reports Server (NTRS)

    Brown, John M.; Varberg, Thomas D.; Evenson, Kenneth M.; Cooksy, Andrew L.

    1994-01-01

    The far-infrared laser magnetic resonance spectra associated with both fine-structure transitions in (N-14)+ in its ground P-3 state have been recorded. This is the first laboratory observation of the J = 1 left arrow 0 transition and its frequency has been determined two orders of magnitude more accurately than previously. The remeasurement of the J = 2 left arrow 1 spectrum revealed a small error in the previous laboratory measurements. The fine-structure splittings (free of hyperfine interactions) determined in this work are (delta)E(sub 10) = 1461.13190 (61) GHz, (delta)E(sub 21) = 2459.38006 (37) GHz. Zero-field transition frequencies which include the effects of hyperfine structure have also been calculated. Refined values for the hyperfine constants and the g(sub J) factors have been obtained.

  8. Atomic oxygen fine-structure splittings with tunable far-infrared spectroscopy

    NASA Technical Reports Server (NTRS)

    Zink, Lyndon R.; Evenson, Kenneth M.; Matsushima, Fusakazu; Nelis, Thomas; Robinson, Ruth L.

    1991-01-01

    Fine-structure splittings of atomic oxygen (O-16) in the ground state have been accurately measured using a tunable far-infrared spectrometer. The 3P0-3pl splitting is 2,060,069.09 (10) MHz, and the 3Pl-3P2 splitting is 4,744,777.49 (16) MHz. These frequencies are important for measuring atomic oxygen concentration in earth's atmosphere and the interstellar medium.

  9. Fine Structure in the Decay of Deformed Proton Emitters: Nonadiabatic Approach

    SciTech Connect

    Kruppa, A. T.; Barmore, B.; Nazarewicz, W.; Vertse, T. [Institute of Nuclear Research of the Hungarian Academy of Sciences, P.O. Box 51, H-4001, Debrecen,

    2000-05-15

    The coupled-channel Schroedinger equation with outgoing wave boundary conditions is employed to study the fine structure seen in the proton decay of deformed even-N , odd-Z rare earth nuclei {sup 131}Eu and {sup 141}Ho . Experimental lifetimes and proton-decay branching ratios are reproduced. Variations with the standard adiabatic theory are discussed. (c) 2000 The American Physical Society.

  10. Enhanced effect of temporal variation of the fine-structure constant in diatomic molecules

    SciTech Connect

    Flambaum, V. V.

    2006-03-15

    We show that the relative effect of variation of the fine-structure constant in microwave transitions between very close and narrow rotational-hyperfine levels may be enhanced 2-3 orders of magnitude in diatomic molecules with unpaired electrons like LaS, LaO, LuS, LuO, YbF, and similar molecular ions. The enhancement is result of cancellation between the hyperfine and rotational intervals.

  11. HRTS observations of the fine structure and dynamics of the solar chromosphere and transition zone

    NASA Technical Reports Server (NTRS)

    Dere, K. P.

    1983-01-01

    Arc-second UV observations of the Sun by the NRL High Resolution Telescope and Spectrograph (HRTS) have led to the discovery of dynamic fine structures such as 400 km/s coronal jets and chromospheric jets (spicules) and have provided new information about the structure and dynamics of the transition zone. These observations are reviewed and their relevance to the origin of the solar wind is discussed.

  12. Mechanism of anion retention from EXAFS and density functional calculations: arsenic (V) adsorbed on gibbsite

    NASA Astrophysics Data System (ADS)

    Ladeira, A. C. Q.; Ciminelli, V. S. T.; Duarte, H. A.; Alves, M. C. M.; Ramos, A. Y.

    2001-04-01

    X-ray absorption fine structure spectroscopy and density functional calculations were used to determine the structural model of arsenic surface complex on gibbsite mineral. The structural environment of arsenic at the solid surface may determine its potential for remobilization and stability. Data were collected for arsenate adsorbed on gibbsite surface at pH 5.5. The X-ray absorption fine structure spectroscopy results showed that As(V) forms an inner sphere bidentate binuclear complex on the surface of Al oxyhydroxyl octaedra. Quantitative results showed an average interatomic As(V)-Al distance of 3.19 ± 0.05 Å and a coordination number of 1.3 ± 1.0 atoms. Four different adsorption sites in which arsenate can interact with gibbsite have been studied using density functional calculations, i.e., bidentate binuclear complex, bidentate mononuclear complex, monodentate mononuclear complex, and monodentate binuclear complex. The density functional calculations confirm that the most stable structure predicted for As(V)-gibbsite system is the bidentate-binuclear complex.

  13. Local, global and electronic structure of supported gold nanoclusters determined by EXAFS, XRD and XPS methods

    NASA Astrophysics Data System (ADS)

    Aldea, Nicolae; Rednic, Vasile; Pintea, Stelian; Marginean, Petru; Barz, Bogdan; Gluhoi, Andreea; Nieuwenhuys, Bernard E.; Neumann, Manfred; Yaning, Xie; Matei, Florica

    2009-07-01

    We analyze gold nanoclusters as supported catalysts by extended X-ray absorption fine structure, X-ray diffraction and X-ray photoelectron spectroscopy in order to determine their local, global and electronic structure. The present study points out a strong deformation of the local structure of the metal due to its interaction with oxide supports. We determine the particle size distribution and microstrain functions of the Au nanoclusters by X-ray diffraction method. Based on X-ray absorption fine structure spectroscopy analysis we show that the entire local structure of the investigated systems is strongly distorted regarding the average Au-Au coordination number. The distances between atoms are practically the same as standard Au foil. The strong metal-support interaction is confirmed by the change in shape of the electron transition probability densities that appear in the Au L III-edge. From XPS investigations we find electronic states corresponding to gold as well as to the oxide supports.

  14. Helium induced fine structure in the electronic spectra of anthracene derivatives doped into superfluid helium nanodroplets

    SciTech Connect

    Pentlehner, D.; Slenczka, A.

    2015-01-07

    Electronic spectra of organic molecules doped into superfluid helium nanodroplets show characteristic features induced by the helium environment. Besides a solvent induced shift of the electronic transition frequency, in many cases, a spectral fine structure can be resolved for electronic and vibronic transitions which goes beyond the expected feature of a zero phonon line accompanied by a phonon wing as known from matrix isolation spectroscopy. The spectral shape of the zero phonon line and the helium induced phonon wing depends strongly on the dopant species. Phonon wings, for example, are reported ranging from single or multiple sharp transitions to broad (Δν > 100 cm{sup −1}) diffuse signals. Despite the large number of example spectra in the literature, a quantitative understanding of the helium induced fine structure of the zero phonon line and the phonon wing is missing. Our approach is a systematic investigation of related molecular compounds, which may help to shed light on this key feature of microsolvation in superfluid helium droplets. This paper is part of a comparative study of the helium induced fine structure observed in electronic spectra of anthracene derivatives with particular emphasis on a spectrally sharp multiplet splitting at the electronic origin. In addition to previously discussed species, 9-cyanoanthracene and 9-chloroanthracene will be presented in this study for the first time.

  15. On the dichotomy in auditory perception between temporal envelope and fine structure cues (L)

    NASA Astrophysics Data System (ADS)

    Zeng, Fan-Gang; Nie, Kaibao; Liu, Sheng; Stickney, Ginger; del Rio, Elsa; Kong, Ying-Yee; Chen, Hongbin

    2004-09-01

    It is important to know what cues the sensory system extracts from natural stimuli and how the brain uses them to form perception. To explore this issue, Smith, Delgutte, and Oxenham [Nature (London) 416, 87-90 (2002)] mixed one sound's temporal envelope with another sound's fine temporal structure to produce auditory chimaeras and found that ``the perceptual importance of the envelope increases with the number of frequency bands, while that of the fine structure diminishes.'' This study addressed two technical issues related to natural cochlear filtering and artificial filter ringing in the chimaerizing algorithm. In addition, this study found that the dichotomy in auditory perception revealed by auditory chimaeras is an epiphenomenon of the classic dichotomy between low- and high-frequency processing. Finally, this study found that the temporal envelope determines sound location as long as the interaural level difference cue is present. The present result reinforces the original hypothesis that the temporal envelope is critical for speech perception whereas temporal fine structure is critical for pitch perception, but does not support the assertion regarding the temporal envelope and fine structure as the acoustic basis for the ``what'' and ``where'' mechanisms.

  16. Effective collision strengths for fine-structure transitions in Si VII

    SciTech Connect

    Sossah, A. M.; Tayal, S. S.

    2014-05-20

    The effective collision strengths for electron-impact excitation of fine-structure transitions in Si VII are calculated as a function of electron temperature in the range 5000-2,000,000 K. The B-spline Breit-Pauli R-matrix method has been used to calculate collision strengths by electron impact. The target wave functions have been obtained using the multi-configuration Hartree-Fock method with term-dependent non-orthogonal orbitals. The 92 fine-structure levels belonging to the 46 LS states of 2s {sup 2}2p {sup 4}, 2s2p {sup 5}, 2p {sup 6}, 2s {sup 2}2p {sup 3}3s, 2s {sup 2}2p {sup 3}3p, 2s {sup 2}2p {sup 3}3d, and 2s2p {sup 4}3s configurations are included in our calculations of oscillator strengths and collision strengths. There are 4186 possible fine-structure allowed and forbidden transitions among the 92 levels. The present excitation energies, oscillator strengths, and collision strengths have been compared with previous theoretical results and available experimental data. Generally, a good agreement is found with the 6 LS-state close-coupling approximation results of Butler and Zeippen and the 44 LS-state distorted wave calculation of Bhatia and Landi.

  17. Prominence fine-structure dynamics as inferred from 2D non-LTE models

    NASA Astrophysics Data System (ADS)

    Gunar, Stanislav; Schmieder, Brigitte; Mein, Pierre; Heinzel, Petr

    2012-07-01

    2D multi-thread prominence fine structure models are able to produce synthetic Lyman spectra in very good agreement with spectral observations by SOHO/SUMER including the spectral line asymmetries. The synthetic differential emission measure curves derived from these models are also in a good agreement with observations. Now we show that these models are also able to produce synthetic H-alpha line profiles in very good agreement with observations which allows us to analyze not only the physical parameters of the prominence fine-structure plasma but also some aspects of its dynamical behaviour. We compare the synthetic H-alpha spectra with the observed spectra of the April 26, 2007 prominence using three statistical parameters: the line integrated intensity, the line full-width at the half-maximum (FWHM), and the Doppler velocity derived from shifts of the line profiles. This statistical analysis allows us to conclude that the overall statistical distribution of the LOS velocities in the April 26, 2007 prominence at the time of the observations was below +/-15 km/s and in the prominence core was close to +/-10 km/s. In combination with the analysis of the Lyman spectra we determine several physical parameters of the observed prominence fine structures which show that the April 26, 2007 prominence was relatively less massive. We are also able to put some constrains on the prominence core temperature that might be relatively low, reaching values below 6000 K.

  18. Non-LTE modelling of prominence fine structures using hydrogen Lyman-line profiles

    NASA Astrophysics Data System (ADS)

    Schwartz, P.; Gunár, S.; Curdt, W.

    2015-05-01

    Aims: We perform a detailed statistical analysis of the spectral Lyman-line observations of the quiescent prominence observed on May 18, 2005. Methods: We used a profile-to-profile comparison of the synthetic Lyman spectra obtained by 2D single-thread prominence fine-structure model as a starting point for a full statistical analysis of the observed Lyman spectra. We employed 2D multi-thread fine-structure models with random positions and line-of-sight velocities of each thread to obtain a statistically significant set of synthetic Lyman-line profiles. We used for the first time multi-thread models composed of non-identical threads and viewed at line-of-sight angles different from perpendicular to the magnetic field. Results: We investigated the plasma properties of the prominence observed with the SoHO/SUMER spectrograph on May 18, 2005 by comparing the histograms of three statistical parameters characterizing the properties of the synthetic and observed line profiles. In this way, the integrated intensity, Lyman decrement ratio, and the ratio of intensity at the central reversal to the average intensity of peaks provided insight into the column mass and the central temperature of the prominence fine structures.

  19. Aqueous Cr(VI) reduction by pyrite: Speciation and characterisation of the solid phases by X-ray photoelectron, Raman and X-ray absorption spectroscopies

    NASA Astrophysics Data System (ADS)

    Mullet, Martine; Demoisson, Frédéric; Humbert, Bernard; Michot, Laurent J.; Vantelon, Delphine

    2007-07-01

    Optical microscopy, confocal Raman micro-spectrometry, X-ray photoelectron micro-spectroscopy (XPS) and synchrotron based micro-X-ray fluorescence (XRF), micro-X-ray absorption near edge spectroscopy (XANES) and micro-extended X-ray absorption fine structure (EXAFS) were used to investigate the reduction of aqueous Cr(VI) by pyrite. Special emphasis was placed on the characterisation of the solid phase formed during the reaction process. Cr(III) and Fe(III) species were identified by XPS analyses in addition to non-oxidised pyrite. Optical microscopy images and the corresponding Raman spectra reveal a strong heterogeneity of the samples with three different types of zones. (i) Reflective areas with Eg and Ag Raman wavenumbers relative to non-oxidised pyrite are the most frequently observed. (ii) Orange areas that display a drift of the Eg and Ag pyrite vibration modes of -3 and -6 cm -1, respectively. Such areas are only observed in the presence of Cr(VI) but are not specifically due to this oxidant. (iii) Bluish areas with vibration modes relative to a corundum-like structure that can be assigned to a solid solution Fe 2- xCr xO 3, x varying between 0.2 and 1.5. The heterogeneity in the spatial distribution of chromium observed by optical microscopy and associated Raman microspectroscopy is confirmed by μ-XRF. In agreement with both solution and XPS analyses, these spectroscopies clearly confirm that chromium is in the trivalent state. XANES spectra in the iron K-edge pre-edge region obtained in rich chromium areas reveal the presence of ferric ion thus revealing a systematic association between Cr(III) and Fe(III). In agreement with Raman analyses, Cr K-edge EXAFS can be interpreted as corresponding to Cr atoms involved in a substituted-type hematite structure Fe 2- xCr xO 3.

  20. Examining the Impact of Early AGB Nucleosynthesis on the Apparent Cosmological Variation in the Fine Structure Constant

    NASA Astrophysics Data System (ADS)

    Ashenfelter, Timothy; Mathews, Grant; Olive, Keith

    2004-10-01

    Evidence from a large sample of quasar absorption-line spectra in damped Lyman-α systems has shown potential cosmological variation of the fine structure constant α. The most statistically significant portion of this sample involves the comparison of Mg and Fe wavelength shifts using the many-multiplet (MM) method. However, this method is sensitive to the heavy isotopes, especially in Mg. We implement recent yields of intermediate mass (IM) stars, which evolve beyond the CNO cycle, to show that the ensuing isotope distribution of Mg can account for the observed variation in α provided early star-formation was particularly rich in IM stars. During the Asymptotic Giant Branch (AGB) phase of IM stars, heavy Mg isotopes are robustly produced via hot-bottom burning and thermal pulsing in helium burning shell. We incorporate these recently appreciated processes in the galactic chemical evolution models of these damped Lyman-α systems (early galaxies) and delve into the consequences of this chemical evolution alternative to an α variation. We find that this analysis adds to the mounting evidence that the low-metallicity Universe was strongly influenced by IM stars beyond the standard power law distribution of stellar masses. Because these AGB stars have a significant influence on other abundances, especially nitrogen, we use measurements of N, Si Fe, C, and O to constrain our models. In this way, we obtain an alternative explanation of the α variation that is consistent with observations.