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Sample records for absorption fine-structure xafs

  1. 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.

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

    NASA Astrophysics Data System (ADS)

    Wu, Z. Y.

    2013-04-01

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

  3. 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

  4. 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.

  5. 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})

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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

  3. 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

  4. 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

  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. 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

    Various II-VI semiconducting nanomaterials such as ZnO-ZnS nanoribbons (NRs), CdSxSe1-x nanostructures, ZnS:Mn NRs, ZnS:Mn,Eu nanoprsims (NPs), ZnO:Mn nanopowders, and ZnO:Co nanopowders were synthesized for study. These materials were characterized by techniques such as scanning electron microscopy, transmission electron microscopy, element dispersive X-ray spectroscopy, selected area electron diffraction, and X-ray diffraction. The electronic and optical properties of these nanomaterials were studied by X-ray absorption fine structure (XAFS) spectroscopy and X-ray excited optical luminescence (XEOL) techniques, using tuneable soft X-rays from a synchrotron light source. The complementary nature ofthe XAFS and XEOL techniques give site, element and chemical specific measurements which allow a better understanding of the interplay and role of each element in the system. Chemical vapour deposition (CVD) of ZnS powder in a limited oxygen environment resulted in side-by-side biaxial ZnO-ZnS NR heterostructures. The resulting NRs contained distinct wurtzite ZnS and wurtzite ZnO components with widths of 10--100 nm and 20 --500 nm, respectively and a uniform interface region of 5-15 nm. XAFS and XEOL measurements revealed the luminescence of ZnO-ZnS NRs is from the ZnO component. The luminescence of CdSxSe1-x nanostructures is shown to be dependent on the S to Se ratio, with the band-gap emission being tunable between that of pure CdS and CdSe. Excitation of the CdSxSe 1-x nanostructures by X-ray in XEOL has revealed new de-excitation channels which show a defect emission band not seen by laser excitation. CVD of Mn2+ doped ZnS results in nanostructures with luminescence dominated by the yellow Mn2+ emission due to energy transfer from the ZnS host to the Mn dopant sites. The addition of EuCl3 to the reactants in the CVD process results in a change in morphology from NR to NP. Zn1-xMnxO and Zn1-xCOxO nanopowders were prepared by sol-gel methods at dopant concentrations

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  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. A Modern Laboratory XAFS Cookbook

    NASA Astrophysics Data System (ADS)

    Seidler, GT; Mortensen, DR; Ditter, AS; Ball, NA; Remesnik, AJ

    2016-05-01

    We have recently demonstrated a very favorable, inexpensive modernization of lab- based x-ray absorption fine structure (XAFS) and high-resolution x-ray emission spectroscopy (XES) using only commercially-available optics and x-ray tube sources. Here, we survey several proven instrument designs that can be readily implemented in any laboratory setting to achieve synchrotron-quality XAFS and XES for many systems in the 5 keV to 10 keV energy range. These approaches are based on our immediate experience with the development of: (1) an inexpensive, low-powered monochromator capable of performing either XAFS or XES, (2) a mid-scale XAFS user facility having 106/sec flux with sub-eV bandwidth on each of two independent beamlines, and (3) multiple XES spectrometers having outstanding performance that can complement synchrotron XAFS studies in battery and actinide research.

  19. 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

  20. 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.

  1. XAFS in dilute magnetic semiconductors.

    PubMed

    Sun, Zhihu; Yan, Wensheng; Yao, Tao; Liu, Qinghua; Xie, Yi; Wei, Shiqiang

    2013-10-14

    X-Ray absorption fine structure (XAFS) spectroscopy has experienced a rapid development in the last four decades and has proved to be a powerful structure characterization technique in the study of local environments in condensed matter. In this article, we first introduce the XAFS basic principles including theory, data analysis and experiment in some detail. Then we attempt to make a review on the applications of XAFS to the study of atomic and electronic structure in dilute magnetic semiconductor (DMS) systems. The power of XAFS in characterizing this interesting material system, such as determining the occupation sites and distribution of the dopants, detecting the presence of metal clusters or secondary phases, as well as identifying the defect types and dopant valence, will be illuminated by selected examples. This review should be of interest both to newcomers in the DMS field and to an interdisciplinary community of researchers working in synthesis, characterization and utilization of DMS materials. PMID:23884341

  2. Aqueous complexation of citrate with neodymium(III) and americium(III): a study by potentiometry, absorption spectrophotometry, microcalorimetry, and XAFS.

    PubMed

    Brown, M Alex; Kropf, A Jeremy; Paulenova, Alena; Gelis, Artem V

    2014-05-01

    The aqueous complexation of Nd(III) and Am(III) with anions of citrate was studied by potentiometry, absorption spectrophotometry, microcalorimetry, and X-ray absorption fine structure (XAFS). Using potentiometric titration data fitting the metal-ligand (L) complexes that were identified for Nd(III) were NdHL, NdL, NdHL2, and NdL2; a review of trivalent metal-citrate complexes is also included. Stability constants for these complexes were calculated from potentiometric and spectrophotometric titrations. Microcalorimetric results concluded that the entropy term of complex formation is much more dominant than the enthalpy. XAFS results showed a dependence in the Debye-Waller factor that indicated Nd(iii)-citrate complexation over the pH range of 1.56-6.12. PMID:24619154

  3. 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+.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. 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.

  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. 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. 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

  3. 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

  4. 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.

  5. 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.

  6. 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).

  7. XAFS SPECTROSCOPY RESULTS FOR PM SAMPLES FROM RESIDUAL FUEL OIL

    EPA Science Inventory

    X-ray absorption fine structure (XAFS spectroscopy data were obtained from particulate samples produced by the combustion of residual fuel oil in a 732-kW fire-tube boiler at EPA's National Risk Management Research Laboratory in North Carolina. Residual oil flyash (ROFA) from fo...

  8. 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

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. A new technique to measure the differential XAFS spectrum

    NASA Astrophysics Data System (ADS)

    Min, Wu; Li-Rong, Zheng; Sheng-Qi, Chu; Ai-Yu, Zhou; Jing, Zhang; Tian-Dou, Hu

    2016-04-01

    A new technique has been developed for direct measurement of the differential X-ray absorption fine structure (XAFS) spectrum by the energy-modulation method. To acquire the energy-oscillating incident X-ray beam, a piezoelectric actuator is used to control the double-crystal monochromator. A logarithmic converter circuit and a lock-in amplifier are used to extract the modulated signals. The normal and differential XAFS spectra of the Mn K-edge of Li2MnO3 have been collected. The X-ray-absorption near-edge-structure (XANES) spectra verify that the signal-to-noise ratio has been greatly improved by the new technique, and the extended X-ray absorption fine structure (EXAFS) spectra demonstrate that this new technique can efficiently enhance the signals of the backscattering atoms. Supported by NSFC (11175202)

  4. 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.

  5. In situ observation of pitting of stainless steel by XAFS.

    PubMed

    Kimura, M; Kaneko, M; Suzuki, T

    2001-03-01

    An in situ observation technique by XAFS (X-ray Absorption Fine Structures) has been developed for observation of metal corrosion. XAFS spectra were obtained with a special electrochemical cell to elucidate pitting: change of concentrations and structures of ions near the interface of solution and metal. It has been successfully shown that the concentrations of Cr and Br are linearly dependent on the distance from the interface. Also, salt formation at the interface and the hydrolysis reaction far from the interface are indicated. PMID:11512824

  6. Characterization of fossil remains using XRF, XPS and XAFS spectroscopies

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    Synchrotron radiation micro-X-Ray Fluorescence (μ-XRF), X-ray photoelectron (XPS) and X-ray Absorption Fine Structure (XAFS) spectroscopies are applied for the study of paleontological findings. More specifically the costal plate of a gigantic terrestrial turtle Titanochelon bacharidisi and a fossilized coprolite of the cave spotted hyena Crocuta crocuta spelaea are studied. Ca L 2,3-edge NEXAFS and Ca 2p XPS are applied for the identification and quantification of apatite and Ca containing minerals. XRF mapping and XAFS are employed for the study of the spatial distribution and speciation of the minerals related to the deposition environment.

  7. XAFS SPECTROSCOPY ANALYSIS OF SELECTED HAP ELEMENTS IN FINE PM DERIVED FROM COAL COMBUSTION

    EPA Science Inventory

    X-ray absorption fine structure (XAFS) spectroscopy has been used to investigate the valence states and molecular structures of sulfur (S), chromium (Cr), arsenic (As), and zinc (Zn) in fine particulate matter (PM) separated from coal flyash produced in a realistic combustion sys...

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

    SciTech Connect

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

    2008-01-01

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

  9. Photon interference effect in x-ray absorption spectra over a wide energy range

    NASA Astrophysics Data System (ADS)

    Nishino, Y.; Ishikawa, T.; Suzuki, M.; Kawamura, N.; Kappen, P.; Korecki, P.; Haack, N.; Materlik, G.

    2002-09-01

    We consider fundamental structures in x-ray absorption spectra over a wide energy range. We formulate the elastic scattering in addition to the photoelectric absorption in recently reported photon interference x-ray absorption fine structureXAFS). The simulations show excellent agreement with experimental x-ray absorption spectra for platinum and tungsten powders far above and below the L absorption edges. πXAFS can be as big as in the order of 10% of XAFS, and cannot be easily neglected in detailed analysis of XAFS and related phenomena.

  10. 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.

  11. 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.

  12. 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

  13. 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

  14. 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

  15. 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}.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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}.

  1. In situ total-electron-yield sulfur K-edge XAFS measurements during exposure of copper to an SO 2-containing humid atmosphere

    NASA Astrophysics Data System (ADS)

    Song, Inho; Rickett, Brett; Janavicius, Paul; Payer, Joe H.; Antonio, Mark R.

    1995-02-01

    A total-electron-yield (TEY) detector was designed and constructed for in situ X-ray absorption fine structure (XAFS) measurements of the sulfur-containing species formed during exposure of copper to a humid atmosphere containing SO 2. Using the detector, gas phase XAFS spectra were also collected for both dry and humid SO 2 atmospheres. This work presents the experimental technique and examples of the sulfur K-edge spectra collected during the study.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  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. 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

  10. SYNCHROTRON RADIATION, FREE ELECTRON LASER, APPLICATION OF NUCLEAR TECHNOLOGY, ETC.: A new cell for X-ray absorption spectroscopy study under high pressure

    NASA Astrophysics Data System (ADS)

    Zheng, Li-Rong; Che, Rong-Zheng; Liu, Jing; Du, Yong-Hua; Zhou, Ying-Li; Hu, Tian-Dou

    2009-08-01

    X-ray absorption fine structure (XAFS) spectroscopy is a powerful technique for the investigation of the local environment around selected atoms in condensed matter. XAFS under pressure is an important method for the synchrotron source. We design a cell for a high pressure XAFS experiment. Sintered boron carbide is used as the anvils of this high pressure cell in order to obtain a full XAFS spectrum free from diffraction peaks. In addition, a hydraulic pump was adopted to make in-suit pressure modulation. High quality XAFS spectra of ZrH2 under high pressure (up to 13 GPa) were obtained by this cell.

  11. 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

  12. 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.

  13. 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

  14. 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.

  15. XAFS studies of gold and silver-gold nanoparticles in aqueous solution

    SciTech Connect

    Shibata, Tomohiro; Tostmann, Holger; Bunker, Bruce; Henglein, Arnim; Meisel, Dan; Cheong, Seong-kyun; Boyanov, Maxim

    2010-09-30

    The X-ray absorption fine structure (XAFS) of colloidal Au and Au/Ag nanoparticles (3.5 nm and 20 nm mean diameter) in an aqueous solution has been investigated. Size dependent alloying was observed upon deposition of Ag on Au core. Ag forms distinct layers around the 20 nm Au nanoparticles. In contrast, random mixing is found for Ag deposited on 3.5 nm Au particles.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Gritty Surface Sample Holder Invented To Obtain Correct X-ray Absorption Fine Structure Spectra for Concentrated Materials by Fluorescence Yield.

    PubMed

    Abe, Hitoshi; Niwa, Yasuhiro; Kimura, Masao; Murakami, Youichi; Yokoyama, Toshiharu; Hosono, Hideo

    2016-04-01

    A gritty surface sample holder has been invented to obtain correct XAFS spectra for concentrated samples by fluorescence yield (FY). Materials are usually mixed with boron nitride (BN) to prepare proper concentrations to measure XAFS spectra. Some materials, however, could not be mixed with BN and would be measured in too concentrated conditions to obtain correct XAFS spectra. Consequently, XAFS spectra will be incorrect typically with decreased intensities of the peaks. We have invented the gritty surface sample holders to obtain correct XAFS spectra even for concentrated materials for FY measurements. Pure Cu and CuO powders were measured mounted on the sample holders, and the same spectra were obtained as transmission spectra of properly prepared samples. This sample holder is useful to measure XAFS for any concentrated materials. PMID:26978034

  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. An in situ XAFS study--the formation mechanism of gold nanoparticles from X-ray-irradiated ionic liquid.

    PubMed

    Ma, Jingyuan; Zou, Yang; Jiang, Zheng; Huang, Wei; Li, Jiong; Wu, Guozhong; Huang, Yuying; Xu, Hongjie

    2013-07-28

    An in situ X-ray absorption fine structure (XAFS) experiment has been performed to observe the evolution of gold nanoparticles in the ionic liquid [BMIM][AuCl4], by hard X-ray irradiation. The ionic liquid acts as both a reducing agent and a protective ligand. A synchrotron-based X-ray plays the role of the irradiation source, which induces the reduction of the gold species, as well as being a real time probe for XAFS measurements. From the extended X-ray absorption fine structure (EXAFS) fitting results for a series of spectra of gold L3-edge, it can be seen clearly that there is a single Au-Cl bond breaking process before the formation of Au-Au bonds, which is different from previous reports on the formation of Au nanoparticles by several chemical methods. PMID:23765109

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. 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.

  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. . 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.

  4. 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.

  5. X-ray absorption spectroscopy using BL11 at SAGA-LS, and its applications for materials science

    NASA Astrophysics Data System (ADS)

    Okajima, T.; Sumitani, K.; Kawamoto, M.; Kobayashi, E.

    2013-04-01

    Beamline BL11 at the Saga Light Source (SAGA-LS) is designed for X-ray absorption fine structure (XAFS) experiments in the energy range 2.1-23 keV using a Si(111) double crystal monochrometer. For XAFS experiments, the sample temperature can be controlled in the range of 15-1073 K using a cryostat and furnaces. Besides the transmission measurement mode, we can obtain XAFS spectra in fluorescence measurement mode and conversion electron yield modes. An XAFS measurement system under atmospheric pressure for soft X-rays with energies under 3.5 keV was also installed on this beamline. In addition, we can perform in situ XAFS measurements under toxic and harmful gas atmospheres by using a quick XAFS measurement system.

  6. 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.

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

    SciTech Connect

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

    2015-01-26

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

  8. 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.

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

    PubMed

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

    2013-02-13

    The electronic structure of individual hybrid particles was studied by nanoscale near-edge X-ray absorption spectromicroscopy. The colloidal particles consist of a solid polystyrene core and a cross-linked poly-N-(isopropylacrylamide) shell with embedded crystalline titanium dioxide (TiO(2)) nanoparticles (d = 6 ± 3 nm). The TiO(2) particles are generated in the carrier network by a sol-gel process at room temperature. The hybrid particles were imaged with photon energy steps of 0.1 eV in their hydrated environment with a cryo transmission X-ray microscope (TXM) at the Ti L(2,3)-edge. By analyzing the image stacks, the obtained near-edge X-ray absorption fine structure (NEXAFS) spectra of our individual hybrid particles show clearly that our synthesis generates TiO(2) in the anastase phase. Additionally, our spectromicroscopy method permits the determination of the density distribution of TiO(2) in single carrier particles. Therefore, NEXAFS spectroscopy combined with TXM presents a unique method to get in-depth insight into the electronic structure of hybrid materials. PMID:23360082

  10. 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

  11. 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

  12. 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.

  13. 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

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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

  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. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  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. 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.

  14. 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

  15. 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

  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. Probing the local structure of high-{Tc} superconductors using XAFS spectroscopy

    SciTech Connect

    Bridges, F.; Booth, C.H.; Li, G.G.; Bauer, E.D.; Boyce, J.; Claeson, T.

    1996-12-31

    X-ray Absorption Fine-Structure (XAFS) is a local structural probe that is complementary to diffraction techniques. The authors discuss the types of information that can be obtained using this probe and then consider several examples, including the distortion about Co in YBa{sub 2}Cu{sub 3}O{sub 7} (YBCO), an unusual negative correlation of atom pair displacements in HgBa{sub 2}CuO{sub 4+{delta}}, and the distortions about the O(4) atom in thin films and single crystals of YBCO.

  18. XAFS study on structural order in highly monodispersed thiol-stabilized Au nanoparticles

    NASA Astrophysics Data System (ADS)

    Huang, Y.; Liu, W.; Yang, L.; Huang, T.; Jiang, Y.; Yao, T.; Wei, S.

    2016-05-01

    Understanding the influence of thiol on nanoparticle size and structure is essential for the fundamental and applied researches. Here, using x-ray absorption fine structure (XAFS) spectroscopy, we investigate the structural order of Au nanoparticles (NPs) in the protection of thiol ligands with different contents. We found that besides protecting Au NPs against aggregation and growth, thiolates can effectively eliminate the dangling bonds of unsaturated Au atoms, and thus increase the structural order. This work enriches our knowledge of Au-S interface interaction and guides the way towards preparing size-controllable nanoparticles with specific physical/chemical properties.

  19. Predicting XAFS scattering path cumulants and XAFS spectra for metals (Cu, Ni, Fe, Ti, Au) using molecular dynamics simulations.

    PubMed

    Karolewski, M A; Cavell, R G; Gordon, R A; Glover, C J; Cheah, M; Ridgway, M C

    2013-07-01

    The ability of molecular dynamics (MD) simulations to support the analysis of X-ray absorption fine-structure (XAFS) data for metals is evaluated. The low-order cumulants (ΔR, σ(2), C3) for XAFS scattering paths are calculated for the metals Cu, Ni, Fe, Ti and Au at 300 K using 28 interatomic potentials of the embedded-atom method type. The MD cumulant predictions were evaluated within a cumulant expansion XAFS fitting model, using global (path-independent) scaling factors. Direct simulations of the corresponding XAFS spectra, χ(R), are also performed using MD configurational data in combination with the FEFF ab initio code. The cumulant scaling parameters compensate for differences between the real and effective scattering path distributions, and for any errors that might exist in the MD predictions and in the experimental data. The fitted value of ΔR is susceptible to experimental errors and inadvertent lattice thermal expansion in the simulation crystallites. The unadjusted predictions of σ(2) vary in accuracy, but do not show a consistent bias for any metal except Au, for which all potentials overestimate σ(2). The unadjusted C3 predictions produced by different potentials display only order-of-magnitude consistency. The accuracy of direct simulations of χ(R) for a given metal varies among the different potentials. For each of the metals Cu, Ni, Fe and Ti, one or more of the tested potentials was found to provide a reasonable simulation of χ(R). However, none of the potentials tested for Au was sufficiently accurate for this purpose. PMID:23765297

  20. Apical Cu-O bond in YBa{sub 2}Cu{sub 3}O{sub 7-{delta}} superconductors by XAFS

    SciTech Connect

    Stern, E.A.; Qian, M.; Yacoby, Y.; Heald, S.M.; Maeda, H.

    1993-04-01

    Careful Cu K-edge X-ray absorption fine structure (XAFS) measurements on oriented powders of YBa{sub 2}CU{sub 3}O{sub 7{minus}} were made as a function of temperature, of {delta}, {Tc} method of preparation and grain size. The XAFS data were analyzed for the Cu(1) - O(4) apical bond distance distribution. AU samples indicated evidence for a double-peak in the distribution with a splitting of 0.1{Angstrom}, with the clearest case for the {delta} {approx} 0 samples occurring for the {Tc} = 89K 20{mu}m grain samples and the least clear one for the 5{mu}m grain {Tc} = 93K sample. There is no significant temperature dependence of the splitting. Because the XAFS evidence for the splitting depends on a small signal, it is prudent to verify its existence by other independent measurements.

  1. 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

  2. Synthesis of 1 nm Pd Nanoparticles in a Microfluidic Reactor: Insights from in Situ X ray Absorption Fine Structure Spectroscopy and Small-Angle X ray Scattering

    SciTech Connect

    Karim, Ayman M.; Al Hasan, Naila M.; Ivanov, Sergei A.; Siefert, Soenke; Kelly, Ryan T.; Hallfors, Nicholas G.; Benavidez, Angelica D.; Kovarik, Libor; Jenkins, Aaron; Winans, R. E.; Datye, Abhaya K.

    2015-06-11

    In this paper we show that the temporal separation of nucleation and growth is not a necessary condition for the colloidal synthesis of monodisperse nanoparticles. The synthesis mechanism of Pd nanoparticles was determined by in situ XAFS and SAXS in a microfluidic reactor capable of millisecond up to an hour time resolution. The SAXS results showed two autocatalytic growth phases, a fast growth phase followed by a very slow growth phase. The steady increase in the number of particles throughout the two growth phases indicates the synthesis is limited by slow continuous nucleation. The transition from fast to slow growth was caused by rapid increase in bonding with the capping agent as shown by XAFS. Based on this fundamental understanding of the synthesis mechanism, we show that 1 nm monodisperse Pd nanoparticles can be synthesized at low temperature using a strong binding capping agent such as trioctylphosphine (TOP).

  3. 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.

  4. 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

  5. Development of dispersive XAFS system for analysis of time-resolved spatial distribution of electrode reaction.

    PubMed

    Katayama, Misaki; Miyahara, Ryota; Watanabe, Toshiki; Yamagishi, Hirona; Yamashita, Shohei; Kizaki, Terue; Sugawara, Yoshimi; Inada, Yasuhiro

    2015-09-01

    Apparatus for a technique based on the dispersive optics of X-ray absorption fine structure (XAFS) has been developed at beamline BL-5 of the Synchrotron Radiation Center of Ritsumeikan University. The vertical axis of the cross section of the synchrotron light is used to disperse the X-ray energy using a cylindrical polychromator and the horizontal axis is used for the spatially resolved analysis with a pixel array detector. The vertically dispersive XAFS (VDXAFS) instrument was designed to analyze the dynamic changeover of the inhomogeneous electrode reaction of secondary batteries. The line-shaped X-ray beam is transmitted through the electrode sample, and then the dispersed transmitted X-rays are detected by a two-dimensional detector. An array of XAFS spectra in the linear footprint of the transmitted X-ray on the sample is obtained with the time resolution of the repetition frequency of the detector. Sequential measurements of the space-resolved XAFS data are possible with the VDXAFS instrument. The time and spatial resolutions of the VDXAFS instrument depend on the flux density of the available X-ray beam and the size of the light source, and they were estimated as 1 s and 100 µm, respectively. The electrode reaction of the LiFePO4 lithium ion battery was analyzed during the constant current charging process and during the charging process after potential jumping. PMID:26289274

  6. 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

  7. 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

  8. XAFS study on liquid selenium under high pressure.

    PubMed

    Katayama, Y

    2001-03-01

    Using large-volume presses, it is now possible to measure X-ray absorption spectra under a wide range of pressure-temperature conditions. X-ray absorption fine structure (XAFS) has successfully been measured at the K edge of crystalline and liquid Se at temperatures up to 1023 K and pressures of about 5 and 8 GPa, and at temperatures up to 1173 K at about 2.5 GPa. Crystalline Se consists of infinite chain molecules. At atmospheric pressure, it is known that the chain structure of Se is largely preserved upon melting. The temperature dependence of the extended X-ray absorption fine structure (EXAFS) at 2.5 GPa indicates that twofold covalent bonds remain upon melting, as at atmospheric pressure. On the other hand, the decrease of EXAFS oscillation upon melting at 8 GPa is larger than that expected from the temperature dependence of EXAFS in the crystalline state, indicating that the covalent bonds are modified in the liquid state. The change of structure of liquid Se is discussed in relation to a proposed semiconductor-metal transition under high pressure. PMID:11512721

  9. 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

  10. A fluorescence XAFS measurement instrument in the soft x-ray region toward observation under operando conditions

    SciTech Connect

    Honda, M. Baba, Y.; Shimoyama, I.; Sekiguchi, T.

    2015-03-15

    X-ray absorption fine structure (XAFS) measurements are widely used for the analysis of electronic structure. Generally, XAFS in the soft X-ray region is measured under vacuum, but chemical structures under vacuum are typically different from those under operando conditions, where chemical species exhibit their function. Here, we developed an XAFS measurement instrument, as a step toward operando fluorescent, which yields XAFS measurement using synchrotron radiation in the soft X-ray region. We applied this method to analyze the local electronic structure of the sulfur atoms in L-cysteine in different pH solutions. In water at pH 7, the hydrogen atom does not dissociate from the thiol (-SH) group in L-cysteine, which forms a structure surrounded by and interacting with water molecules. The XAFS spectrum of L-cysteine in solution was altered by changing the pH. At pH 9, the hydrogen atom dissociated and a thiolate anion was formed. Although the -SH group was oxidized to SO{sub 4}{sup 2−} when L-cysteine was adsorbed on a metal surface and dried, no oxidation was observed in solution. This may be because the water molecules were densely packed and protected the -SH group from oxidation. Our results show that this instrument aimed toward operando fluorescence XAFS measurements in the soft X-ray region is useful for structural analysis of sulfur atoms in organic molecules in air and in solution. The instrument will be applied to the structural analysis of materials containing elements that have absorption edges in soft X-ray region, such as phosphorus and alkali metals (potassium and cesium). It will be also particularly useful for the analysis of samples that are difficult to handle under vacuum and materials that have specific functions in solution.

  11. A fluorescence XAFS measurement instrument in the soft X-ray region toward observation under operando conditions.

    PubMed

    Honda, M; Baba, Y; Shimoyama, I; Sekiguchi, T

    2015-03-01

    X-ray absorption fine structure (XAFS) measurements are widely used for the analysis of electronic structure. Generally, XAFS in the soft X-ray region is measured under vacuum, but chemical structures under vacuum are typically different from those under operando conditions, where chemical species exhibit their function. Here, we developed an XAFS measurement instrument, as a step toward operando fluorescent, which yields XAFS measurement using synchrotron radiation in the soft X-ray region. We applied this method to analyze the local electronic structure of the sulfur atoms in L-cysteine in different pH solutions. In water at pH 7, the hydrogen atom does not dissociate from the thiol (-SH) group in L-cysteine, which forms a structure surrounded by and interacting with water molecules. The XAFS spectrum of L-cysteine in solution was altered by changing the pH. At pH 9, the hydrogen atom dissociated and a thiolate anion was formed. Although the -SH group was oxidized to SO4 (2-) when L-cysteine was adsorbed on a metal surface and dried, no oxidation was observed in solution. This may be because the water molecules were densely packed and protected the -SH group from oxidation. Our results show that this instrument aimed toward operando fluorescence XAFS measurements in the soft X-ray region is useful for structural analysis of sulfur atoms in organic molecules in air and in solution. The instrument will be applied to the structural analysis of materials containing elements that have absorption edges in soft X-ray region, such as phosphorus and alkali metals (potassium and cesium). It will be also particularly useful for the analysis of samples that are difficult to handle under vacuum and materials that have specific functions in solution. PMID:25832271

  12. A fluorescence XAFS measurement instrument in the soft x-ray region toward observation under operando conditions

    NASA Astrophysics Data System (ADS)

    Honda, M.; Baba, Y.; Shimoyama, I.; Sekiguchi, T.

    2015-03-01

    X-ray absorption fine structure (XAFS) measurements are widely used for the analysis of electronic structure. Generally, XAFS in the soft X-ray region is measured under vacuum, but chemical structures under vacuum are typically different from those under operando conditions, where chemical species exhibit their function. Here, we developed an XAFS measurement instrument, as a step toward operando fluorescent, which yields XAFS measurement using synchrotron radiation in the soft X-ray region. We applied this method to analyze the local electronic structure of the sulfur atoms in L-cysteine in different pH solutions. In water at pH 7, the hydrogen atom does not dissociate from the thiol (-SH) group in L-cysteine, which forms a structure surrounded by and interacting with water molecules. The XAFS spectrum of L-cysteine in solution was altered by changing the pH. At pH 9, the hydrogen atom dissociated and a thiolate anion was formed. Although the -SH group was oxidized to SO42- when L-cysteine was adsorbed on a metal surface and dried, no oxidation was observed in solution. This may be because the water molecules were densely packed and protected the -SH group from oxidation. Our results show that this instrument aimed toward operando fluorescence XAFS measurements in the soft X-ray region is useful for structural analysis of sulfur atoms in organic molecules in air and in solution. The instrument will be applied to the structural analysis of materials containing elements that have absorption edges in soft X-ray region, such as phosphorus and alkali metals (potassium and cesium). It will be also particularly useful for the analysis of samples that are difficult to handle under vacuum and materials that have specific functions in solution.

  13. Conformation Analysis of Ferrocene and Decamethylferrocene via Full-Potential Modeling of XANES and XAFS Spectra.

    PubMed

    Bourke, J D; Islam, M T; Best, S P; Tran, C Q; Wang, F; Chantler, C T

    2016-07-21

    Recent high-accuracy X-ray absorption measurements of the sandwich organometallics ferrocene (Fc) and decamethylferrocene (DmFc) at temperatures close to liquid helium are compared with new full-potential modeling of X-ray absorption fine structure (XAFS) covering the near-edge region (XANES) and above up to k = 7 Å(-1). The implementation of optimized calculations of the oscillatory part of the spectrum from the package FDMX allows detailed study of the spectra in regions of the photoelectron momentum most sensitive to differences in the molecular stereochemistry. For Fc and DmFc, this corresponds to the relative rotation of the cyclopentadienyl rings. When applied to high-accuracy XAFS of Fc and DmFc, the FDMX theory gives clear evidence for the eclipsed conformation for Fc and the staggered conformation for DmFc for frozen solutions at ca. 15 K. This represents the first clear experimental assignment of the solution structures of Fc and DmFc and reveals the potential of high-accuracy XAFS for structural analysis. PMID:27391765

  14. Polarized XAFS study of Al K-edge for m-plane AlGaN films

    NASA Astrophysics Data System (ADS)

    Miyanaga, T.; Azuhata, T.; Nakajima, K.; Nagoya, H.; Hazu, K.; Chichibu, S. F.

    2014-04-01

    Local structures around Al atoms in high-quality m-plane AlxGa1-xN films (x=0.32 and 0.58) deposited on m-plane GaN substrates by the NH3 source molecular beam epitaxy method were investigated by Al K-edge X-ray absorption fine structure (XAFS) for the first time. XAFS spectra were measured using a linearly-polarized X-ray source from synchrotron radiation for three different directions; along the c-, a-, and m-axes. The interatomic distances along the a-axis are close to Ga-Ga distance in GaN, indicating that the local structures are strongly affected by GaN substrates. The localization of Al atoms was observed for the Al0.32Ga0.68N film.

  15. Realtime structural electrochemistry of platinum clusters using dispersive XAFS

    SciTech Connect

    Allen, P.G.; Conradson, S.D.; Wilson, M.S.; Gottesfeld, S.; Raistrick, I.D.

    1993-12-31

    Chemical reference tables state that the standard potential for the reaction of Pt with water, Pt + 2H{sub 2}O {r_arrow} Pt(OH){sub 2} + 2H{sup +} + 2e{sup {minus}}, is 0.98 V, and electrochemical studies propose that this reaction may occur at potentials as low as 0.8 V. Using dispersive x-ray absorption fine-structure (XAFS) spectroscopy, the authors have directly probed the structural evolution of a Pt catalyst operating in-situ in a polymer electrolyte fuel cell during cyclic voltammetry. The changes in the number of Pt and O nearest-neighbors and the Pt charge demonstrate a close correspondence with features in the voltammogram. Because dispersive XAFS is very sensitive to detecting structural changes, they have been able to detect the presence of chemisorbed oxygen at potentials of 0.6--0.9 V in the anodic sweep. Since double-layer charging is regarded as the only process in this region for bulk Pt, these results may reflect a limitation of previous (indirect) studies on Pt electrochemistry, or they may indicate that these clusters are different from their bulk metal counterparts. Exploiting the time-resolving capability of dispersive XAFS, they also monitored changes in the Pt charge and the number of O and Pt nearest-neighbors during the electrochemical oxidation and reduction of the Pt clusters in real-time. The results are inconsistent with those expected from the place-exchange mechanism for the formation of the surface oxide on bulk Pt electrodes in aqueous solution; Pt{sub red} (k{sub 1}) {yields} Pt (submonolayer O)(k{sub 2}) {yields} PtO{sub x} (place exchanged Pt and O atoms: k{sub 1} >> k{sub 2}). Their current model for understanding these behaviors is that, relative to bulk Pt, unusual types of surface sites play a major role in determining the reactivity of these clusters.

  16. 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.

  17. XAFS study on Ca local structure in natural glasses and tektite

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    The local structures of tektite and natural glasses were studied by Ca K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) in order to provide quantitative data on bonding distances and coordination numbers. The pre-edge peak intensities of tektites are 10.7-11.7%, and those of peudotachylite, Kirauea volcanic glass, impactite, pitchstone and perlite are 6.7-10.9%. The main peak shoulder intensities of tektites are 68.3-70.7%, and other natural glasses are 63.0-63.9%. XAFS analysis indicated all tektites possess 7-coordinated Ca, but natural glasses possess 6-, 7- and 8- coordinated Ca. This study indicated that different petrogenesis of natural glasses gives different local structures of calcium.

  18. XAF/XANES studies of plutonium-loaded sodalite/glass composite waste forms.

    SciTech Connect

    Aase, S. B.; Kropf, A. J.; Lewis, M. A.; Reed, D. T.; Richmann, M. K.

    1999-07-14

    A sodalite/glass ceramic waste form has been developed to immobilize highly radioactive nuclear wastes in chloride form, as part of an electrochemical cleanup process. Simulated waste forms have been fabricated which contain plutonium and are representative of the salt from the electrometallurgical process to recover uranium from spent nuclear fuel. X-ray absorption fine structure spectroscopy (XAFS) and x-ray absorption near-edge spectroscopy (XANES) studies were performed to determine the location, oxidation state and form of the plutonium within these waste forms. Plutonium, in the non-fission-element case, was found to segregate as plutonium(IV) oxide with a crystallite size of at least 20 nm. With fission elements present, the crystallite size was about 2 nm. No plutonium was observed within the sodalite or glass in the waste form.

  19. 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

  20. An XAFS study of the oxidation of structural iron in biotite mica by solutions containing Br{sub 2} or H{sub 2}O{sub 2}

    SciTech Connect

    Heald, S.M.; Amonette, J.E.; Turner, G.D.; Scott, A.D.

    1994-08-01

    X-ray absorption fine structure (XAFS) measurements were made on the Fe edge for a series of biotite micas oxidized to different extents by solutions containing either Br{sub 2} or H{sub 2}O{sub 2}. The Fe in the Br{sub 2}-treated sample was nearly completely oxidized to Fe(III), while the H{sub 2}O{sub 2}-treated samples showed an intermediate degree of oxidation. Both the near-edge and XAFS for the H{sub 2}O{sub 2} samples could have been fit well by a linear combination of the untreated and Br{sub 2}-treated samples. This indicates that the partially oxidized samples had the two forms of Fe in distinct sites. Detailed analysis for the oxidized site gave a coordination of 5.7 {+-} 0.5 with a Fe-O distance of 1.99 {angstrom}.

  1. 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.

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

    SciTech Connect

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

    2007-02-02

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

  3. 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

  4. Influence of depositional environment in fossil teeth: a micro-XRF and XAFS study

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    The formation of metal-rich phases during the fossilization of vertebrate fossil teeth, recovered from various deposition environments in northern Greece, is studied by means of synchrotron radiation X-ray fluorescence (SR-XRF) as well as Fe and Mn K edge X-ray absorption fine structure (XAFS) spectroscopy. XRF line-scans from the samples' cross-sections revealed different contamination paths for Mn and Fe. The two-dimensional XRF maps illustrate the spatial distribution of P, Ca, Mn and Fe as well as the precipitation of Fe-rich phases in cementum, dentin and dentinal tubules. Goethite, lepidocrocite and ferrihydrite were detected in the samples' cross-section by means of Fe K edge EXAFS spectroscopy. Moreover the Fe and Mn K edge EXAFS revealed the presence of vivianite and birnessite (MnO2) on the external surface of two samples.

  5. XAFS studies of monodisperse Au nanoclusters formation in the etching process

    NASA Astrophysics Data System (ADS)

    Yang, Lina; Huang, Ting; Liu, Wei; Bao, Jie; Huang, Yuanyuan; Cao, Yuanjie; Yao, Tao; Sun, Zhihu; Wei, Shiqiang

    2016-05-01

    Understanding the formation mechanism of gold nanoclusters is essential to the development of their synthetic chemistry. Here, by using x-ray absorption fine-structure (XAFS) spectroscopy, UV-Vis and MS spectra, the formation process of monodisperse Au13 nanoclusters is investigated. We find that a critical step involving the formation of smaller Au8-Au11 metastable intermediate clusters induced by the HCl + HSR etching of the polydisperse Aun precursor clusters occurs firstly. Then these intermediate species undergo a size-growth to Au13 cores, followed by a slow structure rearrangement to reach the final stable structure. This work enriches the understanding of cluster formation chemistry and may guide the way towards the design and the controllable synthesis of nanoclusters.

  6. High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell

    PubMed Central

    Hong, Xinguo; Newville, Matthew; Prakapenka, Vitali B.; Rivers, Mark L.; Sutton, Stephen R.

    2009-01-01

    We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over a small angular range of DAC orientation, e.g., within ±3° relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO2 recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO2 glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO2 glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures. PMID:19655966

  7. High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell

    SciTech Connect

    Hong, X.; Newville, M.; Prakapenka, V.B.; Rivers, M.L.; Sutton, S.R.

    2009-07-31

    We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over a small angular range of DAC orientation, e.g., within {+-}3{sup o} relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO{sub 2} recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO{sub 2} glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO{sub 2} glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.

  8. 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.

  9. XAFS study on the impact of local structure on electrochemical performance for Co3O4 nanowire arrays

    NASA Astrophysics Data System (ADS)

    Jiang, Shan; Cheng, Weiren; He, Jingfu; Huang, Junheng; Liu, Qinghua; Jiang, Yong; Wei, Shiqiang

    2016-05-01

    Determining the local structure of catalyst materials is critical for understanding the mechanism of enhanced electrochemical activity in semiconductor electrode. Here, using X-ray absorption fine structure (XAFS) spectra, we reveal that the local disorder structure is formed for the mixed-phase Co3O4 nanowire arrays due to the interaction between the phases of Co3O4 and Co2(OH)2CO3. Comparing to pure Co3O4 nanowire arrays, the mixed phase sample is richer in Co2+ and the electronic structure is changed by the local structure, which are demonstrated by the X-ray absorption near-edge structure (XANES) spectra. It is deduced that the mixed-phase Co3O4 nanowire arrays with abundant Co2+ sites provide more redox centres in electrochemical reaction than the pure Co3O4 nanowire arrays.

  10. An XAFS Study of Tantalum Chloride in the Ionic Liquid 1-ethyl-3-methyl Imidazolium Chloride/ aluminum Chloride

    SciTech Connect

    D Roeper; K Pandya; G Cheek; W OGrady

    2011-12-31

    Tantalum chloride was studied with extended X-ray absorption fine structure spectroscopy (XAFS) in acidic and basic aluminum chloride/1-ethyl-3-methyl imidazolium chloride ionic liquids (ILs). Anhydrous Ta2Cl10 is more soluble in the basic solution than in the acidic solution and the X-ray absorption data shows that the coordination shell of chlorides around the tantalum is larger in the basic solution. In the acidic solution, tantalum has five chlorides in its coordination shell while in the basic solution; the tantalum is coordinated by seven chlorides. This indicates that the Lewis acidity of the tantalum chloride causes the Ta to coordinate differently in the acidic and the basic solutions.

  11. Hydrothermal diamond anvil cell for XAFS studies of first-row transition elements in aqueous solutions up to supercritical conditions

    USGS Publications Warehouse

    Bassett, William A.; Anderson, Alan J.; Mayanovic, Robert A.; Chou, I.-Ming

    2000-01-01

    A hydrothermal diamond anvil cell (HDAC) has been modified by drilling holes with a laser to within 150 ??m of the anvil face to minimize the loss of X-rays due to absorption and scatter by diamond. This modification enables acquisition of K-edge X-ray absorption fine structure (XAFS) spectra from first-row transition metal ions in aqueous solutions at temperatures ranging from 25??C to 660??C and pressures up to 800 MPa. These pressure-temperature (P-T) conditions are more than sufficient for carrying out experimental measurements that can provide data valuable in the interpretation of fluid inclusions in minerals found in ore-forming hydrothermal systems as well as other important lithospheric processes involving water. (C) 2000 Elsevier Science B.V. All rights reserved.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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

  17. XAFS Model Compound Library

    DOE Data Explorer

    Newville, Matthew

    The XAFS Model Compound Library contains XAFS data on model compounds. The term "model" compounds refers to compounds of homogeneous and well-known crystallographic or molecular structure. Each data file in this library has an associated atoms.inp file that can be converted to a feff.inp file using the program ATOMS. (See the related Searchable Atoms.inp Archive at http://cars9.uchicago.edu/~newville/adb/) This Library exists because XAFS data on model compounds is useful for several reasons, including comparing to unknown data for "fingerprinting" and testing calculations and analysis methods. The collection here is currently limited, but is growing. The focus to date has been on inorganic compounds and minerals of interest to the geochemical community. [Copied, with editing, from http://cars9.uchicago.edu/~newville/ModelLib/

  18. Lead, Uranium, and Nickel Compound Data from the XAFS Library at the Stanford Synchrotron Radiation Laboratory (SSRL)

    DOE Data Explorer

    The x-ray absorption fine structure spectroscopy (XAFS) library at the Stanford Synchrotron Radiation Laboratory is intended to be a reference library of XAFS spectra for various lead, uranium, and nickel compounds. Compounds are organized by central atom and all spectra are transmission data. Molecular Environmental Science (MES) research at SSRL focuses on the fundamental interfacial, molecular- and nano-scale processes that control contaminant and nutrient cycling in the biosphere with the goal of elucidating global elemental cycles and anthropogenic influences on the environment. Key areas of investigation include the: (a) Structural chemistry of water and dissolved solutes, (b) Structural chemistry and reactivity of complex natural environmental materials with respect to heavy metals and metalloids (biominerals, Fe- and Mn-oxides, biofilms, and organic materials), (c) Reactions at environmental interfaces, including sorption, precipitation and dissolution processes that affect the bioavailability of heavy metals and other contaminants, and (d) Microbial transformations of metals and anions. SSRL-based MES research utilizes synchrotron-based x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), small-angle x-ray scattering (SAXS), x-ray standing wave (XSW) spectroscopy, and photoemission spectroscopy (PES) because of their unique capabilities to probe structure/composition relationships in complex, non-crystalline, and dilute materials. [copied from http://www-ssrl.slac.stanford.edu/mes/index.html

  19. On the distribution and bonding environment of Zn and Fe in glasses containing electric arc furnace dust: a mu-XAFS and mu-XRF study.

    PubMed

    Pinakidou, F; Katsikini, M; Paloura, E C; Kavouras, P; Kehagias, Th; Komninou, Ph; Karakostas, Th; Erko, A

    2007-04-01

    We apply synchrotron radiation assisted X-ray fluorescence (SR-XRF), SR-XRF mapping as well as micro- and conventional X-ray absorption fine structure (mu-XAFS and XAFS) spectroscopies in order to study the bonding environment of Fe and Zn in vitrified samples that contain electric arc furnace dust from metal processing industries. The samples are studied in the as-cast state as well as after annealing at 900 degrees C. The SR-XRF results demonstrate that annealing does not induce any significant changes in the distribution of either Fe or Zn, in both the as-cast and annealed glasses. The mu-XAFS spectra recorded at the Fe-K and Zn-K edges reveal that the structural role of both Fe and Zn remains unaffected by the annealing procedure. More specifically, Fe forms both FeO(6) and FeO(4) polyhedra, i.e. acts as an intermediate oxide while Zn occupies tetrahedral sites. PMID:16987597

  20. Determination of iron-ligand bond lengths in ferric and ferrous horse heart cytochrome c using multiple-scattering analyses of XAFS data

    SciTech Connect

    Cheng, M.C.; Rich, A.M.; Armstrong, R.S.; Ellis, P.J.; Lay, P.A.

    1999-12-13

    Cytochrome c (cyt c) is a small heme protein (MW 12 384) that functions as a biological electron-transfer agent. It consists of a single polypeptide chain and a prosthetic heme group and provides a pathway for the transfer of electrons from cyt c reductase to cyt c oxidase in the mitochondrial respiratory chain (oxidative phosphorylation). The protein participates in oxidation-reduction reactions with the heme iron alternating between the oxidized (ferric, Fe{sup III}) state and the reduced (ferrous, Fe{sup II}) state. X-ray absorption fine structure (XAFS) data were obtained from frozen aqueous solutions (10 K) of horse heart ferri- and ferrocyt c. Models of the structure about the Fe center were refined to optimize the fit between the observed XAFS in the range 0 {le} k {le} 16.3 {angstrom}{sup {minus}1} and the XAFS calculated using both single-scattering (SS) and multiple-scattering (MS) calculations. The bond lengths obtained are more accurate and precise than those determined previously for cyt c from various species using X-ray crystallography. The Fe-N bond lengths are 1.98--1.99 {angstrom} for both oxidation states of cyt c. The Fe-S bond of derricyt c (2.33 {angstrom}) is significantly longer than that of ferrocyt c (2.29 {angstrom}). The small changes in the bond lengths are consistent with the small reorganizational energy required for the fast electron-transfer reaction of cyt c.

  1. The BioCAT Microprobe for X-Ray Fluorescence Imaging, MicroXAFS and Microdiffraction Studies on Biological Samples

    SciTech Connect

    Barrea, R.A.; Gore, D.; Kondrashkina, E.; Weng, T.; Heurich, R.; Vukonich, M.; Orgel, J.; Davidson, M.; Collingwood, J.F.; Mikhaylova, A.; Irving, T.C.

    2007-07-31

    Microbeam capabilities have been recently added to the Biophysics Collaborative Access Team (BioCAT) beamline 18-ID at the Advanced Photon Source to allow x-ray elemental mapping, micro x-ray absorption fine structure and microdiffraction studies on biological samples. The microprobe setup comprises a pair of platinum coated silicon KB mirrors; a sample holder mounted in a high precision positioner (100 nm accuracy); fluorescence detectors including a Si drift detector, Fe and Zn Bent Laue analyzers and a Ge detector; and a CCD detector for micro-diffraction experiments. The energy range of the microprobe is from 3.5 keV up to 17 keV. The fast scanning capabilities of the Bio-CAT beamline facilitate rapid acquisition of x-ray elemental images and micro-XAFS spectra. This paper reports the results of commissioning the KB mirror system and its performance in initial x-ray fluorescence mapping and micro-diffraction studies.

  2. Local Structures of Mechanically Alloyed Al70Cu20Fe10 Nanocomposites Studied by XRD and XAFS

    SciTech Connect

    Yin Shilong; Qian Liying; He Bo; Zou Shaobo; Wei Shiqiang; Bian Qing

    2007-02-02

    Ternary Al70Cu20Fe10 alloy nano-composites prepared by mechanical alloying are characterized by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS). The results indicate that after milled for 10 hours, the coordination environment around Cu atoms is changed largely and becomes disordered, but the local structure of Fe atoms still remains as that of {alpha}-Fe. This indicates the forming of inter-metallic compound Al2Cu with body center cubic structure. Even if the milling time is extended to 40 hours, only small amount of {alpha}-Fe can be alloyed to produce Al-Fe-Cu alloy. However, the annealing treatment at 700 deg. C can drive the {alpha}-Fe to incorporate into the Al2Cu compound to form an icosahedral alloy phase.

  3. Metal (Hydr)oxides for the removal of Cr(VI) from drinking water: a XAFS study

    NASA Astrophysics Data System (ADS)

    Pinakidou, F.; Kaprara, E.; Katsikini, M.; Paloura, E. C.; Simeonidis, K.; Mitrakas, M.

    2016-05-01

    The reduction mechanism and adsorption behaviour of Cr(VI) onto Tin(II) oxy- hydroxides are investigated using Cr-K edge X-ray absorption fine structure (XAFS) spectroscopies. The synthesis of the Sn oxy-hydroxide proceeds via hydrolysis of SnSO4. The successful reduction of Cr(VI) was identified by the analysis of the Cr-K edge XANES spectra where only Cr(III) species in octahedral sites are detected. According to the Cr-K edge EXAFS analysis results, Cr(III) forms bidentate inner sphere (binuclear (2C) and mononuclear (2E)) complexes. However, the surface coverage of Cr affects the type of Cr(III)-complexes formed: as the Cr-loading increases, Cr(III)-oxy-anions preferentially sorb in a “combined” 2C and 1V configuration, at the expense of the existing 2E sorption geometry.

  4. 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.

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

    SciTech Connect

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

    2014-08-28

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

  6. X-ray absorption near edge spectroscopy with a superconducting detector for nitrogen dopants in SiC

    PubMed Central

    Ohkubo, M.; Shiki, S.; Ukibe, M.; Matsubayashi, N.; Kitajima, Y.; Nagamachi, S.

    2012-01-01

    Fluorescence-yield X-ray absorption fine structure (FY-XAFS) is extensively used for investigating atomic-scale local structures around specific elements in functional materials. However, conventional FY-XAFS instruments frequently cannot cover trace light elements, for example dopants in wide gap semiconductors, because of insufficient energy resolution of semiconductor X-ray detectors. Here we introduce a superconducting XAFS (SC-XAFS) apparatus to measure X-ray absorption near-edge structure (XANES) of n-type dopant N atoms (4 ×1019 cm−3) implanted at 500°C into 4H-SiC substrates annealed subsequently. The XANES spectra and ab initio multiple scattering calculations indicate that the N atoms almost completely substitute for the C sites, associated with a possible existence of local CN regions, in the as-implanted state. This is a reason why hot implantation is necessary for dopant activation in ion implantation. The SC-XAFS apparatus may play an important role in improving doping processes for energy-saving wide-gap semiconductors and other functional materials. PMID:23152937

  7. MAX: Multiplatform Applications for XAFS

    NASA Astrophysics Data System (ADS)

    Alain, Michalowicz; Jacques, Moscovici; Diane, Muller-Bouvet; Karine, Provost

    2009-11-01

    MAX is a new EXAFS and XANES analysis package, replacing our old "EXAFS pour le Mac" software suite. The major improvement is the ability to work with strictly the same code, compiled at once for Microsoft Windows, Apple MacOSX and LINUX systems, justifying the title "Multiplatform Applications for XAFS". It is organized as four modules: ABSORBIX (X-ray absorbance and fluorescence self-absorption calculations), CHEROKEE (EXAFS and XANES data treatment), ROUNDMIDNIGHT (EXAFS modeling and fit) and CRYSTALFFREV (from crystal structures and molecular modeling to FEFF EXAFS and XANES theoretical calculations). Most features developed in "EXAFS pour le Mac" are still available, but with much improvements in the user's interface, data treatment algorithms and new functionalities.

  8. Ni-induced local distortions in La1.85Sr0.15Cu1-yNiyO4 and their relevance to Tc suppression: An angular-resolved XAFS study

    NASA Astrophysics Data System (ADS)

    Haskel, Daniel; Stern, Edward A.; Polinger, Victor; Dogan, Fatih

    2001-09-01

    We present results from angular-resolved x-ray-absorption fine-structure (XAFS) measurements at the Ni, La, and Sr K edges of oriented powders of La1.85Sr0.15Cu1-yNiyO4, with y=0.01, 0.03, 0.06. A special magnetic alignment procedure allowed us to measure pure ĉ- and ab-oriented XAFS at the Ni K edge in identical fluorescence geometries. Both the x-ray-absorption near-edge structure and the XAFS unequivocally show that the NiO6 octahedra are contracted along the c axis by ~0.32 Å relative to CuO6 octahedra while the in-plane distances of NiO6 and CuO6 octahedra are the same within 0.01 Å. The NiO6 octahedral contraction drives the average ĉ axis contraction measured by diffraction with increasing content of Ni. The local ĉ axis shows strong spatial fluctuations, due to the different NiO6 and CuO6 octahedral configurations and the stronger bonding of a La3+ ion than a Sr2+ ion to the O(2) apical oxygens of such octahedra. We discuss the relevance of these findings to the mechanisms of loss of superconductivity at y~0.03 and hole localization above y~0.05 by Ni dopants.

  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. High-Resolution X-ray Microprobe Using a Spatial Filter and Its Application to Micro-XAFS Measurements

    SciTech Connect

    Terada, Y.; Tanida, H.; Uruga, T.; Takeuchi, A.; Suzuki, Y.; Goto, S.

    2011-09-09

    An x-ray microprobe system with total-reflection mirror optics for trace element analysis has been developed at beamline 37XU of SPring-8. To achieve sub-microprobe, a spatial filter has been installed downstream of a monochromator. Focusing tests have been performed in the x-ray energy range of 6-14 keV. A focused beam size of 0.83 {mu}m(V)x1.35 {mu}m(H) has been obtained at an x-ray energy of 10 keV, and using a spatial filter in the horizontal direction, the beam size is down to 0.84 {mu}m. Micro-x-ray absorption fine structure (XAFS) spectroscopy of submicrometer particles has been done by utilizing the total-reflection mirror optics. It was clearly observed from the nickel K-edge XAFS spectra that the oxidation state of nickel was a mixture of metal and oxide even in the single submicrometer particle.

  11. 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.

  12. XAFS Data Interchange: A single spectrum XAFS data file format

    PubMed Central

    Ravel, B.; Newville, M.

    2016-01-01

    We propose a standard data format for the interchange of XAFS data. The XAFS Data Interchange (XDI) standard is meant to encapsulate a single spectrum of XAFS along with relevant metadata. XDI is a text-based format with a simple syntax which clearly delineates metadata from the data table in a way that is easily interpreted both by a computer and by a human. The metadata header is inspired by the format of an electronic mail header, representing metadata names and values as an associative array. The data table is represented as columns of numbers. This format can be imported as is into most existing XAFS data analysis, spreadsheet, or data visualization programs. Along with a specification and a dictionary of metadata types, we provide an application-programming interface written in C and bindings for programming dynamic languages. PMID:27499797

  13. XAFS Data Interchange: A single spectrum XAFS data file format

    NASA Astrophysics Data System (ADS)

    Ravel, B.; Newville, M.

    2016-05-01

    We propose a standard data format for the interchange of XAFS data. The XAFS Data Interchange (XDI) standard is meant to encapsulate a single spectrum of XAFS along with relevant metadata. XDI is a text-based format with a simple syntax which clearly delineates metadata from the data table in a way that is easily interpreted both by a computer and by a human. The metadata header is inspired by the format of an electronic mail header, representing metadata names and values as an associative array. The data table is represented as columns of numbers. This format can be imported as is into most existing XAFS data analysis, spreadsheet, or data visualization programs. Along with a specification and a dictionary of metadata types, we provide an application-programming interface written in C and bindings for programming dynamic languages.

  14. 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.

  15. Investigation of Room Temperature Oxidation of Cu in Air by Yoneda-XAFS

    SciTech Connect

    Keil, P.; Luetzenkirchen-Hecht, D.; Frahm, R.

    2007-02-02

    The structure of thin copper oxide layers which are formed on metallic Cu due to the exposure to air are investigated with Yoneda-XAFS and ReflEXAFS. The measured Yoneda-XAFS data were compared to quantitative model calculations in the framework of the distorted wave Born approximation (DWBA) assuming different model structures for the oxide layer. Yoneda-XAFS fine structure spectra measured for various different grazing angles show that the experimental data are best described by a model structure consisting of a duplex type oxide layer with an outer layer of CuO (tenorite) in direct contact with the gas atmosphere and an inner Cu2O (cuprite) layer at the interface to the underlying Cu metal.

  16. Conceptual design for a dispersive XAFS beamline in the compact storage ring MIRRORCLE

    NASA Astrophysics Data System (ADS)

    Canestrari, N.; Roger, V.; Jeantet, P.; Leynaud, O.; Ortega, L.; Yamada, H.; Hanashima, T.; Lorenzo, J. E.; Sanchez del Rio, M.

    2011-09-01

    We present the conceptual design of a dispersive X-ray Absorption Fine Structure (XAFS) beamline for MIRRORCLE, a new compact laboratory X-ray source. This machine accelerates electrons up to 1,4,6 or 20MeV (depending upon the model) in a ring and produces X-rays when the electrons collide onto a thin target. The radiation emitted has a white spectrum due to both synchrotron and bremsstrahlung emission. A substantial part of the electrons are recovered after collisions, and the emitted light has high flux, wide energy spectrum and a large angular dispersion. We have opted for a simple beamline design using a collimator, slits, a curved crystal, the sample environment and a CCD. The beamline parameters (position of the mirror, ray of curvature, slit aperture, reflecting angle, etc.) have been optimized by defining and improving a figure of merit. This optimization allows for room constraints (distances among elements), mechanical constraints (minimum curvature radii available) and optical constraints. Further ray tracing simulations using SHADOW3 have been performed to check all the theoretical results, refine the final parameters, quantitative flux calculations and for simulating the image on the CCD camera.

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  18. 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.

  19. Ceria-based Catalysts for the Production of H2 Through the Water-gas-shift Reaction: Time-Resolved XRD and XAFS Studies

    SciTech Connect

    Wang,X.; Rodriguez, J.; Hanson, J.; Gamarra, D.; Marinez-Arias, A.; Fernandez-Garcia, M.

    2008-01-01

    Hydrogen is a potential alternate energy source for satisfying many of our energy needs. In this work, we studied H2 production from the water-gas-shift (WGS) reaction over Ce1-x Cu x O2 catalysts, prepared with a novel microemulsion method, using two synchrotron-based techniques: time-resolved X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS). The results are compared with those reported for conventional CuO x /CeO2 and AuO x /CeO2 catalysts obtained through impregnation of ceria. For the fresh Ce1-x Cu x O2 catalysts, the results of XAFS measurements at the Cu K-edge indicate that Cu is in an oxidation state higher than in CuO. Nevertheless, under WGS reaction conditions the Ce1-x Cu x O2 catalysts undergo reduction and the active phase contains very small particles of metallic Cu and CeO2-x . Time-resolved XRD and XAFS results also indicate that Cud+ and Aud+ species present in fresh CuO x /CeO2 and AuO x /CeO2 catalysts do not survive above 200 C under the WGS conditions. In all these systems, the ceria lattice displayed a significant increase after exposure to CO and a decrease in H2O, indicating that CO reduced ceria while H2O oxidized it. Our data suggest that H2O dissociation occurred on the Ovacancy sites or the Cu-Ovacancy and Au-Ovacancy interfaces. The rate of H2 generation by a Ce0.95Cu0.05O2 catalyst was comparable to that of a 5 wt% CuO x /CeO2 catalyst and much bigger than those of pure ceria or CuO.

  20. Formation of layered single- and double-metal hydroxide precipitates at the mineral/water interface: A multiple-scattering XAFS analysis

    SciTech Connect

    Scheinost, A.C.; Sparks, D.L.

    2000-03-15

    Spectroscopic and microscopic studies have shown that Ni and Co sorption by clay minerals may proceed via formation of surface precipitates. Several studies employing X-ray absorption fine structure (XAFS) spectroscopy suggested the formation of turbostratic, a-type metal hydroxides, of layered double hydroxides (LDH) with Al-for-metal substitution, and of 1:1 or 2:1 phyllosilicates. Distinction of these phases is difficult because they have low crystallinity and/or a small mass compared to the sorbents, and because they have similar metal-metal distances in their hydroxide layers/sheets. Distinction of these phases is crucial, however, because they have substantially differing solubilities. In this paper the authors show that an XAFS beat pattern at about 8 {angstrom} {sup {minus}1} can be used as a fingerprint to unequivocally distinguish LDH from the {alpha}-type hydroxides and phyllosilicates. Full multiple-scattering simulations and experimental spectra of model compounds indicate that the beat pattern is due to focused multiple scattering at Me/Al ratios between 1 and 4(Me = Ni,Co). By applying the fingerprint method to new and to already published XAFS data on Ni and Co surface precipitates, the authors found that LDH preferentially forms in the presence of the Al-containing sorbents pyrophyllite, illite, kaolinite, gibbsite, and alumina above pH 7.0. However, {alpha}-type metal hydroxides form in the presence of the Al-free sorbents talc, silica, and rutile, and in the presence of the Al-containing clay minerals montmorillonite and vermiculite. The authors believe, that the high permanent charge of these latter minerals prevents or retards the release of Al. When Al is available, the formation of LDH seems to be thermodynamically and/or kinetically favored over the formation of {alpha}-type hydroxides.

  1. Formation of Layered Single- and Double-Metal Hydroxide Precipitates at the Mineral/Water Interface: A Multiple-Scattering XAFS Analysis.

    PubMed

    Scheinost; Sparks

    2000-03-15

    Spectroscopic and microscopic studies have shown that Ni and Co sorption by clay minerals may proceed via formation of surface precipitates. Several studies employing X-ray absorption fine structure (XAFS) spectroscopy suggested the formation of turbostratic, alpha-type metal hydroxides, of layered double hydroxides (LDH) with Al-for-metal substitution, and of 1:1 or 2:1 phyllosilicates. Distinction of these phases is difficult because they have low crystallinity and/or a small mass compared to the sorbents, and because they have similar metal-metal distances in their hydroxide layers/sheets. Distinction of these phases is crucial, however, because they have substantially differing solubilities. In this paper we show that an XAFS beat pattern at about 8 Å(-1) can be used as a fingerprint to unequivocally distinguish LDH from the alpha-type hydroxides and phyllosilicates. Full multiple-scattering simulations and experimental spectra of model compounds indicate that the beat pattern is due to focused multiple scattering at Me/Al ratios between 1 and 4 (Me=Ni, Co). By applying the fingerprint method to new and to already published XAFS data on Ni and Co surface precipitates, we found that LDH preferentially forms in the presence of the Al-containing sorbents pyrophyllite, illite, kaolinite, gibbsite, and alumina above pH 7.0. However, alpha-type metal hydroxides form in the presence of the Al-free sorbents talc, silica, and rutile, and in the presence of the Al-containing clay minerals montmorillonite and vermiculite. We believe that the high permanent charge of these latter minerals prevents or retards the release of Al. When Al is available, the formation of LDH seems to be thermodynamically and/or kinetically favored over the formation of alpha-type hydroxides. Copyright 2000 Academic Press. PMID:10700399

  2. Sub-micron spatial resolution of a micro-XAFS electrostatic microscope with bending magnet radiation: Performance assessments and prospects for aberration correction

    NASA Astrophysics Data System (ADS)

    Tonner, B. P.; Dunham, D.

    1994-08-01

    The X-ray photoemission electron microscope (XPEEM) has been shown to be a valuable tool for small-area X-ray absorption fine-structure (XAFS) spectroscopy, and for state-selected imaging. The instrument currently in regular operation on bending-magnet monochromators uses electrostatic optics to create an image of a sample surface in vacuum. The instrument can be operated on a wide variety of X-ray and VUV beamlines, and the spectral resolution is determined by the beamline monochromator. The spatial resolution is determined primarily by the aberrations of the immersion lens accelerating field and the objective lens, although other factors such as surface roughness play an important, though less fundamental role. We have tested the spatial resolution of micro-XAFS with a high quality test object, consisting of a free-standing circular zone plate made of gold. These tests confirm the assessment that chromatic aberration limits the performance of the optics, because of the wide range of kinetic energies of secondary electrons produced in XAFS spectroscopy, and the highly asymmetric intensity distribution of these secondaries. One attempt at solving the chromatic aberration problem is the use of an energy filter, which solves the problem by allowing only a narrow band of electrons to produce an image. We describe an alternative approach, based on chromatic aberration correction, which has great potential for an XPEEM instrument with extremely high transmission, and spatial resolution below 10 nm. We also point out the performance improvements to be expected when XPEEM is adapted to high-throughput undulator beamlines.

  3. Oxidation-resistive copper nanoparticles: photoreduction synthesis and their oxidation state measurements by XAFS and HRTEM

    NASA Astrophysics Data System (ADS)

    Tanaka, H.; Aoki, T.; Yonemura, M.; Miyagawa, M.; Okumura, K.

    2016-05-01

    We examined the synthesis of copper nanoparticles by photoreduction, and characterized them using optical spectroscopy, XAFS measurement, and electron microscopy. Ethanol solution of copper acetate with TiO2 nanoparticles was photoirradated. Optical absorption observation indicated that copper nanoparticles were formed in the solution. XAFS measurement indicated that the nanoparticles were metallic, not oxidized. Electron microscopy observation exhibited that the nanoparticles kept metallic even under exposure to air.

  4. XAFS study of copper and silver nanoparticles in glazes of medieval middle-east lustreware (10th-13th century)

    NASA Astrophysics Data System (ADS)

    Padovani, S.; Puzzovio, D.; Sada, C.; Mazzoldi, P.; Borgia, I.; Sgamellotti, A.; Brunetti, B. G.; Cartechini, L.; D'Acapito, F.; Maurizio, C.; Shokoui, F.; Oliaiy, P.; Rahighi, J.; Lamehi-Rachti, M.; Pantos, E.

    2006-06-01

    It has recently been shown that lustre decoration of medieval and Renaissance pottery consists of silver and copper nanoparticles dispersed in the glassy matrix of the ceramic glaze. Here the findings of an X-ray absorption fine structure (XAFS) study on lustred glazes of shards belonging to 10th and 13rd century pottery from the National Museum of Iran are reported. Absorption spectra in the visible range have been also measured in order to investigate the relations between colour and glaze composition. Gold colour is mainly due to Ag nanoparticles, though Ag+, Cu+ and Cu2+ ions can be also dispersed within the glassy matrix, with different ratios. Red colour is mainly due to Cu nanoparticles, although some Ag nanoparticles, Ag+ and Cu+ ions can be present. The achievement of metallic Cu and the absence of Cu2+ indicate a higher reduction of copper in red lustre. These findings are in substantial agreement with previous results on Italian Renaissance pottery. In spite of the large heterogeneity of cases, the presence of copper and silver ions in the glaze confirms that lustre formation is mediated by a copper- and silver-alkali ion exchange, followed by nucleation and growth of metal nanoparticles.

  5. Extended electron energy loss fine structure simulation of the local boron environment in sodium aluminoborosilicate glasses containing gadolinium

    SciTech Connect

    Qian, Morris; Li, Hong; Li, Liyu ); Strachan, Denis M. )

    2003-10-15

    Gadolinium can be dissolved in sodium-alumino-borosilicate glasses up to 47 wt% in a baseline borosilicate glass (mol%) 20 B2O3, 5 Al2O3, 60 SiO2,and 20 Na2O. Understanding of Gd dissolution in borosilicate melts is important in glass formulation optimization. Electron energy loss fine structure (ELFS) spectroscopy is chosen, which provides well resolved local atomic structure information for both amorphous and crystalline materials with high sensitivity to low Z elements such as Al, B, Na, O, and Si where the x-ray absorption fine structure (XAFS) technique faces experimental difficulty. In this study, we report our results of boron K-edge ELFS study. Two borosilicate glass samples with 30 and 47 mass% Gd2O3, B20Gd30 and B20Gd47were chosen for B K-edge ELFS study. EEL spectra were acquired on a Philips 430 TEM equipped with Gatan PEELS system 666 and EL/P 2.1 software with Custom function AcqLong. The ELFS data analysis was performed using UWELFS, UWXAFS and FEFF software. From our Gd solubility study, the local structure of Gd in the borate environment possibly resembles double chain structure found in crystalline Gd(BO2)3 as proposed by Chakraborty et al. The B/Gd ratio's in both glasses are smaller then 3, which means the excess Gd atoms in the Si-sites would be 17 and 60 mol% of the total Gd atoms, respectively according to the model, yet the local environment of borate sites saturated with Gd should be remained. To verity above hypothesis, the double chain structure model was applied to fit boron K-edge. The model was shown to well fit experimental boron K-edge EELS spectra for both glasses with some degree of distance distortion which is understandable in amorphous structure. Therefore, it is very likely that Gd stabilized in borate sites has a local structure resembling the double chain Gd(BO2)3 structure as proposed by our solubility study and literature.

  6. Structure and electronic properties of Dy@C 82 studied by UV-VIS absorption, X-ray powder diffraction and XAFS

    NASA Astrophysics Data System (ADS)

    Iida, S.; Kubozono, Y.; Slovokhotov, Y.; Takabayashi, Y.; Kanbara, T.; Fukunaga, T.; Fujiki, S.; Emura, S.; Kashino, S.

    2001-04-01

    Two isomers of Dy@C 82 were separated by high performance liquid chromatography (HPLC), and their UV-VIS absorption spectra were measured to characterize these isomers. The crystalline powder of Dy@C 82 was obtained by removing the solvent (toluene) at 250°C under vacuum. The X-ray diffraction pattern can be indexed with fcc crystal lattice, as that in La@C 82. The lattice constant a at 298 K, 15.86(1) Å, is close to that of La@C 82, 15.78 Å. The distances between Dy and the first and second nearest C atoms are determined to be 2.52(2) and 2.86(2) Å, respectively, on the basis of Dy L III-edge EXAFS. The XANES shows that the valence of the Dy atom in Dy@C 82 is +3.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Detection of trace metallic elements in oral lichenoid contact lesions using SR-XRF, PIXE, and XAFS

    PubMed Central

    Sugiyama, Tomoko; Uo, Motohiro; Wada, Takahiro; Omagari, Daisuke; Komiyama, Kazuo; Miyazaki, Serika; Numako, Chiya; Noguchi, Tadahide; Jinbu, Yoshinori; Kusama, Mikio; Mori, Yoshiyuki

    2015-01-01

    Oral lichen planus (OLP) and oral lichenoid contact lesions (OLCL) are chronic inflammatory mucocutaneous reactions with a risk of malignant transformation that alter the epithelium. OLP and OLCL have similar clinical and histopathological features and it is difficult to distinguish one from the other. Metallic restorations are suspected to generate OLCLs. Trace metal analysis of OLCL specimens may facilitate the discrimination of symptoms and identification of causative metallic restorations. The purpose of this study was to assess OLCL tissue samples for the prevalence of metallic elements derived from dental restorations, and to discriminate OLCL from OLP by using synchrotron radiation-excited X-ray fluorescence analysis (SR-XRF), particle-induced X-ray emission (PIXE), and X-ray absorption fine structure (XAFS). Typical elements of dental materials were detected in the OLCL, whereas no obvious element accumulation was detected in OLP and negative control specimens. The origin of the detected metallic elements was presumed to be dental alloys through erosion. Therefore, our findings support the feasibility of providing supporting information to distinguish OLCL from OLP by using elemental analysis. PMID:26085368

  14. Estimation of trace metal elements in oral mucosa specimens by using SR-XRF, PIXE, and XAFS.

    PubMed

    Sugiyama, Tomoko; Uo, Motohiro; Wada, Takahiro; Omagari, Daisuke; Komiyama, Kazuo; Noguchi, Tadahide; Jinbu, Yoshinori; Kusama, Mikio

    2015-02-01

    The effects of dissolved elements from metal dental restorations are a major concern in lesions of the oral mucosa, and the evaluation of accumulated metal elements, especially their distribution and chemical state, is essential for determining the precise effects of trace metals. In this study, X-ray fluorescence with synchrotron radiation (SR-XRF) and particle-induced X-ray emission (PIXE) were applied for distribution analysis of the trace metal elements contained in the oral mucosa, and the chemical states of the elements were estimated using X-ray absorption fine structure (XAFS) analysis. Appropriate combination of these analysis techniques, particularly SR-XRF and PIXE, to visualize the distributions of the elements in the oral mucosa allowed for the observation and evaluation of accumulated metal ions and debris. Importantly, the analyses in this study could be carried out using conventional histopathological specimens without damaging the specimens. Therefore, this method would be applicable for the detection of accumulated trace metal elements in biopsy specimens from the oral mucosa. PMID:25522792

  15. Detection of trace metallic elements in oral lichenoid contact lesions using SR-XRF, PIXE, and XAFS.

    PubMed

    Sugiyama, Tomoko; Uo, Motohiro; Wada, Takahiro; Omagari, Daisuke; Komiyama, Kazuo; Miyazaki, Serika; Numako, Chiya; Noguchi, Tadahide; Jinbu, Yoshinori; Kusama, Mikio; Mori, Yoshiyuki

    2015-01-01

    Oral lichen planus (OLP) and oral lichenoid contact lesions (OLCL) are chronic inflammatory mucocutaneous reactions with a risk of malignant transformation that alter the epithelium. OLP and OLCL have similar clinical and histopathological features and it is difficult to distinguish one from the other. Metallic restorations are suspected to generate OLCLs. Trace metal analysis of OLCL specimens may facilitate the discrimination of symptoms and identification of causative metallic restorations. The purpose of this study was to assess OLCL tissue samples for the prevalence of metallic elements derived from dental restorations, and to discriminate OLCL from OLP by using synchrotron radiation-excited X-ray fluorescence analysis (SR-XRF), particle-induced X-ray emission (PIXE), and X-ray absorption fine structure (XAFS). Typical elements of dental materials were detected in the OLCL, whereas no obvious element accumulation was detected in OLP and negative control specimens. The origin of the detected metallic elements was presumed to be dental alloys through erosion. Therefore, our findings support the feasibility of providing supporting information to distinguish OLCL from OLP by using elemental analysis. PMID:26085368

  16. Cerium oxide as a promoter for the electro-oxidation reaction of ethanol: in situ XAFS characterization of the Pt nanoparticles supported on CeO2 nanoparticles and nanorods.

    PubMed

    Corchado-García, Juan; Betancourt, Luis E; Vélez, Carlos A; Senanayake, Sanjaya D; Stacchiola, Dario; Sasaki, Kotaro; Guinel, Maxime J-F; Zhou, Yunyun; Cheung, Chin Li; Cabrera, Carlos R

    2015-12-28

    In this study we probe the electrocatalytic activity of Pt nanoparticles supported on ceria nanoparticles (NPs) and nanorods (NRs) in the ethanol oxidation reaction (EOR) in alkaline media. The goal of this study was to relate morphology, support structure and composition to the EOR catalytic activity by using in situ X-ray absorption fine structure (XAFS) studies. Cyclic voltammetry experiments showed that both ceria supported catalysts (NP vs. NR) had similar peak current densities at fast scan rates, however at slow scan rates, the ceria NR catalyst showed superior catalytic activity. In situ XAFS studies in KOH showed that both ceria supported catalysts had more electron density in their d-band (with the ceria NR having more electron density overall) than ceria - free Pt/Vulcan standard. However, in an ethanol solution the ceria NR catalyst had the least electron density. We propose that this change is due to the increased charge transfer efficiency between the ceria nanorod support and platinum. In the KOH solution, the increased electron density makes the platinum less electrophilic and hinders Pt-OH bond formation. In the EtOH solution, platinum's increased nucleophilicity facilitates the bond formation between Pt and the electron deficient carbon in ethanol which in turn withdraws the electron density from platinum and increases the white line intensity as observed in the XAS measurements. PMID:26580293

  17. 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.

  18. 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.

  19. 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.

  20. Uranium Speciation As a Function of Depth in Contaminated Hanford Sediments - A Micro-XRF, Micro-XRD, and Micro- And Bulk-XAFS Study

    SciTech Connect

    Singer, David M.; Zachara, John M.; Brown, Gordon E.

    2009-01-05

    Processing ponds at the Hanford, Washington Area 300 site were used for storing basic sodium aluminate and acidic U(VI)-Cu(II)-containing waste from 1943 to 1975. One result of this use is a groundwater plume containing elevated levels of U and Cu beneath the dry ponds and adjacent to the Columbia River. We have used synchrotron-based micro-X-ray fluorescence (μXRF) imaging, micro-X-ray absorption fine structure (μXANES) spectroscopy, and micro-X-ray diffraction (μXRD) techniques combined with bulk U LIII-edge X-ray absorption fine structure (XAFS) spectroscopy to determine the distribution and speciation of U and Cu through the vadose and groundwater zones beneath North Processing Pond #2 (NPP2). Sediment samples were collected from the vadose zone (8’ and 12’ depths), and a sample from the groundwater zone was collected just below the water table (12’-14’ depth). μXRF imaging revealed two major U occurrences within the vadose and groundwater zones: (1) low to moderate concentrations of U(VI) associated with mineral surfaces (particularly chlorite), and (2) high concentration U(VI)-containing micron-sized particles associated with surface coatings on grains of muscovite and chlorite. These U(VI) hot spots are frequently spatially correlated with Cu(II) hot spots. In the groundwater zone, these particles were identified as the copper-uranyl-silicate cuprosklodowskite and the cupper-uranyl-phosphate metatorbernite. In contrast, the U-Cu-containing particles are X-ray amorphous in the vadose zone. Fits of U LIII-edge XAFS spectra by linear-combination fitting indicate that U speciation consists of ~ 75% uranyl sorbed to clays and ~25% metatorbernite-like X-ray amorphous U-Cu-phosphates (8’ depth); nearly 100% sorbed uranyl (12’ depth); and ~70% sorbed uranyl and ~30% cuprosklodowskite/metatorbernite (ground water zone). These findings suggest that the dissolution of U(VI)-Cu(II)-bearing solids as well as the desorption of U(VI), mainly from

  1. High pressure experiments at the XAFS Beamline, INDUS-2

    NASA Astrophysics Data System (ADS)

    Ramanan, Nitya; Lahiri, Debdutta; Garg, Nandini; Bhattacharyya, D.; Jha, S. N.; Sahoo, N. K.; Sharma, Surinder M.

    2012-07-01

    The dispersive XAFS beamline BL-08 at the INDUS-2 synchrotron radiation source, RRCAT, Indore uses a bent Si (111) crystal as dispersive-cum-focusing element and a position sensitive CCD detector to enable instantaneous measurement of the whole XAFS spectrum around the absorption edge of interest. This beamline is ideal for characterisation of materials under high pressure using Diamond Anvil Cell with ~50 μm spot size. For this setup, the theoretically determined spot size (Horizontal × Vertical) varies between 17 × 137 μm and 37 × 142 μm for the x-ray energy range 5 keV-20 keV. To reduce the vertical spot size to <50 μm, we have designed an additional focusing mirror between the polychromator and sample position. The mirror, procured from SESO (France), will be installed shortly. Meanwhile, we have developed a dummy mirror bender setup at CDM (B ARC) and have carried out feasibility tests to confirm reduction in spot size using the same. We have also conducted preliminary XAFS experiments (at BL-08) on SrRuO3 at ~16 keV, under ambient conditions and inside diamond anvil cell, in order to assess the signal intensity and quality. We have obtained reasonably good signal.

  2. 2D XAFS-XEOL Spectroscopy - Some recent developments

    NASA Astrophysics Data System (ADS)

    Ward, M. J.; Smith, J. G.; Regier, T. Z.; Sham, T. K.

    2013-03-01

    The use of optical photons to measure the modulation of the absorption coefficient upon X-ray excitation, or optical XAFS, is of particular interest for application to the study of light emitting semiconducting nanomaterials due to the additional information that may be gained. The potential for site-selectivity, elemental and excitation energy specific luminescence decay channels, and surface vs. bulk effects all make the use of X-ray excited optical luminescence (XEOL) desirable as a detection method. Previous experiments have made use of a monochromator to select the optical emission wavelength used to monitor optical XAFS. This method of detection suffers from the primary limitation of only being able to monitor the optical response at one emission wavelength. By combining the high resolution soft X-ray Spherical Grating Monochromator beam-line at the Canadian Light Source with an Ocean Optics QE 65000 fast CCD spectrophotometer and custom integration software we have developed a technique for collecting 2D XAFS-XEOL spectra, in which the excitation energy is scanned and a XEOL spectra is collected for every energy value. Herein we report the development of this technique and its capabilities using the study of the luminescence emitted from single crystal zinc oxide as an example.

  3. The presence of mercury selenide in various tissues of the striped dolphin: evidence from μ-XRF-XRD and XAFS analyses.

    PubMed

    Nakazawa, Emiko; Ikemoto, Tokutaka; Hokura, Akiko; Terada, Yasuko; Kunito, Takashi; Tanabe, Shinsuke; Nakai, Izumi

    2011-07-01

    Marine mammals accumulate mercury in their tissues at high concentration and detoxify by forming mercury selenide (HgSe, tiemannite) mainly in the liver. We investigated the possibility of formation of HgSe in various tissues (liver, kidney, lung, spleen, pancreas, muscle and brain) other than the liver of the striped dolphin (Stenella coeruleoalba). We applied a combination method of micro-X-ray fluorescence (μ-XRF) imaging and micro-X-ray diffraction (μ-XRD) using a synchrotron radiation X-ray microbeam to analyze the tissue samples directly with minimal sample preparation. By this method, many accumulation points for Hg and Se on a micron scale were found in thin sections of the spleen and liver tissue and consequently, the XRF spectra and the XRD pattern of the hot spots confirmed the presence of tiemannite, HgSe. On the other hand, the insoluble fractions after enzyme digestion of the nuclear and mitochondrial fractions of all tissues were subjected to X-ray absorption fine structure (XAFS) analysis. XAFS analysis confirmed the presence of HgSe in all the tissues examined (liver, kidney, lung, spleen, pancreas, muscle and brain) of the striped dolphin. The presence of HgSe in all the tissues examined suggests that Se would be involved in the detoxification process of Hg in various tissues other than the liver. This contribution seems to be large especially in the liver and spleen but relatively small in the kidney, pancreas and brain, because the proportion of insoluble fraction containing HgSe was lower in these tissues (25 to 46%). This is the first report on the presence of tiemannite HgSe in various tissues of marine mammals. PMID:21468440

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. [CuCln](2-n) Ion-Pair Species in 1-Ethyl-3-Methylimidazolium Chloride Ionic Liquid-Water Mixtures: Ultraviolet-Visible, X-ray Absorbtion Fine Structure, and Density Functional Theory Characterization

    SciTech Connect

    Li, Guosheng; Camaioni, Donald M.; Amonette, James E.; Zhang, Z. Conrad; Johnson, Timothy J.; Fulton, John L.

    2010-10-07

    We report details of the coordination environment about Cu(II) in a pure ionic liquid, 1- ethyl-3-methylimidazolium chloride ([EMIM]Cl) and in mixtures containing varying amounts of water from 0-100% of the [EMIM]Cl. There are many stages in the ion pairing of the divalent cation, Cu(II) including the contact ion pairing of Cu2+ with multiple Cl- to form various CuCln (2-n) polyanions. Thereis also the subsequent solvation and ion pairing of the polychlorometallate anion with the EMIM+ cation. Using a combination of x-ray absorption fine structure (XAFS), UV-Vis spectroscopy and electronic structure calculations (TDDFT) we are able to follow the detailed structural changes about Cu(II). Ion pair formation is strongly promoted in [EMIM]Cl by the low dielectric constant and by the extensive breakdown of the water hydrogen bond network in [EMIM]Cl/water mixtures. In the [EMIM]Cl solvent the CuCl4 2- species dominates and it’s geometry is quite similar to gas-phase structure. These results are important in understanding catalysis and separation processes involving transition metals in ionic liquid systems.

  12. Transformation and Immobilization of Chromium by Arbuscular Mycorrhizal Fungi as Revealed by SEM-EDS, TEM-EDS, and XAFS.

    PubMed

    Wu, Songlin; Zhang, Xin; Sun, Yuqing; Wu, Zhaoxiang; Li, Tao; Hu, Yajun; Su, Dan; Lv, Jitao; Li, Gang; Zhang, Zhensong; Zheng, Lirong; Zhang, Jing; Chen, Baodong

    2015-12-15

    Arbuscular mycorrhizal fungi (AMF), ubiquitous soil fungi that form symbiotic relationships with the majority of terrestrial plants, are known to play an important role in plant tolerance to chromium (Cr) contamination. However, the underlying mechanisms, especially the direct influences of AMF on the translocation and transformation of Cr in the soil-plant continuum, are still unresolved. In a two-compartment root-organ cultivation system, the extraradical mycelium (ERM) of mycorrhizal roots was treated with 0.05 mmol L(-1) Cr(VI) for 12 days to investigate the uptake, translocation, and transformation of Cr(VI) by AMF using inductively coupled plasma mass spectrometry (ICP-MS), scanning electron microscopy equipped with energy-dispersive spectroscopy (SEM-EDS), transmission electron microscopy equipped with energy-dispersive spectroscopy (TEM-EDS), and X-ray-absorption fine structure (XAFS) technologies. The results indicated that AMF can immobilize quantities of Cr via reduction of Cr(VI) to Cr(III), forming Cr(III)-phosphate analogues, likely on the fungal surface. Besides this, we also confirmed that the extraradical mycelium (ERM) can actively take up Cr [either in the form of Cr(VI) or Cr(III)] and transport Cr [potentially in the form of Cr(III)-histidine analogues] to mycorrhizal roots but immobilize most of the Cr(III) in the fungal structures. Based on an X-ray absorption near-edge spectroscopy analysis of Cr(VI)-treated roots, we proposed that the intraradical fungal structures can also immobilize Cr within mycorrhizal roots. Our findings confirmed the immobilization of Cr by AMF, which plays an essential role in the Cr(VI) tolerance of AM symbioses. PMID:26551890

  13. Slow formation and dissolution of Zn precipitates in soil: a combined column-transport and XAFS study.

    PubMed

    Voegelin, Andreas; Scheinost, Andreas C; Bühlmann, Karin; Barmettler, Kurt; Kretzschmar, Ruben

    2002-09-01

    Recent spectroscopic studies have demonstrated the formation of layered double hydroxides (LDH) and phyllosilicates upon sorption of Zn2+, Ni2+, and Co2+ to clay minerals and aluminum oxides at neutral to alkaline pH and at relatively high initial metal concentrations (>1 mM). The intention of the present study was to investigate whether such phases also form in soil under slightly acidic conditions and at lower metal concentrations. Columns packed with a loamy soil were percolated with aqueous solutions containing 0.1 or 0.2 mM Zn, Ni, Co, and Cd in a 10 mM CaCl2 background at pH 6.5. Metal breakthrough curves indicated a rapid initial sorption step, resulting in retarded breakthrough fronts, followed by further slow metal retention during the entire loading period of 42 days (7000 pore volumes). Total metal sorption and the contribution of slow sorption processes decreased in the order Zn > Ni > Co > Cd. Leaching the reacted soil with 10 mM CaCl2 at pH 6.5 remobilized 8% of the total retained Zn, 15% of Ni, 21% of Co, and 77% of Cd. Subsequent leaching with acidified influent (pH 3.0) remobilized most of the remaining metals. X-ray absorption fine-structure (XAFS) spectroscopy revealed that slow Zn sorption was due to the formation of a Zn-Al LDH precipitate. Although Ni, Co, and Cd concentrations were too low for XAFS analysis, their leaching patterns suggest that part of Ni and Co were also incorporated in solid phases, while most sorbed Cd was still present as exchangeable sorption complex after 42 days. A small but significant percentage of the sorbed metals (2-5%) remained in the soil, even after leaching with more than 3000 pore volumes at pH 3.0, which may suggest micropore diffusion or incorporation into more stable mineral phases. PMID:12322747

  14. Origin of Photoluminescence and XAFS Study of (ZnS)1-x(AgInS2)x Nanocrystals

    SciTech Connect

    Rao, M. Jagadeeswara; Shibata, Tomohiro; Chattopadhyay, Soma; Nag, Angshuman

    2014-03-10

    Donor–Acceptor transition was previously suggested as a mechanism for luminescence in (ZnS)1–x(AgInS2)x nanocrystals. Here we show the participation of delocalized valence/conduction band in the luminescence. Two emission pathways are observed: Path-1 involves transition between a delocalized state and a localized state exhibiting higher energy and shorter lifetime (~25 ns) and Path-2 (donor–acceptor) involves two localized defect states exhibiting lower emission energy and longer lifetime (>185 ns). Surprisingly, Path-1 dominates (82% for x = 0.33) for nanocrystals with lower x, in sharp difference with prior assignment. Luminescence peak blue shifts systematically by 0.57 eV with decreasing x because of this large contribution from Path-1. X-ray absorption fine structure (XAFS) study of (ZnS)1–x(AgInS2)x nanocrystals shows larger AgS4 tetrahedra compared with InS4 tetrahedra with Ag–S and In–S bond lengths 2.52 and 2.45 Å respectively, whereas Zn–S bond length is 2.33 Å along with the absence of second nearest-neighbor Zn–S–metal correlation.

  15. Where do the doped holes go in La{sub 2-x}Sr{sub x}CuO{sub 4}? A close look by XAFS

    SciTech Connect

    Haskel, Daniel; Polinger, Victor; Stern, Edward A.

    1999-09-01

    Polarized x-ray absorption fine structure (XAFS) measurements at the La and Sr sites in La{sub 2-x}Sr{sub x}CuO{sub 4} (0.075(less-or-similar sign)x(less-or-similar sign)0.35) indicate that doped holes introduced with Sr are not uniformly distributed in the CuO{sub 2} planes but reside in impurity states with the majority of charge located on CuO{sub 6} octahedra coupled to the Sr dopants by an apical oxygen (denoted as Sr octahedra). A model based on doped hole-induced Jahn Teller (JT) distortions of these Sr octahedra indicates the impurity states are overlapping singlet and triplet ones resulting from pairings of intrinsic and extrinsic holes. The more mobile singlet pairs reside in the CuO{sub 2} planes, are bound by more than 0.1 eV and could Bose-condense into a superconducting state. The predominant appearance of (mostly) out-of plane triplet states at high x intimately related to the 2D-3D crossover in transport properties and could relate to the observed loss of high T{sub c} in the overdoped regime, as confinement of carriers to the CuO{sub 2} planes is reduced. (c) 1999 American Institute of Physics.

  16. 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.

  17. A novel surface-sensitive X-ray absorption spectroscopic detector to study the thermal decomposition of cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Nonaka, Takamasa; Okuda, Chikaaki; Oka, Hideaki; Nishimura, Yusaku F.; Makimura, Yoshinari; Kondo, Yasuhito; Dohmae, Kazuhiko; Takeuchi, Yoji

    2016-09-01

    A surface-sensitive conversion-electron-yield X-ray absorption fine structure (CEY-XAFS) detector that operates at elevated temperatures is developed to investigate the thermal decomposition of cathode materials for Li-ion batteries. The detector enables measurements with the sample temperature controlled from room temperature up to 450 °C. The detector is applied to the LiNi0.75Co0.15Al0.05Mg0.05O2 cathode material at 0% state of charge (SOC) and 50% SOC to examine the chemical changes that occur during heating in the absence of an electrolyte. The combination of surface-sensitive CEY-XAFS and bulk-sensitive transmission-mode XAFS shows that the reduction of Ni and Co ions begins at the surface of the cathode particles at around 150 °C, and propagates inside the particle upon further heating. These changes with heating are irreversible and are more obvious at 50% SOC than at 0% SOC. The fraction of reduced Ni ions is larger than that of reduced Co ions. These results demonstrate the capability of the developed detector to obtain important information for the safe employment of this cathode material in Li-ion batteries.

  18. 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.

  19. 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.

  20. 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.

  1. XAFS study of gadolinium and samarium bisporphyrinate complexes.

    PubMed

    Agondanou, J H; Spyroulias, G A; Purans, J; Tsikalas, G; Souleau, C; Coutsolelos, A G; Bénazeth, S

    2001-11-19

    The comparative X-ray absorption spectroscopy study of gadolinium and samarium bisporphyrinate complexes represented by the formulas Gd(III)H(oep)(tpp), Gd(III)(oep)(2), Gd(III)H(tpp)(2) and Sm(III)H(oep)(tpp), Sm(III)(oep)(2), Sm(III)H(tpp)(2) is reported. The XAFS spectra are recorded on the LURE-DCI storage ring (Orsay, France) in transmission mode on the microcrystalline samples at the Gd and Sm L(3) edges. The local environment for Ln(3+) ions has been reconstructed applying one-shell and two-shell XAFS analysis procedures. The protonated and nonprotonated bisporphyrinate complexes present different XAFS features. After our analysis on the title derivatives, the gadolinium ion (at 80 K) is found to be bonded: (i) to eight nitrogen atoms at R(Gd-N) 2.50 A, for Gd(III)(oep)(2) [Debye-Waller (DW) factor 0.004 A(2)]; (ii) to seven nitrogen atoms at R(Gd-N) 2.49 A, for Gd(III)H(oep)(tpp) [DW factor 0.005 A(2)] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Gd-N) 2.50 A [DW factor 0.006 A(2)] and two nitrogen atoms at long distance for Gd(III)H(tpp)(2). A similar coordination sphere has been detected for the corresponding Sm derivatives. So, the samarium ion (at room temperature) is bonded: (i) to eight nitrogen atoms at R(Sm-N) 2.53 A, for Sm(III)(oep)(2) [DW factor 0.006 A(2)]; (ii) to seven nitrogen atoms at R(Sm-N) 2.53 A, for Sm(III)H(oep)(tpp) [DW factor 0.006 A(2)] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Sm-N) 2.50 A, for Sm(III)H(tpp)(2) [DW factor 0.006 A(2)] and two nitrogen atoms at long distance. As far as concerns Ln(III)(oep)(2) complexes, the increase of Ln-N distance in the series Gd(3+) < Eu(3+) < Sm(3+) reflects an increase in the ionic radii, which are in good agreement with previously published XRD data on Eu(III)(oep)(2). Moreover, the protonated Ln(III)H(oep)(tpp) and Ln(III)H(tpp)(2) complexes possess systematically shorter distances of about 0.02 A between the XAFS and XRD data. This

  2. Local structural studies of oriented high-temperature superconducting cuprates by polarized XAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Haskel, Daniel

    1998-07-01

    Doping (Sr,Ba) in Lasb{2-x}(Sr,Ba)sb{x}CuOsb4 induces high Tsb{c} superconductivity in addition to profound changes in structural, magnetic and normal state electronic properties. The purpose of this thesis is to investigate the structural characteristics accompanying this doping by performing orientation dependent x-ray absorption fine structure (XAFS) measurements on magnetically aligned powders. This type of measurements allowed obtaining critical information at the La/(Sr,Ba) site previously unavailable, as detailed below. The measurements show that hole carriers introduced with Sr are polaronic in nature as evident from the two site configuration found for the O(2) apical neighboring Sr and the lack of temperature dependence in the O(2) distribution, which indicates that the hole states associated with each site are not discrete but rather broader than ksb{B}T up to T = 300K. There is a good theoretical argument suggesting each O(2) site is associated with holes being doped into O(1) 2psb{x,y}-Cu 3dsb{xsp2-ysp2} in-plane and O(2) 2psb{z}-Cu 3dsb{3zsp2-rsp2} out-of-plane electronic bands resulting in two different Jahn-Teller distortions of the CuOsb6 octahedra neighboring Sr, where the doped holes are peaked. Based on this argument, the predominance of out-of-plane character for the doped holes, as evidenced from the concentration dependence of the relative population of O(2) sites, would imply that theories of high Tsb{c} relying only on in-plane character of the doped holes are not complete in describing the properties of these cuprates. Our measurements showed that all structural phase transitions in Lasb{2-x}(Sr,Ba)sb{x}CuOsb4 have a significant order-disorder component, as opposed to the purely displacive models found in crystallographic studies. The CuOsb6 octahedra are locally tilted in the high-doping, high-temperature phases but fail to order over long range resulting in the average structures of the crystallographic studies. A critical parameter in

  3. Uranium speciation as a function of depth in contaminated hanford sediments--a micro-XRF, micro-XRD, and micro- and bulk-XAFS study.

    PubMed

    Singer, David M; Zachara, John M; Brown, Gordon E

    2009-02-01

    The distribution and speciation of U and Cu in contaminated vadose zone and aquifer sediments from the U.S. DOE Hanford site (300 Area) were determined using a combination of synchrotron-based micro-X-ray fluorescence (microXRF) imaging, micro-X-ray absorption near edge structure (microXANES) spectroscopy, and micro-X-ray diffraction (microXRD) techniques combined with bulk U LIII-edge X-ray absorption fine structure (XAFS) spectroscopy. Samples were collected from within the inactive North Process Pond (NPP2) at 8 ft (2.4 m, NPP2-8) depth and 12 ft (3.7 m, NPP2-12) depth in the vadose zone, and fines were isolated from turbid groundwater just below the water Table (12-14 ft, approximately 4 m, NPP2-GW). microXRF imaging, microXRD, and microXANES spectroscopy revealed two major U occurrences within the vadose and groundwater zones: (1) low to moderate concentrations of U(VI) associated with fine-textured grain coatings that were consistently found to contain clinochlore (referred to here as chlorite) observed in all three samples, and (2) U(VI)-Cu(II) hotspots consisting of micrometer-sized particles associated with surface coatings on grains of muscovite and chlorite observed in samples NPP2-8' and NPP2-GW. In the aquifer fines (NPP2-GW), these particles were identified as cuprosklodowskite (cps: Cu[(UO2)(SiO2OH)]2 x 6H2O) and metatorbernite (mtb: Cu(UO2)2(PO4)2 x 8H2O). In contrast, the U-Cu-containing particles in the vadose zone were X-ray amorphous. Analyses of U LIII-edge XAFS spectra by linear-combination fitting indicated that U speciation consisted of (1) approximately 75% uranyl sorbed to chlorite and approximately 25% mtb-like X-ray amorphous U-Cu-phosphates (8 ft depth), (2) nearly 100% sorbed uranyl (12 ft depth), and (3) approximately 70% uranyl sorbed to chlorite and approximately 30% cps/mtb (groundwater zone). These findings suggest that dissolution of U(VI)-Cu(II)-bearing solids as well as desorption of U(VI), mainly from phyllosilicates, are

  4. 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).…

  5. Isolated attosecond soft X-rays and water window XAFS

    NASA Astrophysics Data System (ADS)

    Biegert, Jens

    2016-05-01

    We demonstrate generation of isolated attosecond soft X-ray pulses with duration less than 350 as at the carbon K-edge at 284 eV. This reproducible and CEP stable attosecond soft X-ray continuum covers the entire water window from 200 eV to 550 eV with a flux of 7.3x 107 photons/s and corresponds to a pulse energy of 2.9 pJ. We demonstrate the utility of our table-top source through soft X-ray near-edge fine-structure spectroscopy at K-shell absorption edges in condensed matter and retrieve the specific absorption features corresponding to the binding orbitals. We believe that these results herald attosecond material science by bridging the gap between ultrafast temporal resolution and element specific probing at the fundamental absorption edges of matter.

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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

  13. XAFS data acquisition with 2D-detectors: Transmission mode XAFS and grazing incidence EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Lützenkirchen-Hecht, D.; Gasse, J.-C.; Bögel, R.; Wagner, R.; Frahm, R.

    2016-05-01

    XAFS-experiments in transmission and reflection modes have been performed using a Pilatus 100K pixel detector. Transmission mode XAFS spectra from a Co metal foil and Co3O4 were recorded to evaluate the data quality offered by this 2D-detector. Furthermore, the pixel detector was also used to measure reflection mode grazing incidence EXAFS data. Using different regions of interest in the collected scattering patterns, we will show that the diffuse scattering can be separated for the different contributing surfaces and interfaces, allowing simultaneous investigations of surfaces and buried interfaces within multi-layered samples.

  14. 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.

  15. 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.

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

    NASA Astrophysics Data System (ADS)

    Corrales, Lia

    2016-06-01

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

  17. XAFSmass: a program for calculating the optimal mass of XAFS samples

    NASA Astrophysics Data System (ADS)

    Klementiev, K.; Chernikov, R.

    2016-05-01

    We present a new implementation of the XAFSmass program that calculates the optimal mass of XAFS samples. It has several improvements as compared to the old Windows based program XAFSmass: 1) it is truly platform independent, as provided by Python language, 2) it has an improved parser of chemical formulas that enables parentheses and nested inclusion-to-matrix weight percentages. The program calculates the absorption edge height given the total optical thickness, operates with differently determined sample amounts (mass, pressure, density or sample area) depending on the aggregate state of the sample and solves the inverse problem of finding the elemental composition given the experimental absorption edge jump and the chemical formula.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. Speciation of Energy Critical Elements in Marine Ferromanganese Crusts and Nodules by Principal Component Analysis and Least-squares fits to XAFS Spectra

    NASA Astrophysics Data System (ADS)

    Foster, A. L.; Klofas, J. M.; Hein, J. R.; Koschinsky, A.; Bargar, J.; Dunham, R. E.; Conrad, T. A.

    2011-12-01

    Marine ferromanganese crusts and nodules ("Fe-Mn crusts") are considered a potential mineral resource due to their accumulation of several economically-important elements at concentrations above mean crustal abundances. They are typically composed of intergrown Fe oxyhydroxide and Mn oxide; thicker (older) crusts can also contain carbonate fluorapatite. We used X-ray absorption fine-structure (XAFS) spectroscopy, a molecular-scale structure probe, to determine the speciation of several elements (Te, Bi, Mo, Zr, Pt) in Fe-Mn crusts. As a first step in analysis of this dataset, we have conducted principal component analysis (PCA) of Te K-edge and Mo K-edge, k3-weighted XAFS spectra. The sample set consisted of 12 homogenized, ground Fe-Mn crust samples from 8 locations in the global ocean. One sample was subjected to a chemical leach to selectively remove Mn oxides and the elements associated with it. The samples in the study set contain 50-205 mg/kg Te (average = 88) and 97-802 mg/kg Mo (average = 567). PCAs of background-subtracted, normalized Te K-edge and Mo K-edge XAFS spectra were performed on a data matrix of 12 rows x 122 columns (rows = samples; columns = Te or Mo fluorescence value at each energy step) and results were visualized without rotation. The number of significant components was assessed by the Malinowski indicator function and ability of the components to reconstruct the features (minus noise) of all sample spectra. Two components were significant by these criteria for both Te and Mo PCAs and described a total of 74 and 75% of the total variance, respectively. Reconstruction of potential model compounds by the principal components derived from PCAs on the sample set ("target transformation") provides a means of ranking models in terms of their utility for subsequent linear-combination, least-squares (LCLS) fits (the next step of data analysis). Synthetic end-member models of Te4+, Te6+, and Mo adsorbed to Fe(III) oxyhydroxide and Mn oxide were

  6. 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

  7. 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.

  8. 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

  9. 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

  10. `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.

  11. 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.

  12. 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.

  13. FEFF5: An ab initio multiple scattering XAFS code

    SciTech Connect

    Rehr, J.J.; Zabinsky, S.I.

    1992-12-31

    FEFF5 is an efficient automated code which calculates multiple scattering (MS) curved wave XAFS spectra for molecules and solids. The theoretical ingredients and approximations contained in the code are revised, with the aim of describing the how XAFS spectra are efficiently simulated. The FEFF5 code consists of 4 independent modules: a scattering potential and phase shift module, a path finder module, a scattering amplitude module and an XAFS module. Multiple scattering Debye-Waller factors are built in using a correlated Debye model.

  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. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. XAFS study of Ni (II) aminovinylketone complexes

    NASA Astrophysics Data System (ADS)

    Yalovega, Galina E.; Vlasenko, Valerii G.; Uraev, Ali I.; Garnovskii, Alexander D.; Soldatov, Alexander V.

    2006-11-01

    The functional properties of the active sites in a metalloproteins depend on coordination geometry of metal, the number and the nature of coordination ligands. The Ni K-edge XAFS spectra of novel nickel complexes as models for the MeN 2O 2(S 2) active site in metalloproteins were measured and analyzed. Theoretical analysis of the Ni K-edge XANES was performed using FDMNES code based on the finite difference method (FDM) to solve the Schrödinger equation beyond muffin-tin approximations and self-consistent full multiple-scattering approach (code FEFF8.2). It was found that the spectrum is almost totally formed by the octahedron of the nearest neighbor atoms around Ni ion in the II (Ni) complex. The III (Ni) complex active center exists in square-planar configuration with shorter distances.

  5. [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

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. Analysis of modulated Ho2PdSi3 crystal structure at Pd K and Ho L absorption edges using resonant elastic X-scattering.

    PubMed

    Nentwich, Melanie; Zschornak, Matthias; Richter, Carsten; Novikov, Dmitri; Meyer, Dirk C

    2016-02-17

    Replacing Si atoms with a transition metal in rare earth disilicides results in a family of intermetallic compounds with a variety of complex magnetic phase transitions. In particular, the family R 2PdSi3 shows interesting magnetic behavior arising from the electronic interaction of the R element with the transition metal in the Si network, inducing the specific structure of the related phase. Within this series, the highest degree of superstructural order was reported for the investigated representative Ho2PdSi3, although several competing superstructures have been proposed in literature. The diffraction anomalous fine structure (DAFS) method is highly sensitive to the local structure of chosen atoms at specific positions within the unit cell of a crystalline phase. In combination with x-ray absorption fine structure (XAFS), this sophisticated synchrotron method has been applied in the present work to several selected reflections, i.a. a satellite reflection. Extensive electronic modeling was used to test the most relevant structure proposals. The [Formula: see text] superstructure has been strongly confirmed, although a small amount of disorder in the modulation is very probable. PMID:26788844

  18. Analysis of modulated Ho2PdSi3 crystal structure at Pd K and Ho L absorption edges using resonant elastic X-scattering

    NASA Astrophysics Data System (ADS)

    Nentwich, Melanie; Zschornak, Matthias; Richter, Carsten; Novikov, Dmitri; Meyer, Dirk C.

    2016-02-01

    Replacing Si atoms with a transition metal in rare earth disilicides results in a family of intermetallic compounds with a variety of complex magnetic phase transitions. In particular, the family R 2PdSi3 shows interesting magnetic behavior arising from the electronic interaction of the R element with the transition metal in the Si network, inducing the specific structure of the related phase. Within this series, the highest degree of superstructural order was reported for the investigated representative Ho2PdSi3, although several competing superstructures have been proposed in literature. The diffraction anomalous fine structure (DAFS) method is highly sensitive to the local structure of chosen atoms at specific positions within the unit cell of a crystalline phase. In combination with x-ray absorption fine structure (XAFS), this sophisticated synchrotron method has been applied in the present work to several selected reflections, i.a. a satellite reflection. Extensive electronic modeling was used to test the most relevant structure proposals. The 2× 2× 8 superstructure has been strongly confirmed, although a small amount of disorder in the modulation is very probable.

  19. 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.

  20. Speciation of Cu in a Contaminated Agricultural Soil Measured By XAFS, Mu-XAFS, And Mu-XRF

    SciTech Connect

    Strawn, D.G.; Baker, L.L.

    2009-05-26

    Contamination of agricultural soils with Cu as a result of fungicide application and spills threatens environmental quality and reduces soil quality for crop growth. In this paper advanced spectroscopic and microscopic methods were used to elucidate the Cu speciation in a calcareous soil contaminated since the 1940s. Microscopically focused synchrotron-based XRF ({mu}-SXRF) was used to map the elemental distribution in the soils. Results indicated that most of the Cu was not associated with metal oxides, silicates, phosphates, or carbonates. Bulk and microscopically focused X-absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra indicated that the Cu in the soil was predominantly Cu adsorbed on soil organic matter (SOM). Interpretation of the fitting results suggests that the Cu is complexed to SOM via bidentate inner-sphere coordination with carboxyl or amine ligands. Results presented in this paper provide detailed information on the molecular coordination of Cu in a contaminated soil. Such information is critical for understanding the long-term fate and best management practices for Cu in the environment.

  1. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    SciTech Connect

    Degueldre, Claude Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O₂ lattice in an irradiated (60 MW d kg⁻¹) 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 Am (~0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am³⁺ species within an [AmO₈]¹³⁻ coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix. - Graphical abstract: Americium LIII XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 μm×300 μm beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO₂ matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am³⁺ face an AmO₈¹³⁻coordination environment in the (Pu,U)O₂ matrix. • The americium dioxide is reduced by the uranium dioxide matrix.

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

    PubMed Central

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

    2009-01-01

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

  3. 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

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. 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

  9. 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 ...

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Assessment of XAF1 as A Biomarker to Differentiate Hepatocellular Carcinoma from Nonneoplastic Liver Tissues

    PubMed Central

    Lin, Ying

    2012-01-01

    Objective XIAP-associated factor 1 (XAF1) expression has been shown to be related with apoptosis in hepatocellular carcinoma (HCC). However, the correlation of XAF1 expression with HCC tumor grade has not been intensively assessed. XIAP-associated factor-1 (XAF1) is an important apoptosis inducer in human HCC. The aim of this study is to determine the correlation between XAF1 expression and HCC histopathological grades. Methods The mRNA levels of XAF1 in 24 paired HCC-nonneoplastic specimens were quantified by real-time reverse transcription PCR (RT-PCR). Protein levels of XAF1 in 110 paired HCC-noncancer tissues were investigated by immunostaining specimens on a tissue microarray (TMA). Correlations between XAF1 mRNA levels or protein expression and clinicopathological features were assessed by statistical analysis. Results Both XAF1 mRNA and protein were significantly under-expressed in HCC tissues compared to their non-neoplastic counterparts. No significant relationship was found between XAF1 mRNA or protein expression and histological tumor grade. Conclusion All these data suggest that XAF1 is a potential biomarker for differentiating HCC with noncancerous tissues. PMID:23358741

  1. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    NASA Astrophysics Data System (ADS)

    Degueldre, Claude; Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O2 lattice in an irradiated (60 MW d kg-1) 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 Am (˜0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am3+ species within an [AmO8]13- coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix.

  2. Plutonium-uranium mixed oxide characterization by coupling micro-X-ray diffraction and absorption investigations

    NASA Astrophysics Data System (ADS)

    Degueldre, C.; Martin, M.; Kuri, G.; Grolimund, D.; Borca, C.

    2011-09-01

    Plutonium-uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The potential differences of metal redox state and microstructural developments of the matrix before and after irradiation are commonly analysed by electron probe microanalysis. In this work the structure and next-neighbor atomic environments of Pu and U oxide features within unirradiated homogeneous MOX and irradiated (60 MW d kg -1) MOX samples was analysed by micro-X-ray fluorescence (μ-XRF), micro-X-ray diffraction (μ-XRD) and micro-X-ray absorption fine structure (μ-XAFS) spectroscopy. The grain properties, chemical bonding, valences and stoichiometry of Pu and U are determined from the experimental data gained for the unirradiated as well as for irradiated fuel material examined in the center of the fuel as well as in its peripheral zone (rim). The formation of sub-grains is observed as well as their development from the center to the rim (polygonization). In the irradiated sample Pu remains tetravalent (>95%) and no (<5%) Pu(V) or Pu(VI) can be detected while the fuel could undergo slight oxidation in the rim zone. Any slight potential plutonium oxidation is buffered by the uranium dioxide matrix while locally fuel cladding interaction could also affect the redox of the fuel.

  3. 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.

  4. 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}

  5. Restoration of XAF1 expression induces apoptosis and inhibits tumor growth in gastric cancer.

    PubMed

    Tu, Shui Ping; Liston, Peter; Cui, Jian Tao; Lin, Marie C M; Jiang, Xiao Hua; Yang, Yi; Gu, Qing; Jiang, Shi Hu; Lum, Ching Tung; Kung, Hsiang Fu; Korneluk, Robert G; Wong, Benjamin Chun-Yu

    2009-08-01

    XAF1 (XIAP-associated factor 1) is a novel XIAP binding protein that can antagonize XIAP and sensitize cells to other cell death triggers. Our previous results have shown that aberrant hypermethylation of the CpG sites in XAF1 promoter is strongly associated with lower expression of XAF1 in gastric cancers. In our study, we investigated the effect of restoration of XAF1 expression on growth of gastric cancers. We found that the restoration of XAF1 expression suppressed anchorage-dependent and -independent growth and increased sensitivity to TRAIL and drug-induced apoptosis. Stable cell clones expressing XAF1 exhibited delayed tumor initiation in nude mice. Restoration of XAF1 expression mediated by adenovirus vector greatly increased apoptosis in gastric cancer cell lines in a time- and dose-dependent manner and sensitized cancer cells to TRAIL and drugs-induced apoptosis. Adeno-XAF1 transduction induced cell cycle G2/M arrest and upregulated the expression of p21 and downregulated the expression of cyclin B1 and cdc2. Notably, adeno-XAF1 treatment significantly inhibited tumor growth, strongly enhanced the antitumor activity of TRAIL in a gastric cancer xenograft model in vivo, and significantly prolonged the survival time of animals bearing tumor xenografts. Complete eradication of established tumors was achieved on combined treatment with adeno-XAF1 and TRAIL. Our results document that the restoration of XAF1 inhibits gastric tumorigenesis and tumor growth and that XAF1 is a promising candidate for cancer gene therapy. PMID:19358264

  6. An XAFS Beamline at the SAGA Light Source

    SciTech Connect

    Okajima, Toshihiro; Hara, Kazuhiro; Tabata, Masaaki; Setoyama, Hiroyuki; Yoshimura, Daisuke; Chikaura, Yoshinori

    2007-02-02

    A new hard X-ray beamline, BL15, has been designed and constructed at the SAGA-Light Source. The beamline is optimized for industrial applications of the synchrotron light. X-rays with photon energies from 2.1 keV to 14.2 keV are delivered to the experimental station passing a fixed-exit double-crystal Si(111) monochromator and a bent cylindrical mirror. Basic experimental equipments for XAFS measurement, high resolution diffractometry, various kinds of X-ray imaging and energy-dispersive diffractometry have been prepared for the station. From our initial commissioning and performance testing of the beamline, we show that BL15 can perform XAFS measurements.

  7. 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}.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. An X-ray absorption study of synthesis- and As adsorption-induced microstructural modifications in Fe oxy-hydroxides.

    PubMed

    Pinakidou, F; Katsikini, M; Simeonidis, K; Paloura, E C; Mitrakas, M

    2015-11-15

    Synthetic adsorbents based on Fe oxy-hydroxides (FeOOH) prepared under a wide range of pH-values via intense oxidation conditions of FeSO4 as well as the As(III) and As(V) adsorption mechanism are investigated using X-ray absorption fine structure (XAFS) spectroscopies at the Fe- and As-K-edges. Synthesis in an alkaline environment promotes the face-connectivity of the Fe(O,OH)6 chains at the expense of edge- and corner-sharing linkage, which is consistent with the lower surface charge density and in turn with the lower arsenic adsorption capacity. Microstructural changes are also detected after As(V) adsorption onto FeOOH synthesized at pH 5.5: the ratio of face-/edge-sharing sites increases from approximately 0.4-0.7 as a function of the As(V)-loading. This modification of the polymeric Fe(O,OH)6 structure at higher As/Fe ratios is attributed to strong As(V) bidentate mononuclear ((2)E) and binuclear ((2)C) adsorption. In contrast, no alterations in the FeOOH microstructure were observed, possibly due to the weaker (2)E linkage of As(III). PMID:26057444

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. Development and tests of a new prototype detector for the XAFS beamline at Elettra Synchrotron in Trieste

    NASA Astrophysics Data System (ADS)

    Fabiani, S.; Ahangarianabhari, M.; Baldazzi, G.; Bellutti, P.; Bertuccio, G.; Bruschi, M.; Bufon, J.; Carrato, S.; Castoldi, A.; Cautero, G.; Ciano, S.; Cicuttin, A.; Crespo, M. L.; Dos Santos, M.; Gandola, M.; Giacomini, G.; Giuressi, D.; Guazzoni, C.; Menk, R. H.; Niemela, J.; Olivi, L.; Picciotto, A.; Piemonte, C.; Rashevskaya, I.; Rachevski, A.; Rignanese, L. P.; Sbrizzi, A.; Schillani, S.; Vacchi, A.; Villaverde Garcia, V.; Zampa, G.; Zampa, N.; Zorzi, N.

    2016-02-01

    The XAFS beamline at Elettra Synchrotron in Trieste combines X-ray absorption spectroscopy and X-ray diffraction to provide chemically specific structural information of materials. It operates in the energy range 2.4-27 keV by using a silicon double reflection Bragg monochromator. The fluorescence measurement is performed in place of the absorption spectroscopy when the sample transparency is too low for transmission measurements or the element to study is too diluted in the sample. We report on the development and on the preliminary tests of a new prototype detector based on Silicon Drift Detectors technology and the SIRIO ultra low noise front-end ASIC. The new system will be able to reduce drastically the time needed to perform fluorescence measurements, while keeping a short dead time and maintaining an adequate energy resolution to perform spectroscopy. The custom-made silicon sensor and the electronics are designed specifically for the beamline requirements.

  7. Expression and genetic analysis of XIAP-associated factor 1 (XAF1) in cancer cell lines.

    PubMed

    Fong, W G; Liston, P; Rajcan-Separovic, E; St Jean, M; Craig, C; Korneluk, R G

    2000-11-15

    X-linked inhibitor of apoptosis protein (XIAP) is a potent modulator of programmed cell death. XIAP specifically binds and inhibits the function of caspase-3, -7, and -9, key effector proteases of apoptosis. We recently isolated, by yeast two-hybrid screening, a novel 34-kDa zinc finger protein, XIAP-associated factor 1 (XAF1). Both the caspase inhibiting and the anti-apoptotic abilities of XIAP were found to be blocked by overexpressed XAF1. Here, we report the isolation and characterization of the human XAF1 gene. The xaf1 gene consists of seven exons spanning 18 kb. Fluorescence in situ hybridization analysis localized the xaf1 locus at 17p13.2, telomeric to the p53 gene. The xaf1 locus was further refined to YAC 746C10, approximately 3 cM distal to TP53. Microsatellite analysis of the xaf1 locus using the NCI 60 cell line panel revealed significantly decreased heterozygosity at all three polymorphic markers tested, suggesting that allelic loss of the xaf1 gene is prevalent in cancer cell lines. Examination of the same NCI cell line panel for xaf1 RNA expression demonstrated that cancer cell lines exhibited very low levels of mRNA relative to normal human liver. In contrast, XIAP mRNA levels were relatively high in the majority of cancer cell lines tested. We propose that a high level of XIAP to XAF1 expression in cancer cells may provide a survival advantage through the relative increase of XIAP anti-apoptotic function. PMID:11087668

  8. XAFS Study of As in K-T Boundary Clays

    NASA Astrophysics Data System (ADS)

    Sakai, Shunsuke; Yoshiasa, Akira; Arima, Hiroshi; Okube, Maki; Numako, Chiya; Sato, Tsutomu

    2007-02-01

    Local structure around arsenic atoms in K-T boundary clays was studied by As K-edge XAFS spectroscopy. The threshold E0 energy of As and the characterization of the white peak of XANES spectra agree well with the values of As(+5) minerals like Zn2(AsO4)2(OH)22H2O and CaCu(AsO4)(OH) according to the comparison with several types of arsenic minerals. This indicates that arsenic is in a high oxidation state As(+5) and occupies the AsO4 tetrahedral site of a mineral in K-T boundary clays.

  9. Chemical reactions of As complexation by glutathione: an XAFS study

    NASA Astrophysics Data System (ADS)

    Franco, M. W.; Vasconcelos, I. F.; Modolo, L. V.; Barbosa, F. A. R.

    2016-05-01

    In this study, the chemical reactions between As(III) and As(V) with glutathione, which is a target compound in As biochemistry due to its primordial role in As immobilization and intracellular reduction, in various molar ratios were investigated using As K-edge XAFS spectroscopy. Results showed a gradual substitution of As-O bonds in the coordination of aqueous As(III) and As(V) for three As-S bonds in the As+GSH complex. Moreover, the data showed reduction of As(V) to As(III) prior or concomitant to the As+GSH complex formation.

  10. Is It Homogeneous or Heterogeneous Catalysis Derived from [RhCp*Cl2]2? In Operando-XAFS, Kinetic and Crucial Kinetic Poisoning Evidence for Subnanometer Rh4 Cluster-Based Benzene Hydrogenation Catalysis

    SciTech Connect

    Bayram, Ercan; Linehan, John C.; Fulton, John L.; Roberts, John A.; Szymczak, Nathaniel; Smurthwaite, Tricia D.; Ozkar, Saim; Balasubramanian, Mahalingam; Finke, Richard G.

    2011-11-23

    Determining the true, kinetically dominant catalytically active species, in the classic benzene hydrogenation system pioneered by Maitlis and co-workers 34 years ago starting with [RhCp*Cl2]2 (Cp* = [{eta}5-C5(CH3)5]), has proven to be one of the most challenging case studies in the quest to distinguish single-metal-based 'homogeneous' from polymetallic, 'heterogeneous' catalysis. The reason, this study will show, is the previous failure to use the proper combination of (i) operando spectroscopy to determine the dominant form(s) of the precatalyst's mass under catalysis (i.e., operating) conditions, plus then and crucially also (ii) the previous lack of the necessary kinetic studies, catalysis being a 'wholly kinetic phenomenon' as J. Halpern long ago noted. An important contribution from this study will be to reveal the power of quantitiative kinetic poisoning experiments for distinguishing single-metal, or in this case subnanometer Rh4 cluster-based catalysis from larger, polymetallic Rh(0)n nanoparticle catalysis, at least under favorable conditions. The combined operando-XAFS (X-ray absorption fine structure) spectroscopy and kinetic evidences provide a compelling case for Rh4-based, with average stoichiometry 'Rh4Cp*2.4Cl4Hc', benzene hydrogenation catalysis in 2-propanol with added Et3N and at 100 C and 50 atm initial H2 pressure. The results also reveal, however, that if even ca. 1.4% of the total soluble Rh(0)n had formed nanoparticles, then those Rh(0)n nanoparticles would have been able to account for all the observed benzene hydrogenation catalytic rate (using commercial, ca. 2 nm, polyethyleneglycol-dodecylether hydrosol stabilized Rh(0)n nanoparticles as a model system). The results 'especially the poisoning methodology developed and employed' are of significant, broader interest since determining the nature of the true catalyst continues to be a central, often vexing issue in any and all catalytic reactions. The results are also of fundamental

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Monitoring the role of Mn and Fe in the As-removal efficiency of tetravalent manganese feroxyhyte nanoparticles from drinking water: An X-ray absorption spectroscopy study.

    PubMed

    Pinakidou, F; Katsikini, M; Paloura, E C; Simeonidis, K; Mitraka, E; Mitrakas, M

    2016-09-01

    The implementation of amorphous tetravalent manganese feroxyhyte (TMFx) nanoparticles, prepared via co-precipitation synthesis, as an efficient As(V)-removal material is investigated using X-ray absorption fine structure (XAFS) spectroscopy at the Fe-, Mn- and As-K-edges. The optimum synthesis conditions and chemical composition of the TMFx adsorbent were determined by the degree of polymerization in the adsorbents' microstructure. Under synthesis into mildly acidic conditions, the change in the polymerization of the metal-oxyhydroxyl chains (metal=Fe, Mn) provides more adsorption sites at edges and corner sites in the bonding environment of Fe and Mn, respectively, thereby enhancing As uptake. After exposure to As-polluted water, similar microstructural changes related to As-bidentate and monodentate geometries are generated: As(V) preferentially occupies the high energy adsorption sites ((2)C complexes) available in the Mn-oxyhydroxyl groups and the low energy edge sites offered by Fe ((2)E complexes). It is revealed that optimum arsenic-removal by TMFx occurs into mildly acidic synthesis pH and for iron to manganese molar ratio equal to 3. PMID:27254257

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Assessing the feasibility of low temperature XAFS experiments at Indus-2, India: First results

    NASA Astrophysics Data System (ADS)

    Ramanan, Nitya; Rajput, Parasmani; Jha, S. N.; Lahiri, Debdutta

    2015-05-01

    In this work, we report installation of displex cryostat XAFS sample holder at XAFS beamline (BL-09) of Indus-2 synchrotron facility, India and make critical assessment of feasibility of low-temperature XAFS experiments in terms of data quality and reproducibility, temperature range, calibration and attainable resolution. We adopted the Debye Model-based calibration method by measuring XAFS of standard Au foil with known Debye temperature (ΘDebye)Autheory = 165 K. The data is of good quality and reproducible with international data. By fitting Debye Waller Factor (σexpt2 (T)), we deduced (ΘDebye)Auexpt = 163 K which implies calibration within 2 K. Error bars for σexpt2 (T) correspond to temperature uncertainty ΔT ≤ 5 K, which defines the temperature resolution for low temperature XAFS experiments. Thus, from both calibration and resolution points-of-view, this work demonstrates the feasibility of low temperature XAFS experiments at BL-09, Indus-2. Feasibility of extending XAFS experiments to lower temperature and unknown samples is discussed.

  11. Epigenetic silencing of the XAF1 gene is mediated by the loss of CTCF binding

    PubMed Central

    Victoria-Acosta, Georgina; Vazquez-Santillan, Karla; Jimenez-Hernandez, Luis; Muñoz-Galindo, Laura; Maldonado, Vilma; Martinez-Ruiz, Gustavo Ulises; Melendez-Zajgla, Jorge

    2015-01-01

    XAF1 is a tumour suppressor gene that compromises cell viability by modulating different cellular events such as mitosis, cell cycle progression and apoptosis. In cancer, the XAF1 gene is commonly silenced by CpG-dinucleotide hypermethylation of its promoter. DNA demethylating agents induce transcriptional reactivation of XAF1, sensitizing cancer cells to therapy. The molecular mechanisms that mediate promoter CpG methylation have not been previously studied. Here, we demonstrate that CTCF interacts with the XAF1 promoter in vivo in a methylation-sensitive manner. By transgene assays, we demonstrate that CTCF mediates the open-chromatin configuration of the XAF1 promoter, inhibiting both CpG-dinucleotide methylation and repressive histone posttranslational modifications. In addition, the absence of CTCF in the XAF1 promoter inhibits transcriptional activation induced by well-known apoptosis activators. We report for the first time that epigenetic silencing of the XAF1 gene is a consequence of the loss of CTCF binding. PMID:26443201

  12. 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.

  13. Reexamining X-mode suppression and fine structure in artificial E region field-aligned plasma density irregularities

    NASA Astrophysics Data System (ADS)

    Miceli, R. J.; Hysell, D. L.; Munk, J.; McCarrick, M.; Huba, J. D.

    2013-09-01

    Artificial field-aligned plasma density irregularities (FAIs) were generated in the E region of the ionosphere above the High Frequency Active Auroral Research Program facility during campaigns in May and August of 2012 and observed using a 30 MHz coherent scatter radar imager in Homer, Alaska. The purpose of this ionospheric modification experiment was to measure the threshold pump power required to excite thermal parametric instabilities by O-mode heating and to investigate the suppression of the FAIs by simultaneous X-mode heating. We find that the threshold pump power for irregularity excitation was consistent with theoretical predictions and increased by approximately a factor of 2 when X-mode heating was present. A modified version of the Another Model of the Ionosphere (SAMI2) ionospheric model was used to simulate the threshold experiments and suggested that the increase was entirely due to enhanced D region absorption associated with X-mode heating. Additionally, a remarkable degree of fine structure possibly caused by natural gradient drift instability in the heater-modified volume was observed in experiments performed during geomagnetically active conditions.

  14. Accurate modeling of spectral fine-structure in Earth radiance spectra measured with the Global Ozone Monitoring Experiment.

    PubMed

    van Deelen, Rutger; Hasekamp, Otto P; Landgraf, Jochen

    2007-01-10

    We present what we believe to be a novel approach to simulating the spectral fine structure (<1 nm) in measurements of spectrometers such as the Global Ozone Monitoring Experiment (GOME). GOME measures the Earth's radiance spectra and daily solar irradiance spectra from which a reflectivity spectrum is commonly extracted. The high-frequency structures contained in such a spectrum are, apart from atmospheric absorption, caused by Raman scattering and by a shift between the solar irradiance and the Earth's radiance spectrum. Normally, an a priori high-resolution solar spectrum is used to simulate these structures. We present an alternative method in which all the required information on the solar spectrum is retrieved from the GOME measurements. We investigate two approaches for the spectral range of 390-400 nm. First, a solar spectrum is reconstructed on a fine spectral grid from the GOME solar measurement. This approach leads to undersampling errors of up to 0.5% in the modeling of the Earth's radiance spectra. Second, a combination of the solar measurement and one of the Earth's radiance measurement is used to retrieve a solar spectrum. This approach effectively removes the undersampling error and results in residuals close to the GOME measurement noise of 0.1%. PMID:17268571

  15. FEFF5: An ab initio multiple scattering XAFS code. [In FORTRAN 77

    SciTech Connect

    Rehr, J.J.; Zabinsky, S.I.

    1992-01-01

    FEFF5 is an efficient automated code which calculates multiple scattering (MS) curved wave XAFS spectra for molecules and solids. The theoretical ingredients and approximations contained in the code are revised, with the aim of describing the how XAFS spectra are efficiently simulated. The FEFF5 code consists of 4 independent modules: a scattering potential and phase shift module, a path finder module, a scattering amplitude module and an XAFS module. Multiple scattering Debye-Waller factors are built in using a correlated Debye model.

  16. Understanding the role of structural disorder on spin polarization in CeMnNi4 using XAFS

    SciTech Connect

    Lahiri, D.; Khalid, S.; Modak, P.; Raychaudhuri, P.; Dhar, S.K.; Sharma, S.M.

    2010-02-03

    The role of disorder on ferromagnetism has generally been detrimental. We show how Mn-Ni antisite disorder enhances polarization in CeMnNi{sub 4}. The disorder is determined to be 6% by x-ray absorption fine structure. The electronic structure of pure CeMnNi{sub 4} is pseudo-half-metallic. Site exchange alters the near neighbor bond parameters and modifies the density of states favorably, increasing the polarization (obtained by first-principles calculations) from 13 to 47% (experimental {approx}66%).

  17. An XAFS Study of Niobium chloride in the ionic liquid 1-ethyl-3-methyl imidazolium chloride/ aluminum chloride

    SciTech Connect

    D Roeper; K Pandya; G Cheek; W OGrady

    2011-12-31

    Niobium chloride was studied with extended X-ray absorption fine structure spectroscopy (EXAFS) in acidic and basic aluminum chloride/1-ethyl-3-methyl imidazolium chloride (EMIC) ionic liquids. Although anhydrous Nb2Cl10 is more soluble in the basic melt than in the acidic melt, the EXAFS data shows that the coordination shell around the niobium does not change in the different ionic liquids. Both the acidic and basic melts show a coordination of five chlorides in the first shell. This indicates that in this series of ionic liquids, the Nb2Cl10 breaks up into two NbCl5 entities in both the acidic and the basic melts.

  18. The Effect of Quantum-Mechanical Interference on Precise Measurements of the n = 2 Triplet P Fine Structure of Helium

    SciTech Connect

    Marsman, A.; Horbatsch, M.; Hessels, E. A.

    2015-09-15

    For many decades, improvements in both theory and experiment of the fine structure of the n = 2 triplet P levels of helium have allowed for an increasingly precise determination of the fine-structure constant. Recently, it has been observed that quantum-mechanical interference between neighboring resonances can cause significant shifts, even if such neighboring resonances are separated by thousands of natural widths. The shifts depend in detail on the experimental method used for the measurement, as well as the specific experimental parameters employed. Here, we review how these shifts apply for the most precise measurements of the helium 2{sup 3}P fine-structure intervals.

  19. XAFS study of Ce valence in the Ce 1- xY xFe 2 system

    NASA Astrophysics Data System (ADS)

    Garg, K. B.; Khaled, M.; Venkatesh, S.; Studer, F.; Duc, N. H.; Srivastava, P.

    1995-02-01

    Pseudo binary alloys like R(A 1- xB x) 2 compounds are known to exhibit both negative and positive types of deviation from Vegard's law on substitution of 3d or 4f cations. CeNi 2 based alloys are known to be mixed valence compounds whereas CeFe 2 alloys are probably not. In this study we examine the influence of substitution of rare earth compounds rather than the 3d ions. Ce L III absorption edge XAFS is measured in the single phase Ce 1- xY xFe 2 system ( x = 0.0, 0.1, 0.2, 0.3 and 0.7) using the super ACO synchrotron radiation facility at LURE. The spectra are discussed in terms of the change in the Ce valence as a result of progressive substitution by trivalent Y cation. The problem of Ce valence saturation is also addressed in this work.

  20. The oxidation state and microstructural environment of transition metals (V, Co, and Ni) in magnetite: an XAFS study

    NASA Astrophysics Data System (ADS)

    Liang, Xiaoliang; He, Zisen; Tan, Wei; Liu, Peng; Zhu, Jianxi; Zhang, Jing; He, Hongping

    2015-05-01

    Transition metal-substituted magnetite minerals have attracted increasing attention for their wide application in industry and environmental protection. In this study, the valence and atomic environment of some substituting metals in magnetites (Fe3- x M x O4, M = V, Co, and Ni) were investigated using X-ray absorption fine structure spectroscopy. The results deduced from X-ray absorption near-edge structure spectroscopy indicated that the valences of V, Co, and Ni in Fe3- x M x O4 were +3, +2, and +2, respectively. The valences did not change as the substitution extent increased. Extended X-ray absorption fine structure spectroscopy suggested that the substituting cations occupied octahedral sites in the magnetite structure. The M-O and M-M/Fe distances were consistent with the Feoct-O and Feoct-Fe distances, respectively, in the magnetite (Fe3O4) structure. The occupancy of the substituting cations was assessed by crystal-field theory. We also considered the relationship between the chemical environment of substituting cations and their effects on the physicochemical properties of magnetite, including thermal stability, surface properties, and catalytic reactivity.

  1. XAFS Study on Deterioration of Cathode Materials for Lithium-Ion Batteries

    SciTech Connect

    Nonaka, Takamasa; Okuda, Chikaaki; Kondo, Yasuhito; Seno, Yoshiki; Ukyo, Yoshio

    2007-02-02

    LiNi0.8CO0.15Al0.05O2, being one of the promising cathode materials for lithium-ion batteries, shows a distinct capacity fading after charge/discharge cycling and/or storage at high temperatures. The origin of these deteriorations has been explored by investigating the electronic and structural changes of the cathode material using X-ray absorption spectroscopy. Ni K-edge XAFS measurements were performed in two different modes: surface-sensitive conversion electron yield (CEY) mode and bulk-sensitive transmission mode. The Ni K-edge XANES showed that, after the cycle and aging tests, the Ni valences at the near-surface of the cathode particles became much lower than those in bulk. Whereas, the EXAFS showed that the bulk and surface-averaged Ni-O bond distances remained unchanged after the tests. These electronic and structural changes which occur prominently at near-surface are probably the main cause of the battery deterioration phenomenon.

  2. High Throughput In Situ XAFS Screening of Catalysts

    SciTech Connect

    Tsapatsaris, Nikolaos; Beesley, Angela M.; Weiher, Norbert; Tatton, Helen; Schroeder, Sven L. M.; Dent, Andy J.; Mosselmans, Frederick J. W.; Tromp, Moniek; Russu, Sergio; Evans, John; Harvey, Ian; Hayama, Shu

    2007-02-02

    We outline and demonstrate the feasibility of high-throughput (HT) in situ XAFS for synchrotron radiation studies. An XAS data acquisition and control system for the analysis of dynamic materials libraries under control of temperature and gaseous environments has been developed. The system is compatible with the 96-well industry standard and coupled to multi-stream quadrupole mass spectrometry (QMS) analysis of reactor effluents. An automated analytical workflow generates data quickly compared to traditional individual spectrum acquisition and analyses them in quasi-real time using an HT data analysis tool based on IFFEFIT. The system was used for the automated characterization of a library of 91 catalyst precursors containing ternary combinations of Cu, Pt, and Au on {gamma}-Al2O3, and for the in situ characterization of Au catalysts supported on Al2O3 and TiO2.

  3. High Throughput In Situ XAFS Screening of Catalysts

    NASA Astrophysics Data System (ADS)

    Tsapatsaris, Nikolaos; Beesley, Angela M.; Weiher, Norbert; Tatton, Helen; Dent, Andy J.; Mosselmans, Frederick J. W.; Tromp, Moniek; Russu, Sergio; Evans, John; Harvey, Ian; Hayama, Shu; Schroeder, Sven L. M.

    2007-02-01

    We outline and demonstrate the feasibility of high-throughput (HT) in situ XAFS for synchrotron radiation studies. An XAS data acquisition and control system for the analysis of dynamic materials libraries under control of temperature and gaseous environments has been developed. The system is compatible with the 96-well industry standard and coupled to multi-stream quadrupole mass spectrometry (QMS) analysis of reactor effluents. An automated analytical workflow generates data quickly compared to traditional individual spectrum acquisition and analyses them in quasi-real time using an HT data analysis tool based on IFFEFIT. The system was used for the automated characterization of a library of 91 catalyst precursors containing ternary combinations of Cu, Pt, and Au on γ-Al2O3, and for the in situ characterization of Au catalysts supported on Al2O3 and TiO2.

  4. Global investigation of the fine structure of the isoscalar giant quadrupole resonance

    SciTech Connect

    Shevchenko, A.; Burda, O.; Kalmykov, Y.; Neumann-Cosel, P. von; Ponomarev, V. Yu.; Richter, A.; Wambach, J.; Carter, J.; Sideras-Haddad, E.; Cooper, G. R. J.; Fearick, R. W.; Foertsch, S. V.; Lawrie, J. J.; Neveling, R.; Smit, F. D.; Fujita, H.; Fujita, Y.; Lacroix, D.

    2009-04-15

    Fine structure in the region of the isoscalar giant quadrupole resonance (ISGQR) in {sup 58}Ni, {sup 89}Y, {sup 90}Zr, {sup 120}Sn, {sup 166}Er, and {sup 208}Pb has been observed in high-energy-resolution ({delta}E{sub 1/2}{approx_equal}35-50 keV) inelastic proton scattering measurements at E{sub 0}=200 MeV at iThemba LABS. Calculations of the corresponding quadrupole excitation strength functions performed within models based on the random-phase approximation (RPA) reveal similar fine structure when the mixing of one-particle one-hole states with two-particle two-hole states is taken into account. A detailed comparison of the experimental data is made with results from the quasiparticle-phonon model (QPM) and the extended time-dependent Hartree-Fock (ETDHF) method. For {sup 208}Pb, additional theoretical results from second RPA and the extended theory of finite Fermi systems (ETFFS) are discussed. A continuous wavelet analysis of the experimental and the calculated spectra is used to extract dominant scales characterizing the fine structure. Although the calculations agree with qualitative features of these scales, considerable differences are found between the model and experimental results and amongst different models. Within the framework of the QPM and ETDHF calculations it is possible to decompose the model spaces into subspaces approximately corresponding to different damping mechanisms. It is demonstrated that characteristic scales mainly arise from the collective coupling of the ISGQR to low-energy surface vibrations.

  5. Fine Structure in the Mm-Wavelength Spectra of the Active Region

    NASA Astrophysics Data System (ADS)

    Sawant, H. S.; Cecatto, J. R.

    1990-11-01

    RESUMEN. Faltan observaciones solares espectrosc6picas en la longitud de onda milimetrica. Hay sugerencias de que se puede superponer una fi na estructura en frecuencia a la componente-S de la regi6n solar activa, asi como a la componente del brote en las longitudes de onda milimetri- cas. Se ha desarrollado un receptor de alta sensibilidad de pasos de frecuencia que opera en el intervalo de 23-18 GHz con una resoluci6n de 1 GHz y resoluci6n de tiempo variable entre 1.2 y 96 sec, usando la an- tena de Itapetinga de 13.7-m para estudiar la estructura fina en frecuencia y tiempo. Discutimos el espectro en longitud de onda-mm en re- giones activas y su evoluci6n en el tiempo. El estudio de Ia evoluci6n en el tiempo de la regi6n activa en AR 5569 observada el 29 de junio de 1989, sugiere la existencia de estructuras finas como funci6n deltiempo. ABSTRACT. There is a lack of mm-wavelength spectroscopic solar observations. There are suggestions that a fine structure in frequency may be superimposed on the S-component of solar active region as well as on the burst component at inm-wavelengths. To study fine structure in frequency and time, a high sensitivity step frequency receiver operating in the frequency range 23-18 GHz with frequency resolution of 1 GHz and variable time resolution 1.2 to 96 sec, using 13.7 m diameter Itapetinga radome covered antenna, has been developed. Here, we discuss mm-wavelength spectra of active regions and their time evolution. Study of time evolution of an active region AR 5569 observed on 29th June, 1989 suggests existence of fine structures as a function of time. ( Ck : SUN-ACTIVITY - SUN-RADIO RADIATION

  6. Using XAFS, EDAX and AFM in comparative study of various natural and synthetic emeralds

    NASA Astrophysics Data System (ADS)

    Parikh, P.; Saini, N. L.; Dalela, S.; Bhardwaj, D. M.; Fernandes, S.; Gupta, R. P.; Garg, K. B.

    2003-01-01

    We have performed XAFS, EDAX and AFM studies on some natural and synthetic emeralds. While the XAFS results yield information on changes in the valence of the Cr ion and the n-n distance the AFM is used to determine the areal atomic density on surface of the crystals. It is a pilot study to explore if the three techniques can offer a possible way of distinguishing between the natural and synthetic emeralds and the results are promising.

  7. Fine Structure in Swift Heavy Ion Tracks in Amorphous SiO2

    NASA Astrophysics Data System (ADS)

    Kluth, P.; Schnohr, C. S.; Pakarinen, O. H.; Djurabekova, F.; Sprouster, D. J.; Giulian, R.; Ridgway, M. C.; Byrne, A. P.; Trautmann, C.; Cookson, D. J.; Nordlund, K.; Toulemonde, M.

    2008-10-01

    We report on the observation of a fine structure in ion tracks in amorphous SiO2 using small angle x-ray scattering measurements. Tracks were generated by high energy ion irradiation with Au and Xe between 27 MeV and 1.43 GeV. In agreement with molecular dynamics simulations, the tracks consist of a core characterized by a significant density deficit compared to unirradiated material, surrounded by a high density shell. The structure is consistent with a frozen-in pressure wave originating from the center of the ion track as a result of a thermal spike.

  8. Enhanced Laboratory Sensitivity to Variation of the Fine-Structure Constant using Highly Charged Ions

    SciTech Connect

    Berengut, J. C.; Dzuba, V. A.; Flambaum, V. V.

    2010-09-17

    We study atomic systems that are in the frequency range of optical atomic clocks and have enhanced sensitivity to potential time variation of the fine-structure constant {alpha}. The high sensitivity is due to coherent contributions from three factors: high nuclear charge Z, high ionization degree, and significant differences in the configuration composition of the states involved. Configuration crossing keeps the frequencies in the optical range despite the large ionization energies. We discuss a few promising examples that have the largest {alpha} sensitivities seen in atomic systems.

  9. Extended fine structures in the electron energy loss spectrum of InAs

    NASA Technical Reports Server (NTRS)

    Schowengerdt, F. D.; Grunthaner, F. J.

    1988-01-01

    The possibility of using electron energy loss fine structure (EELFS) for the characterization of thin pseudomorphic quantum wells of InAs and GaAs(100) is investigated. It is shown that the EELFS technique can yield reliable radial distribution functions for bulk InAs, provided beam-induced sample degradation is controlled stringently. Additional improvements in the data collection procedures, including better control of the sample condition, are required as well as more detailed work on separating contributions from multiple edges in the data analysis.

  10. Time evolution of the fine structure constant in a two-field quintessence model

    SciTech Connect

    Bento, M.C.; Bertolami, O.; Santos, N.M.C.

    2004-11-15

    We examine the variation of the fine structure constant in the context of a two-field quintessence model. We find that, for solutions that lead to a transient late period of accelerated expansion, it is possible to fit the data arising from quasar spectra and comply with the bounds on the variation of {alpha} from the Oklo reactor, meteorite analysis, atomic clock measurements, cosmic microwave background radiation, and big bang nucleosynthesis. That is more difficult if we consider solutions corresponding to a late period of permanent accelerated expansion.

  11. On the fine-structure constant in a plasma model of the fluctuating vacuum substratum

    NASA Technical Reports Server (NTRS)

    Cragin, B. L.

    1986-01-01

    The existence of an intimate connection between the quivering motion of electrons and positrons (Zitterbewegung), predicted by the Dirac equation, and the zero-point fluctuations of the vacuum is suggested. The nature of the proposed connection is discussed quantitatively, and an approximate self-consistency relation is derived, supplying a purely mathematical expression that relates the dimensionless coupling strengths (fine-structure constants) alpha sub e and alpha sub g of electromagnetism and gravity. These considerations provide a tentative explanation for the heretofore puzzling number 1/alpha sub e of about 137.036 and suggest that attempts to unify gravity with the electroweak and strong interactions will ultimately prove successful.

  12. Coupled-channels study of fine structure in the {alpha} decay of well deformed nuclei

    SciTech Connect

    Ni Dongdong; Ren Zhongzhou

    2011-06-15

    We formulate a theoretical model for the {alpha} decay of well-deformed even-even nuclei based on the coupled-channel Schroedinger equation. The {alpha}-decay half-lives and fine structures observed in {alpha} decay are well described by the five-channel microscopic calculations. Since the branching ratios to high-spin states are hard to understand in the traditional {alpha}-decay theories, this success could be important to interpret future observations of heavier nuclei. It is also found that the {alpha} transition to high-spin states is a powerful tool to probe the energy spectrum and deformation of daughter nuclei.

  13. Balmer profiles in the geocorona and interstellar space. I - Asymmetries due to fine structure

    NASA Technical Reports Server (NTRS)

    Chamberlain, Joseph W.

    1987-01-01

    While the Doppler profiles of Balmer-alpha and -beta are in principle analyzable in order to derive orbital data concerning both escaping and satellite geocoronal particles, interpretations are in practice hampered by a lack of understanding of profile properties apart from such geocoronal features as an asymmetry, caused by the absence of escape velocity-exceeding, downward-directed particles. Attention is accordingly given to the profiles of H atoms which, while emitting radiation from a complete Maxwellian distribution, also exhibit an H-alpha fine structure-generated asymmetry which is a predictable function of the excitation mechanism.

  14. Fine structure of 25 extragalactic radio sources. [interferometric observations of quasars

    NASA Technical Reports Server (NTRS)

    Wittels, J. J.; Knight, C. A.; Shapiro, I. I.; Hinteregger, H. F.; Rogers, A. E. E.; Whitney, A. R.; Clark, T. A.; Hutton, L. K.; Marandino, G. E.; Niell, A. E.

    1975-01-01

    Interferometric observations taken at 7.8 GHz (gamma approximately = 3.8 cm) with five pairings of antennae of 25 extragalactic radio sources between April, 1972 and May, 1973 are reported. These sources exhibit a broad variety of fine structure from very simple to complex. The total flux and the correlated flux of some of the sources underwent large changes in a few weeks, while the structure and total power of others remained constant during the entire period of observation. Some aspects of the data processing and a discussion of errors are presented. Numerous figures are provided and explained. The individual radio sources are described in detail.

  15. Fine structure of transient waves in a random medium: The correlation and spectral density functions

    NASA Technical Reports Server (NTRS)

    Wenzel, Alan R.

    1994-01-01

    This is essentially a progress report on a theoretical investigation of the propagation of transient waves in a random medium. The emphasis in this study is on applications to sonic-boom propagation, particularly as regards the effect of atmospheric turbulence on the sonic-boom waveform. The analysis is general, however, and is applicable to other types of waves besides sonic-boom waves. The phenomenon of primary concern in this investigation is the fine structure of the wave. A figure is used to illustrate what is meant by finestructure.

  16. Experimental determination of the relativistic fine-structure splitting in pionic Ti and Fe atoms

    SciTech Connect

    Wang, K.; Boehm, F.; Bovet, E.; Hahn, A.A.; Henrikson, H.E.; Miller, J.P.; Powers, R.J.; Vogel, P.; Vuilleumier, J.; Kunselman, A.R.

    1980-09-01

    Using a high-resolution crystal spectrometer we have measured the relativistic angular-momentum splittings of the 5g-4f and 5f-4d transitions in pionic Ti and Fe atoms. The observed fine-structure splittings of 85.3 +- 3.0 eV in ..pi../sup -/ Ti and 158.5 +- 7.8 eV in ..pi../sup -/ Fe agree with the calculated splittings of 88.5 and 167.6 eV, respectively, arising from the Klein-Gordon equation and from small corrections due to vacuum polarization, strong interaction, and electron screening.

  17. Simple surface structure determination from Fourier transforms of angle-resolved photoemission extended fine structure

    SciTech Connect

    Zheng, Y. |; Shirley, D.A.

    1995-02-01

    The authors show by Fourier analyses of experimental data, with no further treatment, that the positions of all the strong peaks in Fourier transforms of angle-resolved photoemission extended fine structure (ARPEFS) from adsorbed surfaces can be explicitly predicted from a trial structure with an accuracy of about {+-} 0.3 {angstrom} based on a single-scattering cluster model together with the concept of a strong backscattering cone, and without any additional analysis. This characteristic of ARPEFS Fourier transforms can be developed as a simple method for determining the structures of adsorbed surfaces to an accuracy of about {+-} 0.1 {angstrom}.

  18. Fine-structure splittings in high-lying {sup 2}F states of rubidium via three-step laser spectroscopy

    SciTech Connect

    Brandenberger, J. R.; Malyshev, G. S.

    2010-03-15

    Three-step laser spectroscopy has been used to measure six additional fine-structure splittings in the n {sup 2}F states of {sup 87}Rb for 11{<=}n{<=}16. When combined with our previous measurements for 4{<=}n{<=}10, they constitute a continuous sequence of 13 measurements suitable for comparison to fine-structure calculations in heavy alkali-metal atoms where relativistic effects, core polarization, configuration mixing, and electron correlation are important.

  19. 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.

  20. Accurate Electron Affinity of Iron and Fine Structures of Negative Iron ions

    PubMed Central

    Chen, Xiaolin; Luo, Zhihong; Li, Jiaming; Ning, Chuangang

    2016-01-01

    Ionization potential (IP) is defined as the amount of energy required to remove the most loosely bound electron of an atom, while electron affinity (EA) is defined as the amount of energy released when an electron is attached to a neutral atom. Both IP and EA are critical for understanding chemical properties of an element. In contrast to accurate IPs and structures of neutral atoms, EAs and structures of negative ions are relatively unexplored, especially for the transition metal anions. Here, we report the accurate EA value of Fe and fine structures of Fe− using the slow electron velocity imaging method. These measurements yield a very accurate EA value of Fe, 1235.93(28) cm−1 or 153.236(34) meV. The fine structures of Fe− were also successfully resolved. The present work provides a reliable benchmark for theoretical calculations, and also paves the way for improving the EA measurements of other transition metal atoms to the sub cm−1 accuracy. PMID:27138292

  1. On the mechanisms involved in the recovery of envelope information from temporal fine structure

    PubMed Central

    Apoux, Frédéric; Millman, Rebecca E.; Viemeister, Neal F.; Brown, Christopher A.; Bacon, Sid P.

    2011-01-01

    Three experiments were designed to provide psychophysical evidence for the existence of envelope information in the temporal fine structure (TFS) of stimuli that were originally amplitude modulated (AM). The original stimuli typically consisted of the sum of a sinusoidally AM tone and two unmodulated tones so that the envelope and TFS could be determined a priori. Experiment 1 showed that normal-hearing listeners not only perceive AM when presented with the Hilbert fine structure alone but AM detection thresholds are lower than those observed when presenting the original stimuli. Based on our analysis, envelope recovery resulted from the failure of the decomposition process to remove the spectral components related to the original envelope from the TFS and the introduction of spectral components related to the original envelope, suggesting that frequency- to amplitude-modulation conversion is not necessary to recover envelope information from TFS. Experiment 2 suggested that these spectral components interact in such a way that envelope fluctuations are minimized in the broadband TFS. Experiment 3 demonstrated that the modulation depth at the original carrier frequency is only slightly reduced compared to the depth of the original modulator. It also indicated that envelope recovery is not specific to the Hilbert decomposition. PMID:21786897

  2. Perceptual weighting of individual and concurrent cues for sentence intelligibility: Frequency, envelope, and fine structure

    PubMed Central

    Fogerty, Daniel

    2011-01-01

    The speech signal may be divided into frequency bands, each containing temporal properties of the envelope and fine structure. For maximal speech understanding, listeners must allocate their perceptual resources to the most informative acoustic properties. Understanding this perceptual weighting is essential for the design of assistive listening devices that need to preserve these important speech cues. This study measured the perceptual weighting of young normal-hearing listeners for the envelope and fine structure in each of three frequency bands for sentence materials. Perceptual weights were obtained under two listening contexts: (1) when each acoustic property was presented individually and (2) when multiple acoustic properties were available concurrently. The processing method was designed to vary the availability of each acoustic property independently by adding noise at different levels. Perceptual weights were determined by correlating a listener’s performance with the availability of each acoustic property on a trial-by-trial basis. Results demonstrated that weights were (1) equal when acoustic properties were presented individually and (2) biased toward envelope and mid-frequency information when multiple properties were available. Results suggest a complex interaction between the available acoustic properties and the listening context in determining how best to allocate perceptual resources when listening to speech in noise. PMID:21361454

  3. The variation of the fine-structure constant from disformal couplings

    NASA Astrophysics Data System (ADS)

    van de Bruck, Carsten; Mifsud, Jurgen; Nunes, Nelson J.

    2015-12-01

    We study a theory in which the electromagnetic field is disformally coupled to a scalar field, in addition to a usual non-minimal electromagnetic coupling. We show that disformal couplings modify the expression for the fine-structure constant, α. As a result, the theory we consider can explain the non-zero reported variation in the evolution of α by purely considering disformal couplings. We also find that if matter and photons are coupled in the same way to the scalar field, disformal couplings itself do not lead to a variation of the fine-structure constant. A number of scenarios are discussed consistent with the current astrophysical, geochemical, laboratory and the cosmic microwave background radiation constraints on the cosmological evolution of α. The models presented are also consistent with the current type Ia supernovae constraints on the effective dark energy equation of state. We find that the Oklo bound in particular puts strong constraints on the model parameters. From our numerical results, we find that the introduction of a non-minimal electromagnetic coupling enhances the cosmological variation in α. Better constrained data is expected to be reported by ALMA and with the forthcoming generation of high-resolution ultra-stable spectrographs such as PEPSI, ESPRESSO, and ELT-HIRES. Furthermore, an expected increase in the sensitivity of molecular and nuclear clocks will put a more stringent constraint on the theory.

  4. Fine structure of epithelial canal cells in petioles of Xanthium pensylvanicum

    SciTech Connect

    Maksymowych, R.; Ledbetter, M.C. Brookhaven National Lab., Upton, NY )

    1987-01-01

    Secretory canals were examined in petioles of Xanthium pensylvanicum (Cocklebur) grown under long day illumination to maintain vegetative growth. The fine structure of the canal and its epithelium was studied by electron microscopy of thin section cut transverse to the principal axis of petioles from leaves in an early stage of development. The canal proper is delimited by walls of epithelial cells which protrude into a scallop shaped cavity. In comparison to the surrounding parenchyma, the epithelial cells are smaller, cytoplasmically more dense, and less vacuolate. The epithelium contains pleomorphic starch-free plastids with planar thylakoids frequently stacked into grana; thus, the plastids are presumed photosynthetically active. Mitochondria are abundant and often dense. The cytoplasm is rich in free polysomes, and smooth endoplasmic reticulum predominates over the rough form. Spheroidal granules averaging about 530 nm in diameter are numerous in the epithelium and appear at lower concentration in neighboring cells. Many features of fine structure of the epithelial cells suggest that a high metabolic activity in present in this tissue during this early stage of development. A possible function of the canals is defense against insect predation and animal grazing.

  5. Accurate Electron Affinity of Iron and Fine Structures of Negative Iron ions.

    PubMed

    Chen, Xiaolin; Luo, Zhihong; Li, Jiaming; Ning, Chuangang

    2016-01-01

    Ionization potential (IP) is defined as the amount of energy required to remove the most loosely bound electron of an atom, while electron affinity (EA) is defined as the amount of energy released when an electron is attached to a neutral atom. Both IP and EA are critical for understanding chemical properties of an element. In contrast to accurate IPs and structures of neutral atoms, EAs and structures of negative ions are relatively unexplored, especially for the transition metal anions. Here, we report the accurate EA value of Fe and fine structures of Fe(-) using the slow electron velocity imaging method. These measurements yield a very accurate EA value of Fe, 1235.93(28) cm(-1) or 153.236(34) meV. The fine structures of Fe(-) were also successfully resolved. The present work provides a reliable benchmark for theoretical calculations, and also paves the way for improving the EA measurements of other transition metal atoms to the sub cm(-1) accuracy. PMID:27138292

  6. Coronal fine structure as seen in the Skylab white light coronagraph

    NASA Technical Reports Server (NTRS)

    Poland, Arthur I.

    1994-01-01

    The white light coronograph (WLC) on Skylab provided an opportunity to study the corona at high spatial and temporal resolution. The spatial resolution of the instrument was approximately 25 cm with images taken approximately one per min. One set of images taken over a 10 min period was digitized, providing ten high spatial resolution images for analysis. The progress in data processing techniques available at the time was not sufficient to permit a reliable study of the fine structure in these images. Using current techniques an investigation of the sizes and lifetimes of the smallest scale features in the data was carried out. A preliminary analysis of an area between 2 and 3 Ro was completed. The results show that very narrow rays extend from at least 2 to 3 Ro. The narrowest of these rays has a thickness of approximately 75 cm. The contrast is so low that they are very close to the noise limit of the data. Most of the rays observed become unrecognizable after 10 min, although some remain visible over the entire time. Some notion seems to be detectable in the fine structure rays, but analysis of more frames will be needed to quantify these results.

  7. Fine structure of uterus and non-functioning paruterine organ in Orthoskrjabinia junlanae (Cestoda, Cyclophyllidea).

    PubMed

    Korneva, Janetta V; Kornienko, Svetlana A; Jones, Malcolm K

    2016-06-01

    Some cyclophyllidean cestodes provide protection for their eggs in the external environment by providing them with additional protective layers around the egg membranes. In attempting to examine such adaptations, the microanatomy and fine structure of the uterus of pregravid and gravid proglottids of the cyclophyllidean cestode Orthoskrjabinia junlanae, a parasite of mammals that inhabit a terrestrial but moist environment, were studied. In the initial stages of uterine development, developing embryos locate freely in the lumen of a saccate uterus that later partitions into chambers. Each chamber that forms encloses several embryos. The chambers are surrounded by muscle cells that synthesize extracellular matrix actively. The paruterine organs consist of stacks of flattened long outgrowths of muscular cells, interspersed with small lipid droplets. In the gravid proglottids, the size of paruterine organ increases and consists of flattened basal and small rounded apical parts separated by constrictions. The fine structure of the organ wall remains the same: sparse nuclei and stacks of flattened cytoplasmic outgrowths but internal invaginations or lumen in the paruterine organ are absent. Completely developed eggs remain localized in the uterus. Based on the comparative morpho-functional analysis of uterine and paruterine organs and uterine capsules in cestodes, we conclude that these non-functioning paruterine organ in O. junlanae is an example of an atavism. We postulate that the life cycle of the parasite, which infects mammals living in wet habitats, where threats of desiccation of parasite ova is reduced, has favoured a reversion to a more ancestral form of uterine development. PMID:26997340

  8. Ne II FINE-STRUCTURE LINE EMISSION FROM THE OUTFLOWS OF YOUNG STELLAR OBJECTS

    SciTech Connect

    Shang, Hsien; Lin, Wei-Chieh; Liu, Chun-Fan J.; Glassgold, Alfred E.

    2010-05-10

    The flux and line shape of the fine-structure transitions of Ne II and Ne III at 12.8 and 15.55 {mu}m and of the forbidden transitions of O I {lambda}6300 are calculated for young stellar objects with a range of mass-loss rates and X-ray luminosities using the X-wind model of jets and the associated wide-angle winds. For moderate and high accretion rates, the calculated Ne II line luminosity is comparable to or much larger than produced in X-ray irradiated disk models. All of the line luminosities correlate well with the main parameter in the X-wind model, the mass-loss rate, and also with the assumed X-ray luminosity-and with one another. The line shapes of an approaching jet are broad and have strong blue-shifted peaks near the effective terminal velocity of the jet. They serve as a characteristic and testable aspect of jet production of the neon fine-structure lines and the O I forbidden transitions.

  9. Accurate Electron Affinity of Iron and Fine Structures of Negative Iron ions

    NASA Astrophysics Data System (ADS)

    Chen, Xiaolin; Luo, Zhihong; Li, Jiaming; Ning, Chuangang

    2016-05-01

    Ionization potential (IP) is defined as the amount of energy required to remove the most loosely bound electron of an atom, while electron affinity (EA) is defined as the amount of energy released when an electron is attached to a neutral atom. Both IP and EA are critical for understanding chemical properties of an element. In contrast to accurate IPs and structures of neutral atoms, EAs and structures of negative ions are relatively unexplored, especially for the transition metal anions. Here, we report the accurate EA value of Fe and fine structures of Fe‑ using the slow electron velocity imaging method. These measurements yield a very accurate EA value of Fe, 1235.93(28) cm‑1 or 153.236(34) meV. The fine structures of Fe‑ were also successfully resolved. The present work provides a reliable benchmark for theoretical calculations, and also paves the way for improving the EA measurements of other transition metal atoms to the sub cm‑1 accuracy.

  10. Position-sensitive change in the transition metal L-edge fine structures

    SciTech Connect

    Gulec, Ahmet; Phillips, Patrick J.; Klie, Robert F.

    2015-10-05

    Studying the structure and composition of solid-state materials on the atomic scale has become nearly routine in transmission electron microscopy with the development of novel electron optics and electron sources. In particular, with spatial resolutions better than 0.1 nm and energy resolution smaller than 100 meV, the stoichiometry, bonding, and coordination can now be examined on similar scales. Aberration-corrected scanning transmission electron microscopy and electron energy-loss spectroscopy (EELS) have played a crucial role in identifying charge ordering, valence, and as spin state transitions in transition metal perovskite oxides. In this letter, we investigate the effects of ever-decreasing electron-probe sizes on the measured near-edge fine-structure of the transition metal core-loss edge using EELS. We find that for certain transition metal perovskites, the position of the electron probe with respect to the atomic column is crucial in determining the correct valence state. Several reasons for the observed position-sensitive EELS fine-structure are discussed.

  11. Fine structure of the red luminescence band in undoped GaN

    SciTech Connect

    Reshchikov, M. A.; Usikov, A.; Helava, H.; Makarov, Yu.

    2014-01-20

    Many point defects in GaN responsible for broad photoluminescence (PL) bands remain unidentified. Their presence in thick GaN layers grown by hydride vapor phase epitaxy (HVPE) detrimentally affects the material quality and may hinder the use of GaN in high-power electronic devices. One of the main PL bands in HVPE-grown GaN is the red luminescence (RL) band with a maximum at 1.8 eV. We observed the fine structure of this band with a zero-phonon line (ZPL) at 2.36 eV, which may help to identify the related defect. The shift of the ZPL with excitation intensity and the temperature-related transformation of the RL band fine structure indicate that the RL band is caused by transitions from a shallow donor (at low temperature) or from the conduction band (above 50 K) to an unknown deep acceptor having an energy level 1.130 eV above the valence band.

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

    SciTech Connect

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

    2007-01-01

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

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

    SciTech Connect

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

    2007-01-01

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

  14. Pleiades luminosity function: fine structure and new Pre-MS models

    NASA Astrophysics Data System (ADS)

    Belikov, A. N.; Piskunov, A. E.; Schilbach, E.

    In order to study a model-dependence of the results achieved in the previous investigations of the Pleiades luminosity function using D'Antona and Mazzitelli (1994) evolutionary tracks, we repeated the computations with the new track system by D'Antona and Mazzitelli (1997). T h e following main conclusions can be drawn: the new models agree better with observations; the helium abundance needed to fit the Hipparcos distance modulus is reduced to a more reasonable value of Y=0.31; the cluster age becomes slightly higher and the slope of the initial mass function somewhat lower. The conclusions on the fine structure of the luminosity function do not change significantly due to the application of the new models.

  15. Strain-driven growth of GaAs(111) quantum dots with low fine structure splitting

    NASA Astrophysics Data System (ADS)

    Yerino, Christopher D.; Simmonds, Paul J.; Liang, Baolai; Jung, Daehwan; Schneider, Christian; Unsleber, Sebastian; Vo, Minh; Huffaker, Diana L.; Höfling, Sven; Kamp, Martin; Lee, Minjoo Larry

    2014-12-01

    Symmetric quantum dots (QDs) on (111)-oriented surfaces are promising candidates for generating polarization-entangled photons due to their low excitonic fine structure splitting (FSS). However, (111) QDs are difficult to grow. The conventional use of compressive strain to drive QD self-assembly fails to form 3D nanostructures on (111) surfaces. Instead, we demonstrate that (111) QDs self-assemble under tensile strain by growing GaAs QDs on an InP(111)A substrate. Tensile GaAs self-assembly produces a low density of QDs with a symmetric triangular morphology. Coherent, tensile QDs are observed without dislocations, and the QDs luminescence at room temperature. Single QD measurements reveal low FSS with a median value of 7.6 μeV, due to the high symmetry of the (111) QDs. Tensile self-assembly thus offers a simple route to symmetric (111) QDs for entangled photon emitters.

  16. Strain-driven growth of GaAs(111) quantum dots with low fine structure splitting

    SciTech Connect

    Yerino, Christopher D.; Jung, Daehwan; Lee, Minjoo Larry; Simmonds, Paul J.; Liang, Baolai; Huffaker, Diana L.; Schneider, Christian; Unsleber, Sebastian; Vo, Minh; Kamp, Martin; Höfling, Sven

    2014-12-22

    Symmetric quantum dots (QDs) on (111)-oriented surfaces are promising candidates for generating polarization-entangled photons due to their low excitonic fine structure splitting (FSS). However, (111) QDs are difficult to grow. The conventional use of compressive strain to drive QD self-assembly fails to form 3D nanostructures on (111) surfaces. Instead, we demonstrate that (111) QDs self-assemble under tensile strain by growing GaAs QDs on an InP(111)A substrate. Tensile GaAs self-assembly produces a low density of QDs with a symmetric triangular morphology. Coherent, tensile QDs are observed without dislocations, and the QDs luminescence at room temperature. Single QD measurements reveal low FSS with a median value of 7.6 μeV, due to the high symmetry of the (111) QDs. Tensile self-assembly thus offers a simple route to symmetric (111) QDs for entangled photon emitters.

  17. Constraints on the Time Variation of the Fine Structure Constant by the 5-Year WMAP Data

    NASA Astrophysics Data System (ADS)

    Nakashima, M.; Nagata, R.; Yokoyama, J.

    2008-12-01

    The constraints on the time variation of the fine structure constant at recombination epoch relative to its present value, Δα/α ≡ (α_{rec} - α_{now})/α_{now}, are obtained from the analysis of the 5-year WMAP cosmic microwave background data. As a result of Markov-Chain Monte-Carlo analysis, it is found that, contrary to the analysis based on the previous WMAP data, the mean value of Δα/α = -0.0009 does not change significantly whether we use the Hubble Space Telescope (HST) measurement of the Hubble parameter as a prior or not. The resultant 95% confidence ranges of Δα/α are -0.028 < Δα/α < 0.026 with HST prior and -0.050 < Δα/α < 0.042 without HST prior.

  18. Highly charged ions for atomic clocks and search for variation of the fine structure constant

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    We review a number of highly charged ions which have optical transitions suitable for building extremely accurate atomic clocks. This includes ions from Hf 12+ to U 34+, which have the 4 f 12 configuration of valence electrons, the Ir 17+ ion, which has a hole in almost filled 4 f subshell, the Ho 14+, Cf 15+, Es 17+ and Es 16+ ions. Clock transitions in most of these ions are sensitive to variation of the fine structure constant, α (α = e2/hbar c). E.g., californium and einsteinium ions have largest known sensitivity to α-variation while holmium ion looks as the most suitable ion for experimental study. We study the spectra of the ions and their features relevant to the use as frequency standards.

  19. Exciton fine-structure splitting in GaN/AlN quantum dots

    NASA Astrophysics Data System (ADS)

    Kindel, C.; Kako, S.; Kawano, T.; Oishi, H.; Arakawa, Y.; Hönig, G.; Winkelnkemper, M.; Schliwa, A.; Hoffmann, A.; Bimberg, D.

    2010-06-01

    Exciton bright-state fine-structure splitting (FSS) in single GaN/AlN quantum dots (QDs) is reported, presenting an important step toward the realization of room temperature single-qubit emitters for quantum cryptography and communication. The FSS in nitride QDs is up to 7 meV and thus much larger than for other QD systems. We find also a surprising dependence of FSS on the QD size, inverse to that of arsenide QDs. Now we are able to explain why FSS can only be observed in small QDs of high-emission energies. Our calculations reveal a shape/strain anisotropy as origin of the large FSS allowing different approaches to control FSS in nitrides.

  20. Fine structure of the isoscalar giant quadrupole resonance in 28Si and 27Al

    NASA Astrophysics Data System (ADS)

    Usman, I. T.; Buthelezi, Z.; Carter, J.; Cooper, G. R. J.; Fearick, R. W.; Förtsch, S. V.; Fujita, H.; Fujita, Y.; von Neumann-Cosel, P.; Neveling, R.; Papakonstantinou, P.; Pysmenetska, I.; Richter, A.; Roth, R.; Sideras-Haddad, E.; Smit, F. D.

    2016-08-01

    The isoscalar giant quadrupole resonance in 28Si and 27Al has been investigated with high-energy-resolution proton inelastic scattering at Ep=200 MeV and at scattering angles close to the maximum of Δ L =2 angular distributions with the K600 magnetic spectrometer of iThemba LABS, South Africa. Characteristic scales are extracted from the observed fine structure with a wavelet analysis and compared for 28Si with random-phase approximation and second random phase approximation calculations with an interaction derived from the Argonne V18 potential by a unitary transformation. A recent extension of the method to deformed nuclei provides the best description of the data, suggesting the significance of Landau damping.

  1. Relation between the synthesis conditions and the fine structure of fiber carbon

    NASA Astrophysics Data System (ADS)

    Tyumentsev, V. A.; Fazlitdinova, A. G.

    2016-03-01

    The fine structure of carbon fibers synthesized under various technological conditions is studied. It is found that the material of the fibers is heterogeneous and its component composition is determined by thermomechanical treatment conditions and the presence of a boron addition and depends on the angle of coherent-domain orientation φ with respect to the fiber axis. The detected dependences of the component composition of the fibers on the heat-treatment temperature and time and the angle of coherent-domain orientation with respect to the fiber axis suggest that the transition of the carbon material of the fibers into a more equilibrium state is likely to proceed through a number of metastable states.

  2. Automated fine structure image analysis method for discrimination of diabetic retinopathy stage using conjunctival microvasculature images

    PubMed Central

    Khansari, Maziyar M; O’Neill, William; Penn, Richard; Chau, Felix; Blair, Norman P; Shahidi, Mahnaz

    2016-01-01

    The conjunctiva is a densely vascularized mucus membrane covering the sclera of the eye with a unique advantage of accessibility for direct visualization and non-invasive imaging. The purpose of this study is to apply an automated quantitative method for discrimination of different stages of diabetic retinopathy (DR) using conjunctival microvasculature images. Fine structural analysis of conjunctival microvasculature images was performed by ordinary least square regression and Fisher linear discriminant analysis. Conjunctival images between groups of non-diabetic and diabetic subjects at different stages of DR were discriminated. The automated method’s discriminate rates were higher than those determined by human observers. The method allowed sensitive and rapid discrimination by assessment of conjunctival microvasculature images and can be potentially useful for DR screening and monitoring. PMID:27446692

  3. New constraints on variations of the fine structure constant from CMB anisotropies

    SciTech Connect

    Menegoni, Eloisa; Melchiorri, Alessandro; Galli, Silvia; Bartlett, James G.; Martins, C. J. A. P.

    2009-10-15

    We demonstrate that recent measurements of cosmic microwave background temperature and polarization anisotropy made by the ACBAR, QUAD, and BICEP experiments substantially improve the cosmological constraints on possible variations of the fine structure constant in the early universe. This data, combined with the five year observations from the WMAP mission, yield the constraint {alpha}/{alpha}{sub 0}=0.987{+-}0.012 at 68% C.L. The inclusion of the new Hubble Space Telescope constraints on the Hubble constant further increases the accuracy to {alpha}/{alpha}{sub 0}=1.001{+-}0.007 at 68% C.L., bringing possible deviations from the current value below the 1% level and improving previous constraints by a factor of {approx}3.

  4. Enhanced sensitivity to the fine-structure-constant variation in the Th IV atomic clock transition

    SciTech Connect

    Flambaum, V. V.; Porsev, S. G.

    2009-12-15

    Our calculations have shown that the 5f{sub 5/2}-7s{sub 1/2} 23 131 cm{sup -1} transition from the ground state in the ion Th{sup 3+} is very sensitive to the temporal variation of the fine-structure constant alpha=e{sup 2}/(Planck constant/2pi)c (q=-75 300 cm{sup -1}). The line is very narrow, the ion has been trapped and laser cooled, and the positive shifter line 5f{sub 5/2}-5f{sub 7/2} 4325 cm{sup -1} (q=+2900 cm{sup -1}) may be used as a reference. A comparison may also be made with a positive shifter in another atom or ion. This makes Th{sup 3+} a good candidate to search for the alpha variation.

  5. Fine structures of organic photovoltaic thin films probed by frequency-shift electrostatic force microscopy

    NASA Astrophysics Data System (ADS)

    Araki, Kento; Ie, Yutaka; Aso, Yoshio; Matsumoto, Takuya

    2016-07-01

    The localized charge and electrostatic properties of organic photovoltaic thin films are predominating factors for controlling energy conversion efficiency. The surface potential and electrostatic structures of organic photovoltaic thin films were investigated by frequency shift mode Kelvin force microscopy (KFM) and electrostatic force microscopy (EFM). The KFM images of a poly[2-methoxy-5-(3‧,7‧-dimethyloctyloxy)-1,4-phenylene vinylene]/phenyl-C61-butyric-acid-methyl ester (PCBM) blend thin film reveals that the PCBM domains precipitate as the topmost layer on the thin films. We find fine structures that were not observed in the topography and KFM images. The bias dependence of the EFM images suggests that the EFM contrast reflects the field-induced polarization, indicating the presence of charge trapping sites.

  6. Fine structural changes in the lateral vestibular nucleus of aging rats

    NASA Technical Reports Server (NTRS)

    Johnson, J. E., Jr.; Miquel, J.

    1974-01-01

    The fine structure of the lateral vestibular nucleus was investigated in Sprague-Dawley rats, that were sacrified at 4 weeks, 6-8 weeks, 6-8 months, and 18-20 months of age. In the neuronal perikaria, the following age-associated changes were seen with increasing frequency with advancing age: rodlike nuclear inclusions and nuclear membrane invaginations; cytoplasmic dense bodies with the characteristics of lipofuscin; and moderate disorganization of the granular endoplasmic reticulum. Dense bodies were also seen in glial cells. Rats 18 to 20 months old showed dendritic swellings, axonal degeneration, and an apparent increase in the number of axosomatic synaptic terminals containing flattened vesicles (presumed to be inhibitory in function).

  7. Semi-empirical analysis of the fine structure and oscillator strengths for atomic strontium

    NASA Astrophysics Data System (ADS)

    Ruczkowski, J.; Elantkowska, M.; Dembczyński, J.

    2016-02-01

    As the result of our studies on the atomic structure of complex atoms we produced high quality wave functions for both even and odd systems of configurations of Sr I. These wave functions were used for the parametrization of the oscillator strengths for electric-dipole transitions, where reliable data were available. The angular coefficients of the transition matrix in pure SL coupling were calculated by means of straightforward Racah algebra. The transition matrix was transformed into the actual intermediate coupling by the fine structure wave functions. The transition integrals were treated as free parameters in the least squares fit to the gf values. This procedure allowed us to obtain the values of the transition integrals and predict the values of oscillator strengths for the transitions from odd levels in a wide spectral range.

  8. Vibrational fine structure of C5 via anion slow photoelectron velocity-map imaging

    NASA Astrophysics Data System (ADS)

    Weichman, Marissa L.; Kim, Jongjin B.; Neumark, Daniel M.

    2013-10-01

    High-resolution anion photoelectron spectra of cryogenically cooled C_5^ - clusters are reported using slow photoelectron velocity-map imaging spectroscopy. We resolve vibronic transitions to the ν2 stretching mode and multiply excited ν5, ν6, and ν7 bending modes of neutral C5 with significantly higher accuracy than previous experiments. Weak transitions to Franck-Condon (FC) forbidden singly excited bending modes are made possible by Herzberg-Teller coupling between electronic states of the neutral cluster. In addition, we resolve vibrational fine structure corresponding to different angular momentum states of multiply excited bending modes. The observation of this multiplet structure, some of which is FC forbidden, is attributed to Renner-Teller coupling between vibrational levels in the C_5^ - ground electronic state.

  9. Confocal imaging reveals three-dimensional fine structure difference between ventral and dorsal nerve roots

    NASA Astrophysics Data System (ADS)

    Wu, Yuxiang; Sui, Tao; Cao, Xiaojian; Lv, Xiaohua; Zeng, Shaoqun; Sun, Peng

    2011-05-01

    Peripheral nerve injury repair is one of the most challenging problems in neurosurgery, partially due to lack of knowledge of three-dimensional (3-D) fine structure and organization of peripheral nerves. In this paper, we explored the structures of nerve fibers in ventral and dorsal nerves with a laser scanning confocal microscopy. Thick tissue staining results suggested that nerve fibers have a different 3-D structure in ventral and dorsal nerves, and reconstruction from serial sectioning images showed that in ventral nerves the nerve fibers travel in a winding form, while in dorsal nerves, the nerve fibers form in a parallel cable pattern. These structural differences could help surgeons to differentiate ventral and dorsal nerves in peripheral nerve injury repair, and also facilitate scientists to get a deeper understanding about nerve fiber organization.

  10. Mechanical Behavior of Agave Americana L. Fibres: Correlation Between Fine Structure and Mechanical Properties

    NASA Astrophysics Data System (ADS)

    Msahli, S.; Chaabouni, Y.; Sakli, F.; Drean, J. Y.

    In this study, results of a mechanical behavior study of fibres extracted from the agave Americana L. plant, the most abundant variety in Tunisia, are presented. These results deal with the principal and mechanical characteristics of these fibres which are the elongation at break, the elasticity modulus and the rupture facture. These results permitted to situate these fibres, compared to the other textile fibres, as materials that can be used in technical applications such as reinforcing composites or geotextile. In order to understand the mechanical properties of these fibres, a correlation study between the properties already cited and the fine structure was done. The obtained results showed that the mechanical properties of agave Americana L. fibres are closely related to the individual fibers deformations and to the natural matrix (lignin and gums) that links these elementary fibres.

  11. Fine-structural changes in the midgut of old Drosophila melanogaster

    NASA Technical Reports Server (NTRS)

    Anton-Erxleben, F.; Miquel, J.; Philpott, D. E.

    1983-01-01

    Senescent fine-structural changes in the midgut of Drosophila melanogaster are investigated. A large number of midgut mitochondria in old flies exhibit nodular cristae and a tubular system located perpendicular to the normal cristae orientation. Anterior intestinal cells show a senescent accumulation of age pigment, either with a surrounding two-unit membrane or without any membrane. The predominant localization of enlarged mitochondria and pigment in the luminal gut region may be related to the polarized metabolism of the intestinal cells. Findings concur with previous observations of dense-body accumulations and support the theory that mitochondria are involved in the aging of fixed post-mitotic cells. Demonstrated by statistical analyses is that mitochondrial size increase is related to mitochondrial variation increase.

  12. The effective fine-structure constant of freestanding graphene measured in graphite.

    PubMed

    Reed, James P; Uchoa, Bruno; Joe, Young Il; Gan, Yu; Casa, Diego; Fradkin, Eduardo; Abbamonte, Peter

    2010-11-01

    Electrons in graphene behave like Dirac fermions, permitting phenomena from high-energy physics to be studied in a solid-state setting. A key question is whether or not these fermions are critically influenced by Coulomb correlations. We performed inelastic x-ray scattering experiments on crystals of graphite and applied reconstruction algorithms to image the dynamical screening of charge in a freestanding graphene sheet. We found that the polarizability of the Dirac fermions is amplified by excitonic effects, improving screening of interactions between quasiparticles. The strength of interactions is characterized by a scale-dependent, effective fine-structure constant, α(g)* (k,ω), the value of which approaches 0.14 ± 0.092 ~ 1/7 at low energy and large distances. This value is substantially smaller than the nominal α(g) = 2.2, suggesting that, on the whole, graphene is more weakly interacting than previously believed. PMID:21051634

  13. Fine structure in the cosmic ray spectrum: Further analysis and the next step

    NASA Astrophysics Data System (ADS)

    Erlykin, A. D.; Wolfendale, A. W.

    2012-01-01

    An analysis is made of the fine structure in the cosmic ray energy spectrum: new facets of present observations and their interpretation and the next step. It is argued that less than about 10% of the intensity of the helium 'peak' at the knee at ≈5 PeV is due to just a few sources (SNR) other than the single source. The apparent concavity in the rigidity spectra of protons and helium nuclei which have maximum curvature at about 200 GV is confirmed by a joint analysis of the PAMELA, CREAM and ATIC experiments. The spectra of heavier nuclei also show remarkable structure in the form of 'ankles' at several hundred GeV/nucleon. Possible mechanisms are discussed. The search for 'pulsar peaks' has not yet proved successful.

  14. Fine structure of spermatozoa in the common pandora (Pagellus erythrinus Linnaeus, 1758) (Perciformes, Sparidae).

    PubMed

    Maricchiolo, G; Genovese, L; Laurà, R; Micale, V; Muglia, U

    2004-10-01

    Scanning and transmission electron microscopy were used to investigate the fine structure of the sperm of the Sparid fish Pagellus erythrinus L. The spermatozoon of pandora has a spherical head lacking an acrosome, a cone-shaped midpiece and a long tail. The midpiece houses a single mitochondrion. The centriolar complex lies inside the nuclear fossa and is composed of a proximal and a distal centriole which are arranged at right angles to each other. The flagellum is inserted medio-laterally into the head, contains the conventional 9+2 axoneme and possesses one pair of lateral fins. On the basis of its ultrastructural organization, the pandora sperm can be regarded as an evolved form of the primitive spermatozoon found in Teleosts. According to the morphological classification proposed by Mattei (1970), the sperm of pandora belongs to a "type I" designation, like that of the other Sparid fish. PMID:15375767

  15. Automated fine structure image analysis method for discrimination of diabetic retinopathy stage using conjunctival microvasculature images.

    PubMed

    Khansari, Maziyar M; O'Neill, William; Penn, Richard; Chau, Felix; Blair, Norman P; Shahidi, Mahnaz

    2016-07-01

    The conjunctiva is a densely vascularized mucus membrane covering the sclera of the eye with a unique advantage of accessibility for direct visualization and non-invasive imaging. The purpose of this study is to apply an automated quantitative method for discrimination of different stages of diabetic retinopathy (DR) using conjunctival microvasculature images. Fine structural analysis of conjunctival microvasculature images was performed by ordinary least square regression and Fisher linear discriminant analysis. Conjunctival images between groups of non-diabetic and diabetic subjects at different stages of DR were discriminated. The automated method's discriminate rates were higher than those determined by human observers. The method allowed sensitive and rapid discrimination by assessment of conjunctival microvasculature images and can be potentially useful for DR screening and monitoring. PMID:27446692

  16. Fine structure in RF spectra of lightning return stroke wave forms

    NASA Technical Reports Server (NTRS)

    Lanzerotti, L. J.; Thomson, D. J.; Maclennan, C. G.; Rinnert, K.; Krider, E. P.

    1988-01-01

    The power spectra of the wide-band (10 Hz to 100 kHz) magnetic-field signals for a number of lightning return strokes measured during a thunderstorm which occurred in Lindau in August, 1984 have been calculated. The RF magnetic field data are obtained with the engineering unit of the Galileo Jupiter Probe lightning experiment. Each return stroke data stream is passed through an adaptive filter designed to whiten its spectrum. The spectra of the magnetic field data definitely show fine structure, with two or three distinct peaks in the spectra of many of the waveforms. A peak at f of about 60-70 kHz is often seen in the power spectra of the waveform time segments preceding and following the rise-to-peak amplitude of the return stroke.

  17. Electric control of the exciton fine structure in nonparabolic quantum dots

    NASA Astrophysics Data System (ADS)

    Welander, Erik; Burkard, Guido

    2012-10-01

    We show that the nonparabolic confinement potential is responsible for the nonmonotonic behavior and sign change of the exciton fine-structure splitting (FSS) in optically active self-assembled quantum dots. This insight is important for the theoretical understanding and practical control by electric fields of the quantum state of the emitted light from a biexciton cascade recombination process. We find that a hard-wall (box) confinement potential leads to a FSS that is in better agreement with experimentally measured FSS than a harmonic potential. We then show that a finite applied electric field can be used to remove the FSS entirely, thus allowing for the creation of maximally entangled photons, being vital to the growing field of quantum communication and quantum key distribution.

  18. PAP-LMPCR for improved, allele-specific footprinting and automated chromatin fine structure analysis

    PubMed Central

    Ingram, R.; Gao, C.; LeBon, J.; Liu, Q.; Mayoral, R. J.; Sommer, S. S.; Hoogenkamp, M.; Riggs, A. D.; Bonifer, C.

    2008-01-01

    The analysis of chromatin fine structure and transcription factor occupancy of differentially expressed genes by in vivo footprinting and ligation-mediated-PCR (LMPCR) is a powerful tool to understand the impact of chromatin on gene expression. However, as with all PCR-based techniques, the accuracy of the experiments has often been reduced by sequence similarities and the presence of GC-rich or repeat sequences, and some sequences are completely refractory to analysis. Here we describe a novel method, pyrophosphorolysis activated polymerization LMPCR or PAP-LMPCR, which is capable of generating accurate and reproducible footprints specific for individual alleles and can read through sequences previously not accessible for analysis. In addition, we have adapted this technique for automation, thus enabling the simultaneous and rapid analysis of chromatin structure at many different genes. PMID:18208840

  19. LETTER TO THE EDITOR: Strong configuration mixing among the fine-structure levels of Cl+

    NASA Astrophysics Data System (ADS)

    Deb, N. C.; Crothers, D. S. F.; Felfli, Z.; Msezane, A. Z.

    2003-01-01

    A large-scale configuration interaction (CI) calculation using Program CIV3 of Hibbert is performed for the lowest 62 fine-structure levels of the singly charged chlorine ion. Our calculated energy levels agree very well with most of the NIST results and confirm the identification of the lowest 1Po as actually 3s2 3p3 (2Do)3d 1Po rather than the generally employed 3s3p5 1Po in measurements and calculations. Discrepancies in the energy positions of some symmetries are found and discussed. Some large oscillator strengths for allowed and intercombination transitions in both length and velocity gauges are presented. Their close agreement gives credence to the accuracy of our CI wavefunctions.

  20. A simulation for gravity fine structure recovery from low-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 low-low SST mission for accurate local recovery of gravitational fine structure, considering the aliasing effects of unsolved for parameters. A 5 degree by 5 degree surface density block representation of the high order geopotential was utilized with the drag-free low-low GRAVSAT configuration in a circular polar orbit at 250 km altitude. Recovery of local sets of density blocks from long data arcs was found not to be feasible due to strong aliasing effects. The error analysis for the recovery of local sets of density blocks using independent short data arcs demonstrated that the estimation strategy of simultaneously estimating a local set of blocks covered by data and two "buffer layers" of blocks not covered by data greatly reduced aliasing errors.

  1. [Histochemical findings of and fine structural changes in motor endplates in diseases with neuromuscular transmission abnormalities].

    PubMed

    Yoshimura, Toshiro; Motomura, Masakatsu; Tsujihata, Mitsuhiro

    2011-07-01

    We herein review the histochemical findings and fine structural changes of motor endplates associated with diseases causing neuromuscular transmission abnormalities. In anti-acetylcholine receptor (AChR) antibody-positive myasthenia gravis (MG), type 2 fiber atrophy is observed, and the motor endplates show a reduction in the nerve terminal area, simplification of the postsynaptic membrane, decreased number of acetylcholine receptors, and deposition of immune complexes. In anti-MuSK antibody-positive MG, the fine structure shows a decrease in the postsynaptic membrane length, but the secondary synaptic cleft is preserved. There is no decrease in the number of AChRs, and there are no deposits of immune complexes at the motor endplates. Patients with Lambert-Eaton myasthenic syndrome show type 2 fiber atrophy, their motor endplates show a decrease in both the mean postsynaptic area and postsynaptic membrane length in the brachial biceps muscle. Congenital myasthenic syndrome with episodic apnea is characterized only by small-sized synaptic vesicles; the postsynaptic area is preserved. In subjects with congenital myasthenic syndrome with acetylcholinesterase deficiency, quantitative electron microscopy reveals a significant decrease in the nerve terminal size and presynaptic membrane length; further, the Schwann cell processes extend into the primary synaptic cleft, and partially or completely occlude the presynaptic membrane. The postsynaptic folds are degenerated, and associated with pinocytotic vesicles and labyrinthine membranous networks. Patients with slow-channel congenital myasthenia syndrome show type 1 fiber predominance, and their junctional folds are typically degenerated with widened synaptic space and loss of AChRs. Patients with AChR deficiency syndrome caused by recessive mutations in AChR subunits also show type 1 fiber predominance, and while most junctional folds are normal, some are simplified and have smaller than normal endplates. Rapsin and Mu

  2. Comparison of Fine Structures of Electron Cyclotron Harmonic Emissions in Aurora

    NASA Astrophysics Data System (ADS)

    Labelle, J. W.; Dundek, M.

    2015-12-01

    Recent discoveries of emissions at four and five times the electron cyclotron frequency in aurora occuring under daylit conditions motivated the modification of radio receivers at South Pole Station, Antarctica, to measure fine structure of such emissions during two consecutive austral summers, 2013-4 and 2014-5. The experiment recorded 347 emission events over 376 days of observation. The seasonal distribution of these events revealed that successively higher harmonics require higher solar zenith angles for occurrence, as expected if they are generated at locations where the upper hybrid frequency matches the cyclotron harmonic, which for higher harmonics requires higher electron densities which are associated with higher solar zenith angles. Detailed examination of 21 cases in which two harmonics occur simultaneously showed that only rarely, about ten percent of the time, are the frequencies of the fine structures of the emissions in exact integer ratio (e.g., 3:2, 4:3, or 5:4 depending on which combination of harmonics is observed). In the remaining approximately ninety percent of the cases, the higher harmonic occurred at a lower ratio than the appropriate integer ratio, as expected if the harmonics are generated independently at their separate matching conditions in the bottomside ionosphere, where the upper hybrid frequency increases with altitude while the gyroharmonics decrease with altitude. (The bottomside is the most likely source of the emissions, since from there the mode converted Z-modes have access to ground-level.) Taken together, these results suggest that the dominant mechanism for the higher harmonics is independent generation at locations where the upper hybrid frequency matches each harmonic, i.e., at a separate source altitude for each harmonic. Generation of higher harmonics through coalescence of lower harmonic waves explains at most a small minority of events.

  3. Comparison of fine structures of electron cyclotron harmonic emissions in aurora

    NASA Astrophysics Data System (ADS)

    LaBelle, J.; Dundek, M.

    2015-10-01

    Recent discoveries of higher harmonic cyclotron emissions in aurora occurring under daylight conditions motivated the modification of radio receivers at South Pole Station, Antarctica, to measure fine structure of such emissions during two consecutive austral summers, 2013-2014 and 2014-2015. The experiment recorded 347 emission events over 376 days of observation. The seasonal distribution of these events reveals that successively higher harmonics require higher solar zenith angles for occurrence, as expected if they are generated at the matching condition fuh = Nfce, which for higher N requires higher electron densities which are associated with higher solar zenith angles. This result implies that generation of higher harmonics from lower harmonics via wave-wave processes explains only a minority of events. Detailed examination of 21 cases in which two harmonics occur simultaneously shows that in almost all events the higher harmonic comes from higher altitudes, and only for a small fraction of events is it plausible that the frequencies of the fine structures of the emissions are correlated and in exact integer ratio. This observation puts an upper bound of 15-20% on the fraction of emissions which can be explained by wave-wave interactions involving Z mode waves at fce and, combined with consideration of source altitudes, puts an upper bound of 75% on the fraction explained by coalescence of Z mode waves at 2fce. Taken together, these results suggest that the dominant mechanism for the higher harmonics is independent generation at the matching points fuh = Nfce and that the wave-wave interaction mechanisms explain a relatively small fraction of events.

  4. Production of fine structures in type III solar radio bursts due to turbulent density profiles

    SciTech Connect

    Loi, Shyeh Tjing; Cairns, Iver H.; Li, Bo

    2014-07-20

    Magnetic reconnection events in the corona release energetic electron beams along open field lines, and the beams generate radio emission at multiples of the electron plasma frequency f{sub p} to produce type III solar radio bursts. Type III bursts often exhibit irregularities in the form of flux modulations with frequency and/or local temporal advances and delays, and a type IIIb burst represents the extreme case where a type III burst is fragmented into a chain of narrowband features called striae. Remote and in situ spacecraft measurements have shown that density turbulence is ubiquitous in the corona and solar wind, and often exhibits a Kolmogorov power spectrum. In this work, we numerically investigate the effects of one-dimensional macroscopic density turbulence (along the beam direction) on the behavior of type III bursts, and find that this turbulence produces stria-like fine structures in the dynamic spectra of both f{sub p} and 2 f{sub p} radiation. Spectral and temporal fine structures in the predicted type III emission are produced by variations in the scattering path lengths and group speeds of radio emission, and in the locations and sizes of emitting volumes. Moderate turbulence levels yield flux enhancements with much broader half-power bandwidths in f{sub p} than 2 f{sub p} emission, possibly explaining the often observed type IIIb-III harmonic pairs as being where intensifications in 2 f{sub p} radiation are not resolved observationally. Larger turbulence levels producing trough-peak regions in the plasma density profile may lead to broader, resolvable intensifications in 2 f{sub p} radiation, which may account for the type IIIb-IIIb pairs that are sometimes observed.

  5. The importance of source positions during solar radio fine structures observations

    NASA Astrophysics Data System (ADS)

    Chernov, Gennady; Tan, Baolin; Fomichev, Valery; Tan, Chengming; Yan, Yihua; Fu, Qijun

    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 of the radio sources for zebra- structure and fiber bursts will testify about the united mechanism for both structures. We demonstrated several events with radio fine structures in which the positional observations could be a determining factor for the selection of the radio emission mechanism. It is very important to determine the size of source in the corona: distributed along the height or point-like. In both models of zebra- structure (on the double plasma resonance (DPR) and with the whistlers) the source must be distributed along the height, but in contrast to the stationary source in the DPR model, in the model with whistlers the source should be moving. Moreover, the direction of the space drift of radio source must correlate with the frequency drift of stripes in the dynamic spectrum. Some models of zebra- structure require the local source, for example, the models based on the Bernstein modes, or on the explosive instability. The selection of the radio emission mechanism for fast broadband pulsations of millisecond duration depends also on the parameters of their radio sources. Now, we hope on the progress of the solar radio spectral imaging observations. The Chinese spectral radioheliograph (CSRH) is a new generation solar radio telescope which will be the largest and most advanced radio imaging telescope for solar corona in the world. It can provide true imaging spectroscope with high temporal, spatial, and spectral resolutions, covering decimeter and centimeter

  6. Fine Structure of Tibetan Kefir Grains and Their Yeast Distribution, Diversity, and Shift

    PubMed Central

    Lu, Man; Wang, Xingxing; Sun, Guowei; Qin, Bing; Xiao, Jinzhou; Yan, Shuling; Pan, Yingjie; Wang, Yongjie

    2014-01-01

    Tibetan kefir grains (TKGs), a kind of natural starter for fermented milk in Tibet, China, host various microorganisms of lactic acid bacteria, yeasts, and occasionally acetic acid bacteria in a polysaccharide/protein matrix. In the present study, the fine structure of TKGs was studied to shed light on this unusual symbiosis with stereomicroscopy and thin sections. The results reveal that TKGs consist of numerous small grain units, which are characterized by a hollow globular structure with a diameter between 2.0 and 9.0 mm and a wall thickness of approximately 200 µm. A polyhedron-like net structure, formed mainly by the bacteria, was observed in the wall of the grain units, which has not been reported previously to our knowledge. Towards the inside of the grain unit, the polyhedron-like net structures became gradually larger in diameter and fewer in number. Such fine structures may play a crucial role in the stability of the grains. Subsequently, the distribution, diversity, and shift of yeasts in TKGs were investigated based on thin section, scanning electron microscopy, cloning and sequencing of D1/D2 of the 26S rRNA gene, real-time quantitative PCR, and in situ hybridization with specific fluorescence-labeled oligonucleotide probes. These show that (i) yeasts appear to localize on the outer surface of the grains and grow normally together to form colonies embedded in the bacterial community; (ii) the diversity of yeasts is relatively low on genus level with three dominant species – Saccharomyces cerevisiae, Kluyveromyces marxianus, and Yarrowia lipolytica; (iii) S. cerevisiae is the stable predominant yeast species, while the composition of Kluyveromyces and Yarrowia are subject to change over time. Our results indicate that TKGs are relatively stable in structure, and culture conditions to some extent shape the microbial community and interaction in kefir grains. These findings pave the way for further study of the specific symbiotic associations between S

  7. Compact Fixed-exit UHV DCM for XAFS

    SciTech Connect

    Rickers, K.; Brueggmann, U.; Drube, W.; Herrmann, M.; Heuer, J.; Welter, E.; Schulte-Schrepping, H.; Schulz-Ritter, H.

    2007-01-19

    A double-crystal, UHV-compatible monochromator for XAFS applications at bending magnet beamlines has been designed. It uses two crystal sets, Si(111) and (311), on a common central rotation axis driven by an ex-vacuo goniometer. All mechanical and electrical components are mounted on a 400 mm UHV flange which is attached to a compact vacuum chamber. The first crystals are water cooled using connector- and bellowless tubing through the fluidic sealed feedthrough of the central rotation. The first crystal set is mounted off-axis and can be translated vertically to keep the fixed exit condition. The second crystal set uses small crystals of the same size as the first. In order to accept the reflected beam of the first crystal at small Bragg angles, it is tangentially translated along the beam. The angle can be varied from 5 deg. to 55.5 deg. resulting in a total energy range 2.4 - 43.4 keV for Si(111)/(311). Crystal sets are interchangeable by translating the vacuum chamber. Angle encoding is achieved by a Renishaw incremental optical encoder in vacuo.

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

    EPA Science Inventory

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

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

    SciTech Connect

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

    2009-02-26

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

  10. Hard X-ray XAFS beamline, BL5S1, at AichiSR

    NASA Astrophysics Data System (ADS)

    Tabuchi, M.; Asakura, H.; Morimoto, H.; Watanabe, N.; Takeda, Y.

    2016-05-01

    A XAFS beamline, BL5S1, had been operated at Aichi Synchrotron Radiation Center, Japan since March 2013. The beamline was designed for the measurements in the energy range from 5 to 20 keV. The photon flux of 6 x 1010 at around 9 keV and beam spot size of 0.5 x 0.3 mm at sample position are as good as designed. For the standard transmission XAFS measurement, both of the step- and quick- scan modes are available. Energy resolution at around 9keV is good enough to discuss the energy shift of the order of 0.1 eV or higher even when the measurements are conducted in the quick-scan mode. With several kinds of detectors for fluorescence and/or CEY detection mode measurements, and various kinds of sample holders which are supported by the XAFS measurement software, users easily obtain spectra for their samples. Such a standard, well operated and easy to access XAFS beamline must be very important to broaden the base of the XAFS society further.

  11. XAF1 directs apoptotic switch of p53 signaling through activation of HIPK2 and ZNF313.

    PubMed

    Lee, Min-Goo; Han, Jikhyon; Jeong, Seong-In; Her, Nam-Gu; Lee, Jin-Hee; Ha, Tae-Kyu; Kang, Min-Ju; Ryu, Byung-Kyu; Chi, Sung-Gil

    2014-10-28

    X-linked inhibitor of apoptosis (XIAP)-associated factor 1 (XAF1) is a tumor suppressor that is frequently inactivated in many human cancers. However, the molecular mechanism underlying its growth-inhibitory function remains largely unknown. Here, we report that XAF1 forms a positive feedback loop with p53 and acts as a molecular switch in p53-mediated cell-fate decisions favoring apoptosis over cell-cycle arrest. XAF1 binds directly to the N-terminal proline-rich domain of p53 and thus interferes with E3 ubiquitin ligase MDM2 binding and ubiquitination of p53. XAF1 stimulates homeodomain-interacting protein kinase 2 (HIPK2)-mediated Ser-46 phosphorylation of p53 by blocking E3 ubiquitin ligase Siah2 interaction with and ubiquitination of HIPK2. XAF1 also steps up the termination of p53-mediated cell-cycle arrest by activating zinc finger protein 313 (ZNF313), a p21(WAF1)-targeting ubiquitin E3 ligase. XAF1 interacts with p53, Siah2, and ZNF313 through the zinc finger domains 5, 6, and 7, respectively, and truncated XAF1 isoforms preferentially expressed in cancer cells fail to form a feedback loop with p53. Together, this study uncovers a novel role for XAF1 in p53 stress response, adding a new layer of complexity to the mechanisms by which p53 determines cell-fate decisions. PMID:25313037

  12. Local ordering of nanostructured Pt probed by multiple-scattering XAFS

    NASA Astrophysics Data System (ADS)

    Witkowska, Agnieszka; di Cicco, Andrea; Principi, Emiliano

    2007-09-01

    We present detailed results of a multiple-scattering (MS) extended x-ray absorption fine structure (EXAFS) data analysis of crystalline and nanocrystalline platinum. Advanced MS EXAFS analysis has been applied to raw x-ray absorption data including the background, using the expansion of the absorption cross section in terms of local two-body and three-body configurations. Present EXAFS results on bulk Pt are found to be in agreement with previous structural and vibrational data, and has been used as a reference for reliable structural refinement of nanosized systems. EXAFS structural refinement of Pt nanoparticles has been performed in combination with electron microscopy and x-ray diffraction, showing the importance of considering the actual size distribution and morphology of the samples. Present samples were unsupported and supported Pt nanocrystalline systems with size distributions showing clusters of quasispherical shape in the 1-7nm range. In particular, EXAFS spectra have been analyzed accounting for the reduction of the coordination number and degeneracy of three-body configurations, resulting from the measured size distribution and expected surface atom contributions. The importance of a correct account of the reduction of the number of neighbors for calculating MS contributions is emphasized in the paper. EXAFS results have been found compatible with x-ray diffraction and transmission electron microscopy investigations. We estimate that EXAFS could be used to study cluster shapes only for sizes below 2nm using present methods and quality of the experimental data. We have also shown that the local distribution of distances and angles probed by EXAFS is broader than in bulk Pt, with first-neighbor bond length variance and asymmetry increasing upon reducing the particle size. Methods and results presented in this paper have been found to be successful for a robust structural refinement of monatomic nanocrystalline systems and represents a solid starting

  13. Detection of bright trion states using the fine structure emission of single CdSe/ZnS colloidal quantum dots.

    PubMed

    Fernée, Mark J; Littleton, Bradley N; Rubinsztein-Dunlop, Halina

    2009-11-24

    We report direct observation of the lowest two states of the band-edge exciton fine structure in the photoluminescence from single CdSe/ZnS core/shell nanocrystals at cryogenic temperatures. The temperature dependence of this spectral fingerprint reveals exciton spin relaxation rates as low as 10 micros(-1). The fine structure is also dependent on the nanocrystal charge state facilitating the identification of a bright negatively charged trion state with a quantum yield comparable to that of neutral emission. PMID:19835398

  14. Fine Structure of the Gamow-Teller Resonance in {sup 90}Nb and Level Density of 1{sup +} States

    SciTech Connect

    Kalmykov, Y.; Neumann-Cosel, P. von; Ponomarev, V.Yu.; Richter, A.; Shevchenko, A.; Wambach, J.; Adachi, T.; Fujita, Y.; Shimbara, Y.; Berg, G.P.A.; Fujita, K.; Hatanaka, K.; Kamiya, J.; Nakanishi, K.; Sakamoto, N.; Sakemi, Y.; Shimizu, Y.; Wakasa, T.; Fujita, H.; Smit, F.D.

    2006-01-13

    The fine structure of the Gamow-Teller resonance in a medium-heavy nucleus is observed for the first time in a high-resolution {sup 90}Zr({sup 3}He,t){sup 90}Nb experiment at the Research Center for Nuclear Physics, Osaka. Using a novel wavelet analysis technique, it is possible to extract characteristic energy scales and to quantify their relative importance for the generation of the fine structure. This method combined with the selectivity of the reaction permits an extraction of the level density of 1{sup +} states in {sup 90}Nb.

  15. Manifestation of Quasilinear Diffusion on Whistlers in the Fine-Structure Radio Sources of Solar Radio Bursts

    SciTech Connect

    Chernov, G.P.

    2005-04-15

    The zebra structure and fiber bursts in the dynamic spectra of the solar type IV radio burst recorded on October 25, 1994, are analyzed using observational data from ground-based stations and Earth-orbiting satellites. The fine structure is observed when new hot magnetic loops, in which high- and low-frequency plasma instabilities develop, ascend to the solar corona. The frequency range of the fine structure is determined by the dimensions of these loops. The main features of the zebra structure are analyzed in terms of the interaction of plasma waves with whistlers. The results obtained are compared to the predictions from the double plasma resonance model.

  16. Hazards analysis for the E.O. Lawrence Berkeley National Laboratory x-ray absorption experiments to be performed at Stanford Synchrotron Radiation Laboratory

    SciTech Connect

    Edelstein, N.M.; Shuh, D.K.; Bucher, J.B.

    1995-04-01

    The objective of this experiment is to determine the oxidation state(s) of neptunium (Np) in mouse skeleton and in soft tissue by X-ray Absorption Near Edge Structure (XANES). If Np is present in sufficient concentration, X-ray Absorption Fine Structure (XAFS) data will be obtained in order to further identify the Np species present. These data will be crucial in understanding the metabolic pathway of Np in mammals which will help in the design of reagents which can eliminate Np from mammals in the event of accidental exposure. It is proposed to run these experiments at the Standard Synchrotron Radiation Laboratory (SSRL). This laboratory is a DOE national user facility located at the Stanford Linear Accelerator Center (SLAC). The {sup 237}Np nucleus decays by the emission of an alpha particle and this particle emission is the principal hazard in handling Np samples. This hazard is mitigated by physical containment of the sample which stops the alpha particles within the containment. The total amount of Np material that will be shipped to and be at SSRL at any one time will be less than 1 gram. This limit on the amount of Np will ensure that SLAC remains a low hazard, non-nuclear facility. The Np samples will be solids or Np ions in aqueous solution. The Np samples will be shipped to SSRL/SLAC OHP. SLAC OHP will inventory the samples and swipe the containers holding the triply contained samples, and then bring them to the SSRL Actinide trailer located outside building 131. The QA counting records from the samples, as measured at LBNL, will be provided to SSRL and SLAC OHP prior to the arrival of the samples at SLAC OHP. In addition, strict monitoring of the storage and experimental areas will be performed in accordance with SLAC/OHP radiation protection procedures to ensure against the release of contamination.

  17. A study on adsorption mechanism of organoarsenic compounds on ferrihydrite by XAFS

    NASA Astrophysics Data System (ADS)

    Tanaka, M.; Takahashi, Y.; Yamaguchi, N.

    2013-04-01

    Anthropogenic organoarsenic compounds which were used such as agrochemicals, pesticides, and herbicides can have a potential as a source of arsenic pollution in water. In the process, the adsorption of arsenic onto mineral surface in soil may play an important role to affect arsenic distribution in solid-water interface. However, adsorption structures of organoarsenic compounds on the iron-(oxyhydr)oxides are not well known. In this study, extended X-ray absorption fine structure (EXAFS) spectroscopy was employed to know the adsorption structure of methyl- and phenyl-substituted organoarsenic compounds (methylarsonic acid (MMA), dimethylarsinic acid (DMA), phenylarsonic acid (PAA), and diphenylarsinic acid (DPAA) onto ferrihydrite which can be a strong adsorbent of arsenic. EXAFS analysis suggests that the formation of inner-sphere surface complex for all organoarsenic compounds with ferrihydrite regardless of the organic functional groups and the number of substitution. The As-Fe distances are around 3.27 , which suggests both mono-and bi-dentate inner-sphere complexes by DFT calculations. The corresponding coordination numbers (CNs) are less than two, suggesting that coexistence of both structures of inner-sphere complexes.

  18. Low temperature XAFS investigation on the lutetium binding changes during the 2-line ferrihydrite alteration process.

    PubMed

    Dardenne, K; Schäfer, T; Lindqvist-Reis, P; Denecke, M A; Plaschke, M; Rothe, J; Kim, J I

    2002-12-01

    The time dependent changes of Lu speciation (used as Am(III) homologue), initially sorbed onto 2-line ferrihydrite at pH 5.9, during tempering (70 degrees C) to stable crystalline transformation products, goethite and hematite, is studied. Microscopies (AFM, SEM), XRD and FTIR spectroscopy confirm transformation to both goethite and hematite, with a predominance of hematite. XRD investigation of another transformation series at pH 8.0 (75 degrees C, [Lu(III)initial] 7 times higher) shows that the cell volume of hematite increases, suggesting the incorporation of Lu in the crystal structure. Extended X-ray absorption fine structure (EXAFS) (pH 5.9 series, 70 degrees C) reveals a shortening of the Lu-O bond distance and an increase in asymmetry of the first shell with increasing tempering time in the intermediate temper time samples. The intensity of the second peak in the Fourier transform (FT) of the EXAFS increases and splits into two components. The EXAFS data of the end product can be modeled well using a hematite-like cluster, with an isotropic expansion of distances to account for incorporation of Lu into the hematite structure. These results demonstrate that the Lu is incorporated in the crystal lattice of the transformation product, as opposed to being occluded or remaining a sorbed species on the surface. PMID:12523425

  19. Distorted Tonotopic Coding of Temporal Envelope and Fine Structure with Noise-Induced Hearing Loss

    PubMed Central

    Kale, Sushrut

    2016-01-01

    People with cochlear hearing loss have substantial difficulty understanding speech in real-world listening environments (e.g., restaurants), even with amplification from a modern digital hearing aid. Unfortunately, a disconnect remains between human perceptual studies implicating diminished sensitivity to fast acoustic temporal fine structure (TFS) and animal studies showing minimal changes in neural coding of TFS or slower envelope (ENV) structure. Here, we used general system-identification (Wiener kernel) analyses of chinchilla auditory nerve fiber responses to Gaussian noise to reveal pronounced distortions in tonotopic coding of TFS and ENV following permanent, noise-induced hearing loss. In basal fibers with characteristic frequencies (CFs) >1.5 kHz, hearing loss introduced robust nontonotopic coding (i.e., at the wrong cochlear place) of low-frequency TFS, while ENV responses typically remained at CF. As a consequence, the highest dominant frequency of TFS coding in response to Gaussian noise was 2.4 kHz in noise-overexposed fibers compared with 4.5 kHz in control fibers. Coding of ENV also became nontonotopic in more pronounced cases of cochlear damage. In apical fibers, more classical hearing-loss effects were observed, i.e., broadened tuning without a significant shift in best frequency. Because these distortions and dissociations of TFS/ENV disrupt tonotopicity, a fundamental principle of auditory processing necessary for robust signal coding in background noise, these results have important implications for understanding communication difficulties faced by people with hearing loss. Further, hearing aids may benefit from distinct amplification strategies for apical and basal cochlear regions to address fundamentally different coding deficits. SIGNIFICANCE STATEMENT Speech-perception problems associated with noise overexposure are pervasive in today's society, even with modern digital hearing aids. Unfortunately, the underlying physiological deficits in

  20. Hall effect and fine structures in magnetic reconnection with high plasma {beta}

    SciTech Connect

    Jin, S.P.; Yang, H.A.; Wang, X.G.

    2005-04-15

    Magnetic reconnection with various plasma {beta} (the ratio of plasma pressure to the magnetic pressure) is studied numerically using a 2.5 dimensional Hall magnetohydrodynamics (MHD) code developed from a multistep implicit scheme. The initial state of the Hall MHD simulation is an equilibrium Harris sheet with L{sub c}=0.5d{sub i} (where L{sub c} is the half-width of the equilibrium current layer and d{sub i} is the ion inertial length) and a zero guide field (i.e., B{sub y0}=0 at t=0). Driven by a constant boundary inflow a quasisteady fast reconnection occurs in the plasma with a low uniform resistivity. The out-of-plane magnetic field component B{sub y} is then spontaneously generated and its quadrupolar structure is shown around the X point. It is demonstrated by the comparing studies that the reconnection dynamics is controlled by the Hall effect and the effect of scalar electron pressure gradient is negligible in the generalized Ohm's law. It is also found that the openness of the magnetic separatrix angle and associated quadrupolar B{sub y} structure is enlarged as {beta} increases. When {beta}>2.0 fine structures of B{sub y} contours with reversed sign emerge. The numerical results indicate that the variations in electron velocity V{sub e} are greater than those in ion velocity V{sub i} and the decoupling of electron and ion occurs in larger scale lengths than d{sub i} as {beta} increases. Clearly, the reserve current, which is associated with the relative motion between electrons and ions, generates the fine structures of B{sub y} contours in the outflow region. Then the corresponding profile of B{sub y} component exhibits a static whistler wave signature. Enhanced wave activities observed during a Cluster crossing of the high-{beta} exterior cusp region [Y. Khotyaintsev, A. Vaivads, Y. Ogawa, B. Popielawska, M. Andre, S. Buchert, P. Decreau, B. Lavraud, and H. Reme, Ann. Geophys. 22, 2403 (2004)] might be related to the Hall effects of magnetic