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Sample records for absorption near-edge structures

  1. Three Dimensional Mapping of Nicle Oxidation States Using Full Field Xray Absorption Near Edge Structure Nanotomography

    SciTech Connect

    Nelson, G.J.; Chu, Y.; Harris, W.M.; Izzo, J.R.; Grew, K.N., Chiu, W.K.S.; Yi, J.; Andrews, J.C.; Liu, Y., Pierro, P.

    2011-04-28

    The reduction-oxidation cycling of the nickel-based oxides in composite solid oxide fuel cells and battery electrodes is directly related to cell performance. A greater understanding of nickel redox mechanisms at the microstructural level can be achieved in part using transmission x-ray microscopy (TXM) to explore material oxidation states. X-ray nanotomography combined with x-ray absorption near edge structure (XANES) spectroscopy has been applied to study samples containing distinct regions of nickel and nickel oxide (NiO) compositions. Digitally processed images obtained using TXM demonstrate the three-dimensional chemical mapping and microstructural distribution capabilities of full-field XANES nanotomography.

  2. Silicon 1s near edge X-ray absorption fine structure spectroscopy of functionalized silicon nanocrystals

    NASA Astrophysics Data System (ADS)

    Ritchie, A.; Cao, W.; Dasog, M.; Purkait, T. K.; Senger, C.; Hu, Y. F.; Xiao, Q. F.; Veinot, J. G. C.; Urquhart, S. G.

    2016-10-01

    Silicon 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of silicon nanocrystals have been examined as a function of nanocrystal size (3-100 nm), varying surface functionalization (hydrogen or 1-pentyl termination), or embedded in oxide. The NEXAFS spectra are characterized as a function of nanocrystal size and surface functionalization. Clear spectroscopic evidence for long range order is observed silicon nanocrystals that are 5-8 nm in diameter or larger. Energy shifts in the silicon 1s NEXAFS spectra of covalently functionalized silicon nanocrystals with changing size are attributed to surface chemical shifts and not to quantum confinement effects.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  4. X-ray absorption near edge structure/electron energy loss near edge structure calculation using the supercell orthogonalized linear combination of atomic orbitals method

    NASA Astrophysics Data System (ADS)

    Ching, Wai-Yim; Rulis, Paul

    2009-03-01

    Over the last eight years, a large number of x-ray absorption near edge structure (XANES) and/or electron energy loss near edge structure (ELNES) spectroscopic calculations for complex oxides and nitrides have been performed using the supercell-OLCAO (orthogonalized linear combination of atomic orbitals) method, obtaining results in very good agreement with experiments. The method takes into account the core-hole effect and includes the dipole matrix elements calculated from ab initio wavefunctions. In this paper, we describe the method in considerable detail, emphasizing the special advantages of this method for large complex systems. Selected results are reviewed and several hitherto unpublished results are also presented. These include the Y K edge of Y ions segregated to the core of a Σ31 grain boundary in alumina, O K edges of water molecules, C K edges in different types of single walled carbon nanotubes, and the Co K edge in the cyanocobalamin (vitamin B12) molecule. On the basis of these results, it is argued that the interpretation of specific features of the calculated XANES/ELNES edges is not simple for complex material systems because of the delocalized nature of the conduction band states. The long-standing notion of the 'fingerprinting' technique for spectral interpretation of experimental data is not tenable. A better approach is to fully characterize the structure under study, using either crystalline data or accurate ab initio modeling. Comparison between calculated XANES/ELNES spectra and available measurements enables us to ascertain the validity of the modeled structure. For complex crystals or structures, it is necessary to use the weighted sum of the spectra from structurally nonequivalent sites for comparison with the measured data. Future application of the supercell-OLCAO method to complex biomolecular systems is also discussed.

  5. Structural analysis of sulfur in natural rubber using X-ray absorption near-edge spectroscopy.

    PubMed

    Pattanasiriwisawa, Wanwisa; Siritapetawee, Jaruwan; Patarapaiboolchai, Orasa; Klysubun, Wantana

    2008-09-01

    X-ray absorption near-edge spectroscopy (XANES) has been applied to natural rubber in order to study the local environment of sulfur atoms in sulfur crosslinking structures introduced in the vulcanization process. Different types of chemical accelerators in conventional, semi-efficient and efficient vulcanization systems were investigated. The experimental results show the good sensitivity and reproducibility of XANES to characterize the local geometry and electronic environment of the sulfur K-shell under various conditions of vulcanization and non-vulcanization of natural rubber. Several applications of XANES in this study demonstrate an alternative way of identifying sulfur crosslinks in treated natural rubber based on differences in their spectra and oxidation states. PMID:18728323

  6. 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.

  7. Sulfur speciation in heavy petroleums: Information from X-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Waldo, Geoffrey S.; Carlson, Robert M. K.; Moldowan, J. Michael; Peters, Kenneth E.; Penner-hahn, James E.

    1991-03-01

    The chemical speciation of sulfur in heavy petroleums, petroleum source rock extracts, and source rock pyrolysis products was studied using X-ray absorption near-edge structure (XANES) spectroscopy. The good energy resolution (ca. 0.5 eV) at the sulfur K edge and the strong dependence of XANES on the sulfur environment combine to give excellent sensitivity to changes in the electronic and structural environment of the sulfur. This has permitted identification and approximate quantitation of different classes of sulfur-containing compounds (e.g., sulfur, sulfides (including disulfides and polysulfides as a group), thiophenes, sulfoxides, sulfones, sulfinic acids, sulfonic acids, and sulfate) in a series of petroleums and petroleum source rocks. Our results indicate that the sulfur speciation of geological samples can be correlated with differences in source depositional environment, thermal maturity, and aromaticity. We report organosulfur compositions for the asphaltene, maltene, and liquid Chromatographie fractions of two sulfur-rich oils. In addition, we find that the organosulfur species in some, but not all, oils are subject to oxidation upon storage and thus may also be susceptible to oxidation in shallow reservoirs exposed to oxic waters. This work illustrates the utility of XANES as a direct spectroscopic probe for the quantitative determination of sulfur species in geological samples.

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

    NASA Astrophysics Data System (ADS)

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

    2006-11-01

    The changes in the structure and composition of vapor-deposited ice films irradiated at 20K with soft x-ray photons (3-900eV) and their subsequent evolution with temperatures between 20 and 150K have been investigated by near-edge x-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K edge. We observe the hydroxyl OH, the atomic oxygen O, and the hydroperoxyl HO2 radicals, as well as the oxygen O2 and hydrogen peroxide H2O2 molecules in irradiated porous amorphous solid water (p-ASW) and crystalline (Icryst) ice films. The evolution of their concentrations with the temperature indicates that HO2, O2, and H2O2 result from a simple step reaction fuelled by OH, where O2 is a product of HO2 and HO2 a product of H2O2. The local order of ice is also modified, whatever the initial structure is. The crystalline ice Icryst becomes amorphous. The high-density amorphous phase (Iah ) of ice is observed after irradiation of the p-ASW film, whose initial structure is the normal low-density form of the amorphous ice (Ial). The phase Iah is thus peculiar to irradiated ice and does not exist in the as-deposited ice films. A new "very high density" amorphous phase—we call Iavh—is obtained after warming at 50K the irradiated p-ASW ice. This phase is stable up to 90K and partially transforms into crystalline ice at 150K.

  9. Solving local structure around dopants in metal nanoparticles with ab initio modeling of X-ray absorption near edge structure

    DOE PAGES

    Timoshenko, J.; Shivhare, A.; Scott, R. W.; Lu, D.; Frenkel, A. I.

    2016-06-30

    We adopted ab-initio X-ray Absorption Near Edge Structure (XANES) modelling for structural refinement of local environments around metal impurities in a large variety of materials. Our method enables both direct modelling, where the candidate structures are known, and the inverse modelling, where the unknown structural motifs are deciphered from the experimental spectra. We present also estimates of systematic errors, and their influence on the stability and accuracy of the obtained results. We illustrate our approach by following the evolution of local environment of palladium atoms in palladium-doped gold thiolate clusters upon chemical and thermal treatments.

  10. Structural changes of nucleic acid base in aqueous solution as observed in X-ray absorption near edge structure (XANES)

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    X-ray absorption near edge structure (XANES) spectra for adenine-containing nucleotides, adenosine 5‧-monophosphate (AMP) and adenosine 5‧-triphosphate (ATP) in aqueous solutions at the nitrogen K-edge region were measured. The two intense peaks in XANES spectra are assigned to transitions of 1s electrons to the π∗ orbitals of different types of N atoms with particular bonding characteristics. The difference between their spectra is ascribed to protonation of a particular N atom. Similarity observed in XANES spectra of guanosine 5‧-monophosphate (GMP) and ATP is also interpreted as similar bonding characters of the N atoms in the nucleobase moiety.

  11. Oxygen on Ni(111): A multiple-scattering analysis of the near-edge x-ray-absorption fine structure

    NASA Astrophysics Data System (ADS)

    Pedio, M.; Becker, L.; Hillert, B.; D'addato, S.; Haase, J.

    1990-04-01

    Oxygen chemisorption and oxide formation on a Ni(111) surface have been monitored by using the near-edge x-ray-absorption fine-structure technique. The adsorption site of oxygen in the p(2×2) and (√3 × √3 )R30° superstructures has been determined by a multiple-scattering analysis. In both structures the oxygen occupies a threefold-coordinated fcc site with a nearest-neighbor O-Ni bond length of 1.85+/-0.05 Å on a Ni(111) surface relaxed outwards by ~0.15 Å.

  12. 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.

  13. Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography

    SciTech Connect

    Nelson, George J.; Harris, William M.; Izzo, John R. Jr.; Grew, Kyle N.; Chiu, Wilson K. S.; Chu, Yong S.; Yi, Jaemock; Andrews, Joy C.; Liu Yijin; Pianetta, Piero

    2011-04-25

    The reduction-oxidation cycling of the nickel-based oxides in composite solid oxide fuel cells and battery electrodes is directly related to cell performance. A greater understanding of nickel redox mechanisms at the microstructural level can be achieved in part using transmission x-ray microscopy (TXM) to explore material oxidation states. X-ray nanotomography combined with x-ray absorption near edge structure (XANES) spectroscopy has been applied to study samples containing distinct regions of nickel and nickel oxide (NiO) compositions. Digitally processed images obtained using TXM demonstrate the three-dimensional chemical mapping and microstructural distribution capabilities of full-field XANES nanotomography.

  14. Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography

    NASA Astrophysics Data System (ADS)

    Nelson, George J.; Harris, William M.; Izzo, John R.; Grew, Kyle N.; Chiu, Wilson K. S.; Chu, Yong S.; Yi, Jaemock; Andrews, Joy C.; Liu, Yijin; Pianetta, Piero

    2011-04-01

    The reduction-oxidation cycling of the nickel-based oxides in composite solid oxide fuel cells and battery electrodes is directly related to cell performance. A greater understanding of nickel redox mechanisms at the microstructural level can be achieved in part using transmission x-ray microscopy (TXM) to explore material oxidation states. X-ray nanotomography combined with x-ray absorption near edge structure (XANES) spectroscopy has been applied to study samples containing distinct regions of nickel and nickel oxide (NiO) compositions. Digitally processed images obtained using TXM demonstrate the three-dimensional chemical mapping and microstructural distribution capabilities of full-field XANES nanotomography.

  15. Study on Coloration Mechanism of Chinese Ancient Ceramics by X-ray Absorption Near-edge Structure

    NASA Astrophysics Data System (ADS)

    Peng, Y. H.; Xie, Z.; He, J. F.; Liu, Q. H.; Pan, Z. Y.; Cheng, W. R.; Wei, S. Q.

    2013-04-01

    The Fe K-edge X-ray absorption near-edge structure (XANES) spectra of a series of ceramic shards were measured by fluorescence mode to reveal the color-generating techniques of Chinese porcelain. The analysis disclosed relationships among the chemical form of the iron, the firing conditions and the colors of the ceramics. The results indicate that the coloration for different ceramics depend on the valence states of iron as the main color element in glaze and the proportion of Fe2+ and Fe3+ was attributed to the baking technology. The findings provide important information for archaeologist on the coloration researches.

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

    SciTech Connect

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

    2009-12-11

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

  17. Reduced chromium in olivine grains from lunar basalt 15555 - X-ray Absorption Near Edge Structure (XANES)

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Jones, K. W.; Gordon, B.; Rivers, M. L.; Bajt, S.; Smith, J. V.

    1993-01-01

    The oxidation state of Cr in 200-micron regions within individual lunar olivine and pyroxene grains from lunar basalt 15555 was inferred using X-ray Absorption Near Edge Structure (XANES). Reference materials had previously been studied by optical absorption spectroscopy and included Cr-bearing borosilicate glasses synthesized under controlled oxygen fugacity and Cr-doped olivines. The energy dependence of XANES spectral features defined by these reference materials indicated that Cr is predominantly divalent in the lunar olivine and trivalent in the pyroxene. These results, coupled with the apparent f(02)-independence of partitioning coefficients for Cr into olivine, imply that the source magma was dominated by divalent Cr at the time of olivine crystallization.

  18. 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.

  19. 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.

  20. Diffraction Anomalous Near-Edge Structure

    NASA Astrophysics Data System (ADS)

    Moltaji, Habib O., Jr.

    1995-11-01

    To determine the atomic structure about atom of an element in a sample of a condensed multicomponent single crystal, contrast radiation is proposed with the use of Diffraction Anomalous Near-Edge Structure (DANES), which combines the long-range order sensitivity of the x-ray diffraction and short-range order of the x-ray absorption near-edge techniques. This is achieved by modulating the photon energy of the x-ray beam incident on the sample over a range of energies near an absorption edge of the selected element. Due to anomalous dispersion, x-ray diffraction, and x-ray absorption, the DANES intensity with respect to the selected element is obtained in a single experiment. I demonstrate that synchrotron DANES measurements for the single crystal of thin film and the powder samples and provide the same local atomic structural information as the x-ray absorption near-edge with diffraction condition and can be used to provide enhanced site selectivity. I demonstrate calculations of DAFS intensity and measurements of polarized DANES and XANES intensity.

  1. Anisotropy of chemical bonds in collagen molecules studied by X-ray absorption near-edge structure (XANES) spectroscopy.

    PubMed

    Lam, Raymond S K; Metzler, Rebecca A; Gilbert, Pupa U P A; Beniash, Elia

    2012-03-16

    Collagen type I fibrils are the major building blocks of connective tissues. Collagen fibrils are anisotropic supramolecular structures, and their orientation can be revealed by polarized light microscopy and vibrational microspectroscopy. We hypothesized that the anisotropy of chemical bonds in the collagen molecules, and hence their orientation, might also be detected by X-ray photoemission electron spectromicroscopy (X-PEEM) and X-ray absorption near-edge structure (XANES) spectroscopy, which use linearly polarized synchrotron light. To test this hypothesis, we analyzed sections of rat-tail tendon, composed of parallel arrays of collagen fibrils. The results clearly indicate that XANES-PEEM is sensitive to collagen fibril orientation and, more specifically, to the orientations of carbonyl and amide bonds in collagen molecules. These data suggest that XANES-PEEM is a promising technique for characterizing the chemical composition and structural organization at the nanoscale of collagen-based connective tissues, including tendons, cartilage, and bone.

  2. Interaction between Pt nanoparticles and carbon nanotubes An X-ray absorption near edge structures (XANES) study

    NASA Astrophysics Data System (ADS)

    Zhou, Jigang; Zhou, Xingtai; Sun, Xuhui; Li, Ruying; Murphy, Michael; Ding, Zhifeng; Sun, Xueliang; Sham, Tsun-Kong

    2007-04-01

    The interaction between Pt and carbon in Pt nanoparticles (NPs)-carbon nanotubes (CNTs) composite has been investigated with Pt M 3-edge and C K-edge X-ray absorption near edge structures (XANES) recorded in surface-sensitive total electron yield (TEY) and bulk-sensitive fluorescence yield (FLY). XANES in TEY shows that Pt NPs on CNTs have a fcc structure and the white-line features of the XANES strongly support that the crystalline Pt NPs interact with CNTs through synergic bonding involving charge redistribution between C 2p-derived states and Pt 5d bands. Such interaction facilitates the immobilization of Pt NPs on CNT surface without generating oxygenated functional groups.

  3. Nitrogen K-edge x-ray absorption near edge structure of pyrimidine-containing nucleotides in aqueous solution

    SciTech Connect

    Shimada, Hiroyuki Minami, Hirotake; Okuizumi, Naoto; Sakuma, Ichiro; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    2015-05-07

    X-ray absorption near edge structure (XANES) was measured at energies around the N K-edge of the pyrimidine-containing nucleotides, cytidine 5′-monophosphate (CMP), 2′-deoxythymidine 5′-monophosphate (dTMP), and uridine 5′-monophosphate (UMP), in aqueous solutions and in dried films under various pH conditions. The features of resonant excitations below the N K-edge in the XANES spectra for CMP, dTMP, and UMP changed depending on the pH of the solutions. The spectral change thus observed is systematically explained by the chemical shift of the core-levels of N atoms in the nucleobase moieties caused by structural changes due to protonation or deprotonation at different proton concentrations. This interpretation is supported by the results of theoretical calculations using density functional theory for the corresponding nucleobases in the neutral and protonated or deprotonated forms.

  4. Grazing exit versus grazing incidence geometry for x-ray absorption near edge structure analysis of arsenic traces

    SciTech Connect

    Meirer, F.; Streli, C.; Wobrauschek, P.; Zoeger, N.; Pepponi, G.

    2009-04-01

    In the presented study the grazing exit x-ray fluorescence was tested for its applicability to x-ray absorption near edge structure analysis of arsenic in droplet samples. The experimental results have been compared to the findings of former analyses of the same samples using a grazing incidence (GI) setup to compare the performance of both geometries. Furthermore, the investigations were accomplished to gain a better understanding of the so called self-absorption effect, which was observed and investigated in previous studies using a GI geometry. It was suggested that a normal incidence-grazing-exit geometry would not suffer from self-absorption effects in x-ray absorption fine structure (XAFS) analysis due to the minimized path length of the incident beam through the sample. The results proved this assumption and in turn confirmed the occurrence of the self-absorption effect for GI geometry. Due to its lower sensitivity it is difficult to apply the GE geometry to XAFS analysis of trace amounts (few nanograms) of samples but the technique is well suited for the analysis of small amounts of concentrated samples.

  5. 3D Imaging of Nickel Oxidation States using Full Field X-ray Absorption Near Edge Structure Nanotomography

    SciTech Connect

    Nelson, George; Harris, William; Izzo, John; Grew, Kyle N.

    2012-01-20

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

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

    NASA Astrophysics Data System (ADS)

    Benuzzi Mounaix, Alessandra

    2011-06-01

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

  7. 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.

  8. In situ micro X-ray absorption near edge structure study of microbiologically reduced selenite (SeO 32-)

    NASA Astrophysics Data System (ADS)

    Oger, Phil M.; Daniel, I.; Cournoyer, B.; Simionovici, A.

    2004-10-01

    The possibility exists that life originated from high-pressure, high-temperature environments fueled by the reduction of metal ions. These environments or their modern equivalent cannot be studied by standard microbiological techniques, but, metal reduction and oxidation kinetics may be accessible to X-ray analyses. We have evaluated the compatibility, the sensitivity and the efficiency of μX-ray absorption near edge structure (μXANES) and μX-ray fluorescence (μXRF) to study the kinetics of selenite reduction by prokaryotes under controlled pressure and temperature using a dedicated diamond anvil cell. These tests were performed in quartz capillaries, but the experimental set up was designed so as to accommodate the diamond anvil cell. Using μXRF coupled with μXANES, we show that we can detect and quantify Se species in solution from as low as 2 ppm. Lower quantification levels could be readily obtained by increasing counting time or incident flux and changing detectors. The chemical composition of mixtures of different selenium species has been directly determined by a combination of individual μXANES spectra made from standard solutions. The sensitivity of this method is sufficiently high to allow the study of the speciation of selenium in solution in situ and in vivo in the diamond anvil cell under controlled pressure and temperature.

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

    NASA Astrophysics Data System (ADS)

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

    1997-02-01

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

  10. [Chlorine speciation and concentration in cultivated soil in the northeastern China studied by X-ray absorption near edge structure].

    PubMed

    Li, Jing; Lang, Chun-Yan; Ma, Ling-Ling; Xu, Dian-Dou; Zheng, Lei; Lu, Yu-Nanz; Cui Li-Rui; Zhang, Xiao-Meng

    2014-10-01

    A procedure has been proposed to determine chlorine speciation and concentration in soil with X-ray absorption near edge structure (XANES), and this method was applied to study the cultivated soil (bog, dark brown and black cultivated soil) in the Northeastern China. Qualitative analysis was carried out by least-squares fitting of sample spectra with standard spectra of three model compounds (NaCl, 3-chloropropionic acid, chlorophenol red). Linear correlation between the absolute fluorescence intensity of a series of NaCl standards and the Cl concentration was used as quantification standard for measuring the total Cl concentration in samples. The detection limits,relative standard deviation (RSD), recoveries were 2 mg · kg(-1), 0%-5% and 77%-133%, respectively. The average concentration of total Cl was 19 mg · kg(-1). The average relative content was as high as 61% of organochlorine with the concentration of 1-2 times as high as the concentration of inorganic chloride. The distribution trend of the total Cl, inorganic chloride and organic chlorine in different types of soil was: bog arable soil > dark brown soil > black soil. In conclusion, XANES is a reliable method to nondestructively characterize the speciation and concentration of chlorine in soil, which would provide some basic data for the future study of the chlorine's biogeochemical transformations.

  11. The speciation of soluble sulphur compounds in bacterial culture fluids by X-ray absorption near edge structure spectroscopy.

    PubMed

    Franz, Bettina; Lichtenberg, Henning; Hormes, Josef; Dahl, Christiane; Prange, Alexander

    2009-11-01

    Over the last decade X-ray absorption near edge structure (XANES) spectroscopy has been used in an increasing number of microbiological studies. In addition to other applications it has served as a valuable tool for the investigation of the sulphur globules deposited intra- or extracellularly by certain photo- and chemotrophic sulphur-oxidizing (Sox) bacteria. For XANES measurements, these deposits can easily be concentrated by filtration or sedimentation through centrifugation. However, during oxidative metabolism of reduced sulphur compounds, such as sulphide or thiosulphate, sulphur deposits are not the only intermediates formed. Soluble intermediates such as sulphite may also be produced and released into the medium. In this study, we explored the potential of XANES spectroscopy for the detection and speciation of sulphur compounds in culture supernatants of the phototrophic purple sulphur bacterium Allochromatium vinosum. More specifically, we investigated A. vinosum DeltasoxY, a strain with an in frame deletion of the soxY gene. This gene encodes an essential component of the thiosulphate-oxidizing Sox enzyme complex. Improved sample preparation techniques developed for the DeltasoxY strain allowed for the first time not only the qualitative but also the quantitative analysis of bacterial culture supernatants by XANES spectroscopy. The results thus obtained verified and supplemented conventional HPLC analysis of soluble sulphur compounds. Sulphite and also oxidized organic sulphur compounds were shown by XANES spectroscopy to be present, some of which were not seen when standard HPLC protocols were used.

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

    PubMed

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

    2015-09-01

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

  13. Sulfur 1s near edge x-ray absorption fine structure spectroscopy of thiophenic and aromatic thioether compounds

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

    Thiophenic compounds are major constituents of fossil fuels and pose problems for fuel refinement. The quantification and speciation of these compounds is of great interest in different areas such as biology, fossil fuels studies, geology, and archaeology. Sulfur 1s Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy has emerged as a qualitative and quantitative method for sulfur speciation. A firm understanding of the sulfur 1s NEXAFS spectra of organosulfur species is required for these analytical studies. To support this development, the sulfur 1s NEXAFS spectra of simple thiols and thioethers were previously examined, and are now extended to studies of thiophenic and aromatic thioether compounds, in the gas and condensed phases. High-resolution spectra have been further analyzed with the aid of Improved Virtual Orbital (IVO) and Δ(self-consistent field) ab initio calculations. Experimental sulfur 1s NEXAFS spectra show fine features predicted by calculation, and the combination of experiment and calculation has been used to improve the assignment of spectroscopic features important for the speciation and quantification of sulfur compounds. Systematic differences between gas and condensed phases are also explored; these differences suggest a significant role for conformational effects in the NEXAFS spectra of condensed species.

  14. Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Mikhlin, Yu.; Tomashevich, Ye.

    2005-05-01

    Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe2+, small quantity of Fe3+, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe3+ and a form of high-spin Fe2+ with the energy of the 3d orbitals increased by 0.3 0.8 eV; low-spin Fe2+ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe3+ and reduced density of S s Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit eg band of singlet Fe2+ along with minor contributions attributable to high-spin Fe2+ and Fe3+. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe3+ species and sulphur in oxidation state between +2 and +4.

  15. 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.

  16. 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

  17. 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

  18. Quantitative analysis of deconvolved X-ray absorption near-edge structure spectra: a tool to push the limits of the X-ray absorption spectroscopy technique.

    PubMed

    D'Angelo, Paola; Migliorati, Valentina; Persson, Ingmar; Mancini, Giordano; Della Longa, Stefano

    2014-09-15

    A deconvolution procedure has been applied to K-edge X-ray absorption near-edge structure (XANES) spectra of lanthanoid-containing solid systems, namely, hexakis(dmpu)praseodymium(III) and -gadolinium(III) iodide. The K-edges of lanthanoids cover the energy range 38 (La)-65 (Lu) keV, and the large widths of the core-hole states lead to broadening of spectral features, reducing the content of structural information that can be extracted from the raw X-ray absorption spectra. Here, we demonstrate that deconvolution procedures allow one to remove most of the instrumental and core-hole lifetime broadening in the K-edge XANES spectra of lanthanoid compounds, highlighting structural features that are lost in the raw data. We show that quantitative analysis of the deconvolved K-edge XANES spectra can be profitably used to gain a complete local structural characterization of lanthanoid-containing systems not only for the nearest neighbor atoms but also for higher-distance coordination shells. PMID:25171598

  19. Near-edge x-ray absorption fine structure examination of chemical bonding in sputter deposited boron and boron-nitride films

    SciTech Connect

    Jankowski, A.F.; Hayes, J.P.; Suthreland, D.G.J.

    1996-05-01

    Near-edge x-ray absorption fine structure (NEXAFS) is used to examine the chemical bonding in boron and boron-nitride films sputter deposited from a fully-dense, pure boron target. Reactive sputtering is used to prepare the boron-nitride and multilayered films. Although the process of sputter deposition often produces films that lack long range order, NEXAFS reveals the distinguishing features of sp{sup 2} and sp{sup 3} hybridization that are associated with different crystalline structures. The sensitivity of NEXAFS to local order further provides details in bonding modifications that exist in these films.

  20. Electronic structure of octane on Cu(1 1 1) and Ni(1 1 1) studied by near edge X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Kiguchi, Manabu; Entani, Shiro; Ikeda, Susumu; Yoshikawa, Genki; Nakai, Ikuyo; Kondoh, Hiroshi; Ohta, Toshiaki; Saiki, Koichiro

    2007-09-01

    The electronic structure of an octane film grown on Cu(1 1 1) and Ni(1 1 1) was studied using C K-edge near edge X-ray absorption fine structure (NEXAFS). A pre-peak was observed on the bulk edge onset for the 1 ML thick octane films on the metal substrates. The pre-peak originated from metal induced gap states (MIGS) in the band gap of octane. The intensity of the pre-peak for octane/Ni(1 1 1) was the same as that of octane/Cu(1 1 1), suggesting that there was little difference in the density of unoccupied MIGS between the octane film on Ni(1 1 1) and Cu(1 1 1). We discuss the metal dependence of the density of unoccupied MIGS on the band structure of the metals.

  1. Micro-X-ray absorption near edge structure spectroscopy investigations of baroque tin-amalgam mirrors at BESSY using a capillary focusing system

    NASA Astrophysics Data System (ADS)

    Bartoll, J.; Röhrs, S.; Erko, A.; Firsov, A.; Bjeoumikhov, A.; Langhoff, N.

    2004-10-01

    An elliptically shaped glass monocapillary with a spatial resolution of 5 μm has been used for the fine focusing of the pre-focused X-ray beam produced by the graded-crystal monochromator beamline, KMC-2. The flux density gain of 50 was experimentally measured. The microprobe has been used in the energy range of 3.5-15 keV. Micro-X-ray fluorescence analysis (μXFA) and micro-X-ray absorption near edge structure spectroscopy (μXANES) measurements on test samples and investigations of baroque tin-amalgam mirrors were done.

  2. Development of achromatic full-field hard x-ray microscopy and its application to x-ray absorption near edge structure spectromicroscopy

    NASA Astrophysics Data System (ADS)

    Matsuyama, S.; Emi, Y.; Kino, H.; Kohmura, Y.; Yabashi, M.; Ishikawa, T.; Yamauchi, K.

    2014-09-01

    An achromatic and high-resolution hard X-ray microscope was developed, in which advanced Kirkpatrick-Baez mirror optics with four total-reflection mirrors was employed as an objective. A fine test pattern with a 100 nm feature size could successfully be resolved. Full-field imaging, in combination with X-ray absorption near edge structure (XANES) spectroscopy, was used to characterize tungsten particles. XANES spectra were obtained over the entire observation area, showing good agreement with the XANES spectrum of pure tungsten.

  3. 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.

  4. Na-induced bonding and bond-length changes for CO on Pt(111): A near-edge x-ray-absorption fine-structure study

    NASA Astrophysics Data System (ADS)

    Sette, F.; Stöhr, J.; Kollin, E. B.; Dwyer, D. J.; Gland, J. L.; Robbins, J. L.; Johnson, A. L.

    1985-03-01

    Near-edge x-ray absorption fine-structure studies above the C and O K edges for CO on Pt(111) reveal a 4-eV shift of the σ shape resonance when Na(0.2 monolayer) is coabsorbed. This allows determination of a Na-induced (0.12+/-0.03)-Å expansion of the C-O bond. Na does not affect the vertical molecular orientation on the surface. Reduction and broadening of the 1s-->2π* resonance and the CO bond lengthening in the presence of Na signifies substantially increased metal to CO backbonding.

  5. 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

  6. X-ray structure analysis of a metalloprotein with enhanced active-site resolution using in situ x-ray absorption near edge structure spectroscopy.

    PubMed

    Arcovito, Alessandro; Benfatto, Maurizio; Cianci, Michele; Hasnain, S Samar; Nienhaus, Karin; Nienhaus, G Ulrich; Savino, Carmelinda; Strange, Richard W; Vallone, Beatrice; Della Longa, Stefano

    2007-04-10

    X-ray absorption spectroscopy is exquisitely sensitive to the coordination geometry of an absorbing atom and therefore allows bond distances and angles of the surrounding atomic cluster to be measured with atomic resolution. By contrast, the accuracy and resolution of metalloprotein active sites obtainable from x-ray crystallography are often insufficient to analyze the electronic properties of the metals that are essential for their biological functions. Here, we demonstrate that the combination of both methods on the same metalloprotein single crystal yields a structural model of the protein with exceptional active-site resolution. To this end, we have collected an x-ray diffraction data set to 1.4-A resolution and Fe K-edge polarized x-ray absorption near edge structure (XANES) spectra on the same cyanomet sperm whale myoglobin crystal. The XANES spectra were quantitatively analyzed by using a method based on the multiple scattering approach, which yielded Fe-heme structural parameters with +/-(0.02-0.07)-A accuracy on the atomic distances and +/-7 degrees on the Fe-CN angle. These XANES-derived parameters were subsequently used as restraints in the crystal structure refinement. By combining XANES and x-ray diffraction, we have obtained an cyanomet sperm whale myoglobin structural model with a higher precision of the bond lengths and angles at the active site than would have been possible with crystallographic analysis alone.

  7. Femtosecond laser-induced modification of potassium-magnesium silicate glasses: An analysis of structural changes by near edge x-ray absorption spectroscopy

    SciTech Connect

    Seuthe, T.; Eberstein, M.; Hoefner, M.; Eichler, H. J.; Grehn, M.; Reinhardt, F.; Tsai, W. J.; Bonse, J.

    2012-05-28

    The effects of femtosecond laser pulse irradiation on the glass structure of alkaline silicate glasses were investigated by x-ray absorption near edge structure spectroscopy using the beamline of the Physikalisch-Technische Bundesanstalt at the electron synchrotron BESSY II in Berlin (Germany) by analyzing the magnesium K-edge absorption peak for different laser fluences. The application of fluences above the material modification threshold (2.1 J/cm{sup 2}) leads to a characteristic shift of {approx}1.0 eV in the K-edge revealing a reduced ({approx}3%) mean magnesium bond length to the ligated oxygen ions (Mg-O) along with a reduced average coordination number of the Mg ions.

  8. In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

    SciTech Connect

    McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.; Majidi, Hasti; Bunker, Bruce A.; Baxter, Jason B.

    2010-12-03

    Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example, this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.

  9. Near-edge x-ray absorption fine-structure fingerprints of bulk-amorphous and nanostructured Pd-based alloys

    SciTech Connect

    Kapaklis, V.; Poulopoulos, P.; Wilhelm, F.; Jaouen, N.; Rogalev, A.; Politis, C.

    2005-08-15

    Bulk amorphous PdCuNiP alloys have been prepared from the liquid state by means of solidification under an argon atmosphere. The addition of a small amount of Fe ({approx}5 at. %) results in the formation of nanocrystalline inclusions inside the residual amorphous matrix. Element-specific near-edge x-ray absorption fine-structure spectroscopy provides information on the electronic structure and symmetry properties of the samples. In combination with conventional {theta}-2{theta} x-ray diffraction measurements, it allows for the investigation of the modifications in structure after the addition of Fe, as well as for the determination of the most probable crystalline phases. The results are discussed in terms of thermodynamics.

  10. Temperature dependent evolution of the local electronic structure of atmospheric plasma treated carbon nanotubes: Near edge x-ray absorption fine structure study

    SciTech Connect

    Roy, S. S.; Papakonstantinou, P.; Okpalugo, T. I. T.; Murphy, H.

    2006-09-01

    Near edge x-ray absorption fine structure (NEXAFS) spectroscopy has been employed to obtain the temperature dependent evolution of the electronic structure of acid treated carbon nanotubes, which were further modified by dielectric barrier discharge plasma processing in an ammonia atmosphere. The NEXAFS studies were performed from room temperature up to 900 deg. C. The presence of oxygen and nitrogen containing functional groups was observed in C K edge, N K edge, and O K edge NEXAFS spectra of the multiwalled carbon nanotubes. The N K edge spectra revealed three types of {pi}* features, the source of which was decisively identified by their temperature dependent evolution. It was established that these features are attributed to pyridinelike, NO, and graphitelike structures, respectively. The O K edge indicated that both carbonyl (C=O), {pi}*(CO), and ether C-O-C, {sigma}*(CO), functionalities were present. Upon heating in a vacuum to 900 deg. C the {pi}*(CO) resonances disappeared while the {sigma}*(CO) resonances were still present confirming their higher thermal stability. Heating did not produce a significant change in the {pi}* feature of the C K edge spectrum indicating that the tabular structure of the nanotubes is essentially preserved following the thermal decomposition of the functional groups on the nanotube surface.

  11. Scanning transmission X-ray microscopy and X-ray absorption near-edge structure studies of N-doped carbon nanotubes sealed with N2 gas

    NASA Astrophysics Data System (ADS)

    Xie, Tian; Zhao, Yu; Zhong, Jun; Hu, Zheng; Sun, Xuhui

    2012-06-01

    N-doped carbon nanotubes (NCNTs) were synthesized and their electronic structures have been explored by X-ray absorption near-edge structure (XANES) spectroscopy. With a surface sensitive mode, XANES confirms the N-doping in NCNTs. However, with a more bulk sensitive detection mode of XANES, large amount of gaseous N2 have been found to be sealed in NCNTs, even in a high vacuum environment. The encapsulation of the ferrocene residues in carbon nanotubes had been revealed by scanning transmission X-ray microscopy (STXM), which may help for the N2 sealing. The results suggest that the easily sealed gas should be taken into consideration for CNT-based applications.

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

    SciTech Connect

    Klues, Michael; Witte, Gregor; Hermann, Klaus

    2014-01-07

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

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  15. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  17. X-ray-absorption near-edge structure of 3d transition elements in tetrahedral coordination: The effect of bond-length variation

    NASA Astrophysics Data System (ADS)

    Bianconi, A.; Fritsch, E.; Calas, G.; Petiau, J.

    1985-09-01

    The x-ray-absorption near-edge structure (XANES) of transition elements in tetrahedral coordination in crystals and glasses has been studied. We have identified the XANES features in the continuum that can be assigned to multiple scattering within the first coordination shell. The energy positions Er of the XANES peaks in the continuum follow the rule (Er-Eb)d2= const, where Eb is the energy of the prepeak, defined as the first core excitation to the bound antibonding state of T2 symmetry, and d is the interatomic distance. This plot allows us to determine the tetrahedral coordination of a vanadium impurity in a SiO2 glass and to get an estimation of the vanadium-oxygen distance (1.77+/-0.05 Å).

  18. Near-edge X-ray absorption fine structure study of disordering in Gd2(Ti1-yZry)2O7 pyrochlores.

    PubMed

    Nachimuthu, Ponnusamy; Thevuthasan, Suntharampillai; Adams, Evan M; Weber, William J; Begg, Bruce D; Mun, Bongjin S; Shuh, David K; Lindle, Dennis W; Gullikson, Eric M; Perera, Rupert C C

    2005-02-01

    Disorder in Gd2(Ti(1-y)Zry)2O7 pyrochlores, for y = 0.0-1.0, is investigated by Ti 2p and O 1s near-edge X-ray absorption fine structure spectroscopy. Ti(4+) ions are found to occupy octahedral sites in Gd2Ti2O7 with a tetragonal distortion induced by vacant oxygen sites. As Zr substitutes for Ti, the tetragonal distortion decreases, and Zr coordination increases from 6 to 8. The migration of oxygen ions from 48f or 8b sites to vacant 8a sites compensate for the increased Zr coordination, thereby reducing the number of vacant 8a sites, which further reduces the tetragonal distortion and introduces more disorder around Ti. This is evidence for simultaneous cation disorder with anion migration.

  19. Interaction of Nanostructured Calcium Silicate Hydrate with Ibuprofen Drug Molecules: X-ray Absorption Near Edge Structure (XANES) Study at the Ca, Si and O K-edge

    NASA Astrophysics Data System (ADS)

    Guo, X. X.; Sham, T. K.; Zhu, Y. J.; Hu, Y. F.

    2013-04-01

    Mesoporous calcium silicate hydrate (CSH) nanostructure has been proven to be bioactive and biocompatible, and has a bright future in the application of bone treatment among other applications. X-ray absorption near edge structure (XANES) is a powerful tool for the study of the interactions of calcium silicate hydrates with drug molecules because it is element specific and it probes the unoccupied electronic states. Herein, we report the use of the calcium, silicon and oxygen K-edge XANES spectroscopy to identify how drug molecules interact with different groups in calcium silicate hydrate mesoporous nano-carriers with different morphologies. Significant changes are observed in XANES spectra after drug loading into the calcium silicate hydrate system, especially at the Si and O K-edge. The implications of these findings are discussed.

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    The N K-edge X-ray absorption near edge structure (XANES) spectra of the purine-containing nucleotide, guanosine 5'-monophosphate (GMP), in aqueous solution are measured under various pH conditions. The spectra show characteristic peaks, which originate from resonant excitations of N 1s electrons to π* orbitals inside the guanine moiety of GMP. The relative intensities of these peaks depend on the pH values of the solution. The pH dependence is explained by the core-level shift of N atoms at specific sites caused by protonation and deprotonation. The experimental spectra are compared with theoretical spectra calculated by using density functional theory for GMP and the other purine-containing nucleotides, adenosine 5'-monophosphate, and adenosine 5'-triphosphate. The N K-edge XANES spectra for all of these nucleotides are classified by the numbers of N atoms with particular chemical bonding characteristics in the purine moiety.

  2. F K-edge X-ray absorption near-edge structure (XANES) of AlF3 polymorphs: combining ab initio calculations with Walsh correlation diagrams.

    PubMed

    Schroeder, Sven L M; Weiher, Norbert

    2006-04-21

    The X-ray absorption near-edge structures (XANES) at the F K-edge of alpha-AlF(3), beta-AlF(3) and a tetragonal AlF(3) phase are analysed by a combination of ab initio calculations with the FEFF8 code and a phenomenological discussion of local molecular orbital (MO) symmetries at the absorbing fluorine atoms. By means of a Walsh correlation diagram it is shown that the two intense absorption bands observed at the F K-edges of the AlF(3) polymorphs can be interpreted as transitions to anti-bonding MOs in [Al-F-Al]-units that have C(2v) and D(infinity h) point group symmetries. The energies of both anti-bonding orbitals are very insensitive to the angle between the Al-F bonds, which explains the close similarity of the XANES signatures from the three polymorphs. The FEFF8 analysis shows that the increased broadening of the XANES structure for beta-AlF(3) and the tetragonal AlF(3) phase is due to the superposition of the individual absorption spectra from the crystallographically distinct F species. The interpretation in terms of local MOs provides for the first time a "chemically intuitive" approach to investigations of solid fluorides by XANES spectroscopy and provides a simple conceptual framework for the discussion of the electronic structure in AlF(3) materials.

  3. 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.

  4. Near Edge X-ray Absorption Spectroscopy of Polymers

    NASA Astrophysics Data System (ADS)

    Dhez, Olivier; Ade, Harald; Urquhart, Stephen

    2001-03-01

    Synthetic and natural polymers exhibit a rich carbon, nitrogen and oxygen K-edge Near Edge X-ray Absorption Fine Structure (NEXAFS). The spectroscopic variations with chemical structure and composition are interesting in their own right. In addition, the large spectroscopic variability can be utilized for the compositional analysis of materials. This is particularly useful for high spatial resolution NEXAFS microanalysis at lateral spatial resolutions exceeding that achievable with more traditional compositional analysis tools such as Infrared and NMR spectroscopy. To increase our understanding of NEXAFS spectra and to start a database for microanalysis, we acquired carbon NEXAFS spectra of the following polymers: polycarbonate, poly(oxybenzoate-co-2,6oxynaphthoate), poly (p-phenylene terephtalamide), toluene diisocyanate polyurethane, toluene diisocyanate polyurea, 4,4'-methylene di-p-phenylene isocyanate polyurethane, 4,4'-methylene di-p-phenylene isocyanate polyurea, poly(ether ether ketone), poly(alpha-methylstyrene), poly-styrene, poly bromostyrene, poly(2-vinyl styrene), polyethylene, poly(ethylene oxide), polypropylene, poly(propylene oxide), polyisobutylene, ethylene propylene rubber, poly(methyl -metacrylate). These spectra were obtained in transmission with an energy resolution of 150 meV. The energy scale was carefully calibrated in-situ utilizing C02 gas as a reference. Spectral assignments are made based on model compounds and theoretical calculations.

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

    NASA Astrophysics Data System (ADS)

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

    1989-11-01

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

  6. Photoemission and near-edge X-ray absorption fine structure studies of the bacterial surface protein layer of Bacillus sphaericus NCTC 9602.

    PubMed

    Vyalikh, Denis V; Kirchner, Alexander; Danzenbächer, Steffen; Dedkov, Yuriy S; Kade, Andreas; Mertig, Michael; Molodtsov, Serguei L

    2005-10-01

    The electronic structure of the regular, two-dimensional bacterial surface protein layer of Bacillus sphaericus NCTC 9602 has been examined by photoemission (PE) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Both the O 1s and the N 1s core-level PE spectra show a single structure, whereas the C 1s core-level spectrum appears manifold, suggesting similar chemical states for each oxygen atom and also for each nitrogen atom, while carbon atoms exhibit a range of chemical environments in the different functional groups of the amino acids. This result is supported by the element-specific NEXAFS spectra of the unoccupied valence electronic states, which exhibit a series of characteristic NEXAFS peaks that can be assigned to particular molecular orbitals of the amino acids by applying a phenomenological building-block model. The relative contributions of the C-O, C-N, and C-C bond originating signals into the C 1s PE spectrum are in good agreement with the number ratios of the corresponding bonds calculated from the known primary structure of the bacterial surface protein. First interpretation of the PE spectrum of the occupied valence states is achieved on the basis of electronic density-of-states calculations performed for small peptides. It was found that mainly the pi clouds of the aromatic rings contribute to both the lowest unoccupied and the highest occupied molecular orbitals.

  7. Detection of intrinsic stress in cubic boron nitride films by x-ray absorption near-edge structure: Stress relaxation mechanisms by simultaneous ion implantation during growth

    SciTech Connect

    Gago, R.; Abendroth, B.; Moeller, W.; Cerda, J. I.; Jimenez, I.

    2007-11-01

    The bonding structure of cubic boron nitride (cBN) films with different levels of intrinsic stress (1-10 GPa) has been studied from the K-shell x-ray absorption near-edge structure (XANES). The stress level was tuned by the damage induced from simultaneous medium-energy ion implantation (1-10 keV) during growth. The films show a dominant sp{sup 3} arrangement for damage values below a certain threshold, with an appreciable sp{sup 3} to sp{sup 2} transformation taking place above this limit. Interestingly, the degree of stress in sp{sup 3} structures is reflected in the B 1s spectral line shape, which progressively converges to that of stress-free cBN powder for increasing ion damage. These results indicate that stress buildup and release occur at a microscopic level. The changes in the spectral line shape are correlated with modifications in the electronic structure due to the presence of intrinsic stress and bond distortion within the cubic network, as predicted by density functional theory calculations. Our findings reveal the potential of XANES spectroscopy to detect stress in disordered BN systems.

  8. 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

  9. 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

  10. X-ray-absorption near-edge structure of CuGaSe2 and ZnSe: Experiment and theory

    NASA Astrophysics Data System (ADS)

    Šipr, O.; Machek, P.; Šimůnek, A.; Vackář, J.; Horák, J.

    1997-11-01

    X-ray-absorption near-edge structure (XANES) spectra of a ternary semiconductor CuGaSe2 at the Cu, Ga, and Se edges were measured and compared with Zn and Se spectra of ZnSe, taken from the literature. Having all five absorbing atoms in nearly identical coordination environments, we investigate the influence of the electronic structure on the XANES spectra. The spectra of CuGaSe2 and of ZnSe were calculated using a real-space multiple-scattering approach and using a pseudopotential band-structure technique. Both computational methods yield spectra that are in a good agreement with experiment. The effect of the size of the cluster involved in the real-space calculation on the calculated XANES spectra is investigated. Using self-consistent muffin-tin potentials does not lead to significantly different CuGaSe2 spectra than using non-self-consistent potentials. Real-space multiple-scattering spectra calculated without core holes exhibit only minor differences with respect to those obtained for relaxed screened core holes, the largest effect being found for Zn spectrum of ZnSe. Employing unrelaxed or unscreened core hole potentials resulted in spectra that did not agree with experiment. Contrary to earlier reports, no effect of charge transfer on the calculated XANES spectra of ZnSe was found.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  12. 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

  13. X-ray absorption near-edge structure and nuclear magnetic resonance study of the lithium-sulfur battery and its components.

    PubMed

    Patel, Manu U M; Arčon, Iztok; Aquilanti, Giuliana; Stievano, Lorenzo; Mali, Gregor; Dominko, Robert

    2014-04-01

    Understanding the mechanism(s) of polysulfide formation and knowledge about the interactions of sulfur and polysulfides with a host matrix and electrolyte are essential for the development of long-cycle-life lithium-sulfur (Li-S) batteries. To achieve this goal, new analytical tools need to be developed. Herein, sulfur K-edge X-ray absorption near-edge structure (XANES) and (6,7) Li magic-angle spinning (MAS) NMR studies on a Li-S battery and its sulfur components are reported. The characterization of different stoichiometric mixtures of sulfur and lithium compounds (polysulfides), synthesized through a chemical route with all-sulfur-based components in the Li-S battery (sulfur and electrolyte), enables the understanding of changes in the batteries measured in postmortem mode and in operando mode. A detailed XANES analysis is performed on different battery components (cathode composite and separator). The relative amounts of each sulfur compound in the cathode and separator are determined precisely, according to the linear combination fit of the XANES spectra, by using reference compounds. Complementary information about the lithium species within the cathode are obtained by using (7) Li MAS NMR spectroscopy. The setup for the in operando XANES measurements can be viewed as a valuable analytical tool that can aid the understanding of the sulfur environment in Li-S batteries.

  14. Characterization of Oxygen Containing Functional Groups on Carbon Materials with Oxygen K-edge X-ray Absorption Near Edge Structure Spectroscopy

    SciTech Connect

    K Kim; P Zhu; L Na; X Ma; Y Chen

    2011-12-31

    Surface functional groups on carbon materials are critical to their surface properties and related applications. Many characterization techniques have been used to identify and quantify the surface functional groups, but none is completely satisfactory especially for quantification. In this work, we used oxygen K-edge X-ray absorption near edge structure (XANES) spectroscopy to identify and quantify the oxygen containing surface functional groups on carbon materials. XANES spectra were collected in fluorescence yield mode to minimize charging effect due to poor sample conductivity which can potentially distort XANES spectra. The surface functional groups are grouped into three types, namely carboxyl-type, carbonyl-type, and hydroxyl-type. XANES spectra of the same type are very similar while spectra of different types are significantly different. Two activated carbon samples were analyzed by XANES. The total oxygen contents of the samples were estimated from the edge step of their XANES spectra, and the identity and abundance of different functional groups were determined by fitting of the sample XANES spectrum to a linear combination of spectra of the reference compounds. It is concluded that oxygen K-edge XANES spectroscopy is a reliable characterization technique for the identification and quantification of surface functional groups on carbon materials.

  15. Three-dimensional Fe speciation of an inclusion cloud within an ultradeep diamond by confocal μ-X-ray absorption near edge structure: evidence for late stage overprint.

    PubMed

    Silversmit, Geert; Vekemans, Bart; Appel, Karen; Schmitz, Sylvia; Schoonjans, Tom; Brenker, Frank E; Kaminsky, Felix; Vincze, Laszlo

    2011-08-15

    A stream of 1-20 μm sized mineral inclusions having the negative crystal shape of its host within an "ultra-deep" diamond from Rio Soriso (Juina area, Mato Grosso State, Brazil) has been studied with confocal μ-X-ray absorption near edge structure (μXANES) at the Fe K and Mn K edges. This technique allows the three-dimensional nondestructive speciation of the Fe and Mn containing minerals within the inclusion cloud. The observed Fe-rich inclusions were identified to be ferropericlase (Fe,Mg)O, hematite and a mixture of these two minerals. Confocal μ-X-ray fluorescence (μXRF) further showed that Ca-rich inclusions were present as well, which are spatially separated from or in close contact with the Fe-rich inclusions. The inclusions are aligned along a plane, which most likely represents a primary growth zone. In the close vicinity of the inclusions, carbon coated planar features are visible. The three-dimensional distribution indicates a likely fluid overprint along an open crack. Our results imply that an imposed negative diamond shape of an inclusion alone does not exclude epigenetic formation or intense late stage overprint. PMID:21707095

  16. A laboratory-based hard x-ray monochromator for high-resolution x-ray emission spectroscopy and x-ray absorption near edge structure measurements

    SciTech Connect

    Seidler, G. T. Mortensen, D. R.; Remesnik, A. J.; Pacold, J. I.; Ball, N. A.; Barry, N.; Styczinski, M.; Hoidn, O. R.

    2014-11-15

    We report the development of a laboratory-based Rowland-circle monochromator that incorporates a low power x-ray (bremsstrahlung) tube source, a spherically bent crystal analyzer, and an energy-resolving solid-state detector. This relatively inexpensive, introductory level instrument achieves 1-eV energy resolution for photon energies of ∼5 keV to ∼10 keV while also demonstrating a net efficiency previously seen only in laboratory monochromators having much coarser energy resolution. Despite the use of only a compact, air-cooled 10 W x-ray tube, we find count rates for nonresonant x-ray emission spectroscopy comparable to those achieved at monochromatized spectroscopy beamlines at synchrotron light sources. For x-ray absorption near edge structure, the monochromatized flux is small (due to the use of a low-powered x-ray generator) but still useful for routine transmission-mode studies of concentrated samples. These results indicate that upgrading to a standard commercial high-power line-focused x-ray tube or rotating anode x-ray generator would result in monochromatized fluxes of order 10{sup 6}–10{sup 7} photons/s with no loss in energy resolution. This work establishes core technical capabilities for a rejuvenation of laboratory-based hard x-ray spectroscopies that could have special relevance for contemporary research on catalytic or electrical energy storage systems using transition-metal, lanthanide, or noble-metal active species.

  17. Identification of sources of lead in the atmosphere by chemical speciation using X-ray absorption near-edge structure (XANES) spectroscopy.

    PubMed

    Sakata, Kohei; Sakaguchi, Aya; Tanimizu, Masaharu; Takaku, Yuichi; Yokoyama, Yuka; Takahashi, Yoshio

    2014-02-01

    Sources of Pb pollution in the local atmosphere together with Pb species, major ions, and heavy metal concentrations in a size-fractionated aerosol sample from Higashi-Hiroshima (Japan) have been determined by X-ray absorption near-edge structure (XANES) spectroscopy, ion chromatography, and ICP-MS/AES, respectively. About 80% of total Pb was concentrated in fine aerosol particles. Lead species in the coarse aerosol particles were PbC2O4, 2PbCO3 Pb(OH)2, and Pb(NO3)2, whereas Pb species in the fine aerosol particles were PbC2O4, PbSO4, and Pb(NO3)2. Chemical speciation and abundance data suggested that the source of Pb in the fine aerosol particles was different from that of the coarse ones. The dominant sources of Pb in the fine aerosol particles were judged to be fly ash from a municipal solid waste incinerator and heavy oil combustion. For the coarse aerosol particles, road dust was considered to be the main Pb source. In addition to Pb species, elemental concentrations in the aerosols were also determined. The results suggested that Pb species in size-fractionated aerosols can be used to identify the origin of aerosol particles in the atmosphere as an alternative to Pb isotope ratio measurement.

  18. Phosphorus speciation in sequentially extracted agro-industrial by-products: evidence from X-ray absorption near edge structure spectroscopy.

    PubMed

    Kruse, Jens; Negassa, Wakene; Appathurai, Narayana; Zuin, Lucia; Leinweber, Peter

    2010-01-01

    The phosphorus (P) in agro-industrial by-products--a potential source of freshwater eutrophication but also a valuable fertilizer--needs to be speciated to evaluate its fate in the environment. We investigated to what extent X-ray absorption near edge structure (XANES) spectroscopy at the P K- and L2.3-edges reflected differences in sequentially extracted filter cakes from sugarcane (Saccharum officinarum L.) (FIC) and niger seed (Guizotia abyssinica Cass.; NIC) processing industry in Ethiopia. The P fractionation removed more labile (54%) and H2SO4-P (28%) from FIC than from NIC (18% labile, 12% H2SO4-P). For the FIC residues after each extraction step, linear combination (LC) fitting of P K-edge spectra provided evidence for the enrichment of Ca-P after the NaOH-extraction and its almost complete removal after the H2SO4-treatment. The LC-fitting was unsuccessful for the NIC samples, likely because of the predominance of organic P compounds. The different proportions of Ca-P compounds between FIC (large) and NIC (small) were more distinctive in L2-than in the K-edge XANES spectra. In conclusion, the added value of complementary P K- and L2.3-edge XANES was clearly demonstrated, and the P fractionation and speciation results together justify using FIC and NIC as soil amendments in the tropics.

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

    USGS Publications Warehouse

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

    2016-01-01

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

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

    SciTech Connect

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

    2014-08-07

    The N K-edge X-ray absorption near edge structure (XANES) spectra of the purine-containing nucleotide, guanosine 5{sup ′}-monophosphate (GMP), in aqueous solution are measured under various pH conditions. The spectra show characteristic peaks, which originate from resonant excitations of N 1s electrons to π* orbitals inside the guanine moiety of GMP. The relative intensities of these peaks depend on the pH values of the solution. The pH dependence is explained by the core-level shift of N atoms at specific sites caused by protonation and deprotonation. The experimental spectra are compared with theoretical spectra calculated by using density functional theory for GMP and the other purine-containing nucleotides, adenosine 5{sup ′}-monophosphate, and adenosine 5{sup ′}-triphosphate. The N K-edge XANES spectra for all of these nucleotides are classified by the numbers of N atoms with particular chemical bonding characteristics in the purine moiety.

  1. A laboratory-based hard x-ray monochromator for high-resolution x-ray emission spectroscopy and x-ray absorption near edge structure measurements

    NASA Astrophysics Data System (ADS)

    Seidler, G. T.; Mortensen, D. R.; Remesnik, A. J.; Pacold, J. I.; Ball, N. A.; Barry, N.; Styczinski, M.; Hoidn, O. R.

    2014-11-01

    We report the development of a laboratory-based Rowland-circle monochromator that incorporates a low power x-ray (bremsstrahlung) tube source, a spherically bent crystal analyzer, and an energy-resolving solid-state detector. This relatively inexpensive, introductory level instrument achieves 1-eV energy resolution for photon energies of ˜5 keV to ˜10 keV while also demonstrating a net efficiency previously seen only in laboratory monochromators having much coarser energy resolution. Despite the use of only a compact, air-cooled 10 W x-ray tube, we find count rates for nonresonant x-ray emission spectroscopy comparable to those achieved at monochromatized spectroscopy beamlines at synchrotron light sources. For x-ray absorption near edge structure, the monochromatized flux is small (due to the use of a low-powered x-ray generator) but still useful for routine transmission-mode studies of concentrated samples. These results indicate that upgrading to a standard commercial high-power line-focused x-ray tube or rotating anode x-ray generator would result in monochromatized fluxes of order 106-107 photons/s with no loss in energy resolution. This work establishes core technical capabilities for a rejuvenation of laboratory-based hard x-ray spectroscopies that could have special relevance for contemporary research on catalytic or electrical energy storage systems using transition-metal, lanthanide, or noble-metal active species.

  2. Multiple-scattering calculations of the uranium {ital L}{sub 3}-edge x-ray-absorption near-edge structure

    SciTech Connect

    Hudson, E.A.; Rehr, J.J.; Bucher, J.J.

    1995-11-15

    A theoretical study of the uranium {ital L}{sub 3}-edge x-ray absorption near-edge structure (XANES) is presented for several uranium compounds, including oxides, intermetallics, uranyl fluoride, and {alpha}-uranium. Calculations were performed using FEFF6, an {ital ab} {ital initio} multiple-scattering (MS) code that includes the most important features of current theories. The results, which account for both the fine structure {chi} and the atomiclike background {mu}{sub 0} of the absorption coefficient {mu}, are compared to new and previously measured experimental spectra, reavealing very good agreement for most systems. For several compounds, a more detailed theoretical analysis determined the influence of cluster size and scattering order upon the calculated spectra. Results indicate that MS paths and scattering paths that include rather distant atoms make significant contributions for UO{sub 2}, whereas XANES for crystals with lower symmetry and density can be modeled using only shorter single-scattering paths. In most cases, assumption of a screened final state in the calculation gives better agreement with experiment than use of an unscreened final state. The successful modeling of spectra for a variety of different uranium compounds, with differing spectral features, indicates that the semirelativistic treatment of XANES used here is adequate even for heavy elements. The well-known resonance, observed experimentally for uranyl (UO{sub 2}{sup 2+}) compounds {approx}15 eV above the white line, is successfully modeled here for the first time, using multiple-scattering paths within the O-U-O axial bonds. Overlapping muffin-tin spheres were required in the calculation, probably as a result of the short uranyl axial bonds.

  3. High-resolution X-ray absorption near edge structure studies of monophasic Tl 2Ba 2Ca 2Cu 3O 10-δ (Tl-2223) superconductor

    NASA Astrophysics Data System (ADS)

    Chen, J. M.; Chung, S. C.; Liu, R. S.

    1996-08-01

    High-resolution O K-edge and Cu L 23-edge X-ray-absorption near-edge-structure (XANES) spectra of a monophasic high-T c Tl 2Ba 2Ca 2Cu 3O 10-δ (Tl-2223) superconductor in powder form were measured using the total-electron yield (TEY) and total-X-ray-fluorescence yield (TFY) techniques. Near the O 1s edge, three distinct pre-edge peaks with maxima at 528.3, 529.6, and 530.8 eV are revealed in the TFY spectrum. On the contrary, these pre-edge peaks have almost diminished in the TEY spectrum. The observed differences between the TFY and TEY spectra can be explained by the presence of an oxygen depletion layer. We ascribe these pre-edge peaks to the core-level excitations of O 1s electrons to O 2p holes located in the CuO 2 planes, in the BaO planes, and in the TlO planes, respectively. This assignment is supported by the local-density approximation (LDA) band-structure calculations. Moreover, based on the Cu L 23-edge TFY spectrum, the high-energy structures at ˜ 932.8 and 953.0 eV are attributed to the transitions from the Cu(2p {3}/{2}, {1}/{2})3d 9L ground states to the Cu(2p {3}/{2}, {1}/{2}) -13d 10L excited states, where L denotes the O 2p ligand hole.

  4. 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.

  5. 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.

  6. 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.

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

    SciTech Connect

    Willey, Trevor M.

    2004-04-01

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

  9. Infrared and X-ray Absorption Near Edge Structure Spectroscopy Analyses of the Titan Haze Simulation (THS) Aerosols Produced at Low Temperature (200 K)

    NASA Astrophysics Data System (ADS)

    Sciamma-O'Brien, Ella; Salama, Farid

    2016-10-01

    We present our latest results on the Titan Haze Simulation (THS) experiment developed on the COSmIC simulation chamber at NASA Ames. In Titan's atmosphere, a complex organic chemistry induced by UV radiation and electron bombardment occurs between N2 and CH4 and leads to the production of larger molecules and solid aerosols. In the THS, Titan's chemistry is simulated by pulsed plasma in the stream of a supersonic expansion, at Titan-like temperature (200 K). The residence time of the gas in the pulsed plasma discharge is ~3 µs, hence the chemistry is truncated allowing us to probe the first and intermediate steps of the chemistry, by adding heavier precursors into the initial N2-CH4 gas mixture. Experiments have been performed in different gas mixtures from the simpler N2-CH4 (98:2 and 95:5), to more complex mixtures: N2-CH4-C2H2 (91:5:4 and 94.5:5:0.5), N2-CH4-C6H6 (90:5:5) and N2-CH4-C2H2-C6H6 (86:5:4:5). Both the gas and solid phases have been analyzed using a combination of in situ and ex situ diagnostics.A recent mass spectrometry analysis of the gas phase demonstrated that the THS is a unique tool to monitor the different steps of the N2-CH4 chemistry [1]. The results of the solid phase study are consistent with the chemical growth evolution observed in the gas phase. The solid phase products are in the form of grains produced in volume and not from interaction on the substrate's surface. Scanning Electron Microscopy images have shown that more complex mixtures produce larger aggregates (100-500 nm in N2-CH4, up to 5 µm in N2-CH4-C2H2-C6H6). Moreover, the morphology of the grains seems to depend on the precursors, a finding that could have an impact on Titan haze microphysical models. We will present the latest results of the infrared and x-ray absorption near edge structure spectroscopic measurements that have been performed on all four mixtures. These results provide information on the nature of the different functional groups present in our samples as

  10. Systematic oxidation of polystyrene by ultraviolet-ozone, characterized by near-edge X-ray absorption fine structure and contact angle.

    PubMed

    Klein, Robert J; Fischer, Daniel A; Lenhart, Joseph L

    2008-08-01

    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 O=C 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 degrees , due primarily to chemical heterogeneity. Annealing above T(g) allows oxygenated species to move short distances away from the surface but not diffuse further than 1-2 nm.

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

    SciTech Connect

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

    2014-11-21

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  13. X-ray absorption near edge structure and extended X-ray absorption fine structure analysis of standards and biological samples containing mixed oxidation states of chromium(III) and chromium(VI).

    PubMed

    Parsons, J G; Dokken, K; Peralta-Videa, J R; Romero-Gonzalez, J; Gardea-Torresdey, J L

    2007-03-01

    For the first time a method has been developed for the extended X-ray absorption fine structure (EXAFS) data analyses of biological samples containing multiple oxidation states of chromium. In this study, the first shell coordination and interatomic distances based on the data analysis of known standards of potassium chromate (Cr(VI)) and chromium nitrate hexahydrate (Cr(III)) were investigated. The standards examined were mixtures of the following molar ratios of Cr(VI):Cr(III), 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0. It was determined from the calibration data that the fitting error associated with linear combination X-ray absorption near edge structure (LC-XANES) fittings was approximately +/-10% of the total fitting. The peak height of the Cr(VI) pre-edge feature after normalization of the X-ray absorption (XAS) spectra was used to prepare a calibration curve. The EXAFS fittings of the standards were also investigated and fittings to lechuguilla biomass samples laden with different ratios of Cr(III) and Cr(VI) were performed as well. An excellent agreement between the XANES data and the data presented in the EXAFS spectra was observed. The EXFAS data also presented mean coordination numbers directly related to the ratios of the different chromium oxidation states in the sample. The chromium oxygen interactions had two different bond lengths at approximately 1.68 and 1.98 A for the Cr(VI) and Cr(III) in the sample, respectively. PMID:17389076

  14. X-Ray Absorption Near Edge Structure And Extended X-Ray Absorption Fine Structure Analysis of Standards And Biological Samples Containing Mixed Oxidation States of Chromium(III) And Chromium(VI)

    SciTech Connect

    Parsons, J.G.; Dokken, K.; Peralta-Videa, J.R.; Romero-Gonzalez, J.; Gardea-Torresdey, J.L.

    2009-06-02

    For the first time a method has been developed for the extended X-ray absorption fine structure (EXAFS) data analyses of biological samples containing multiple oxidation states of chromium. In this study, the first shell coordination and interatomic distances based on the data analysis of known standards of potassium chromate (Cr(VI)) and chromium nitrate hexahydrate (Cr(III)) were investigated. The standards examined were mixtures of the following molar ratios of Cr(VI):Cr(III), 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0. It was determined from the calibration data that the fitting error associated with linear combination X-ray absorption near edge structure (LC-XANES) fittings was approximately {+-}10% of the total fitting. The peak height of the Cr(VI) pre-edge feature after normalization of the X-ray absorption (XAS) spectra was used to prepare a calibration curve. The EXAFS fittings of the standards were also investigated and fittings to lechuguilla biomass samples laden with different ratios of Cr(III) and Cr(VI) were performed as well. An excellent agreement between the XANES data and the data presented in the EXAFS spectra was observed. The EXFAS data also presented mean coordination numbers directly related to the ratios of the different chromium oxidation states in the sample. The chromium oxygen interactions had two different bond lengths at approximately 1.68 and 1.98 {angstrom} for the Cr(VI) and Cr(III) in the sample, respectively.

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

    PubMed Central

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

    2016-01-01

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

  16. Element distribution and iron speciation in mature wheat grains (Triticum aestivum L.) using synchrotron X-ray fluorescence microscopy mapping and X-ray absorption near-edge structure (XANES) imaging.

    PubMed

    De Brier, Niels; Gomand, Sara V; Donner, Erica; Paterson, David; Smolders, Erik; Delcour, Jan A; Lombi, Enzo

    2016-08-01

    Several studies have suggested that the majority of iron (Fe) and zinc (Zn) in wheat grains are associated with phytate, but a nuanced approach to unravel important tissue-level variation in element speciation within the grain is lacking. Here, we present spatially resolved Fe-speciation data obtained directly from different grain tissues using the newly developed synchrotron-based technique of X-ray absorption near-edge spectroscopy imaging, coupling this with high-definition μ-X-ray fluorescence microscopy to map the co-localization of essential elements. In the aleurone, phosphorus (P) is co-localized with Fe and Zn, and X-ray absorption near-edge structure imaging confirmed that Fe is chelated by phytate in this tissue layer. In the crease tissues, Zn is also positively related to P distribution, albeit less so than in the aleurone. Speciation analysis suggests that Fe is bound to nicotianamine rather than phytate in the nucellar projection, and that more complex Fe structures may also be present. In the embryo, high Zn concentrations are present in the root and shoot primordium, co-occurring with sulfur and presumably bound to thiol groups. Overall, Fe is mainly concentrated in the scutellum and co-localized with P. This high resolution imaging and speciation analysis reveals the complexity of the physiological processes responsible for element accumulation and bioaccessibility. PMID:27038325

  17. Element distribution and iron speciation in mature wheat grains (Triticum aestivum L.) using synchrotron X-ray fluorescence microscopy mapping and X-ray absorption near-edge structure (XANES) imaging.

    PubMed

    De Brier, Niels; Gomand, Sara V; Donner, Erica; Paterson, David; Smolders, Erik; Delcour, Jan A; Lombi, Enzo

    2016-08-01

    Several studies have suggested that the majority of iron (Fe) and zinc (Zn) in wheat grains are associated with phytate, but a nuanced approach to unravel important tissue-level variation in element speciation within the grain is lacking. Here, we present spatially resolved Fe-speciation data obtained directly from different grain tissues using the newly developed synchrotron-based technique of X-ray absorption near-edge spectroscopy imaging, coupling this with high-definition μ-X-ray fluorescence microscopy to map the co-localization of essential elements. In the aleurone, phosphorus (P) is co-localized with Fe and Zn, and X-ray absorption near-edge structure imaging confirmed that Fe is chelated by phytate in this tissue layer. In the crease tissues, Zn is also positively related to P distribution, albeit less so than in the aleurone. Speciation analysis suggests that Fe is bound to nicotianamine rather than phytate in the nucellar projection, and that more complex Fe structures may also be present. In the embryo, high Zn concentrations are present in the root and shoot primordium, co-occurring with sulfur and presumably bound to thiol groups. Overall, Fe is mainly concentrated in the scutellum and co-localized with P. This high resolution imaging and speciation analysis reveals the complexity of the physiological processes responsible for element accumulation and bioaccessibility.

  18. Thermo-Active Behavior of Ethylene-Vinyl Acetate | Multiwall Carbon Nanotube Composites Examined by in Situ near-Edge X-ray Absorption Fine-Structure Spectroscopy

    PubMed Central

    2015-01-01

    NEXAFS spectroscopy was used to investigate the temperature dependence of thermally active ethylene-vinyl acetate | multiwall carbon nanotube (EVA|MWCNT) films. The data shows systematic variations of intensities with increasing temperature. Molecular orbital assignment of interplaying intensities identified the 1s → π*C=C and 1s → π*C=O transitions as the main actors during temperature variation. Furthermore, enhanced near-edge interplay was observed in prestrained composites. Because macroscopic observations confirmed enhanced thermal-mechanical actuation in prestrained composites, our findings suggest that the interplay of C=C and C=O π orbitals may be instrumental to actuation. PMID:24803975

  19. Temperature dependent electronic structure of Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film probed by X-ray absorption near edge structure

    SciTech Connect

    Zhang, Bangmin; Sun, Cheng-Jun E-mail: msecgm@nus.edu.sg; Heald, Steve M.; Chen, Jing-Sheng; Moog Chow, Gan E-mail: msecgm@nus.edu.sg; Venkatesan, T.

    2014-05-07

    The Mn K edge X-ray absorption near edge structures (XANES) of Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film (100 nm) on (001) LaAlO{sub 3} substrate was measured at different temperatures to probe the MnO{sub 6} octahedron distortion and corresponding electronic structure. The absorption of high temperature paramagnetic-insulator phase differed from that of the low temperature ferromagnetic-metal phase. The temperature-dependent absorption intensity of Mn K edge XANES was correlated with the relaxation of distorted MnO{sub 6} octahedron, which changed the crystal field acting on the Mn site and the related electronic structure and properties. At low temperature, the splitting of Mn majority e{sub g} orbitals decreased and the density of states above the Fermi level increased in the relaxed MnO{sub 6} octahedron, as reflected by a wider separation between two sub-peaks in the pre-edge XANES spectra.

  20. X-ray absorption near-edge structure (XANES) studies on Sb-doped Bi2UO6 at Bi and U edges

    NASA Astrophysics Data System (ADS)

    Yadav, A. K.; Misra, N. L.; Dhara, Sangita; Phatak, Rohan; Poswal, A. K.; Jha, S. N.; Bhattacharyya, D.

    2013-02-01

    X-ray absorption spectroscopy (XAS) measurements at Bi and U LIII edges with synchrotron radiation have been carried out on Bi2-xSbxUO6 samples for x= 0.04, 0.08, 0.12, 0.16 and 0.40 which are possible by-products of Bi based coolant and Uranium based fuels in advanced high temperature nuclear reactors. The chemical shift of the Bi absorption edges in the samples have been determined accurately from the XANES region of the X-ray absorption spectra and have been explained in terms of the difference in electronegativity values of Sb and Bi. The chemical shift of absorption edges show systematic variation only upto x = 0.08 (i.e., 4% Sb doping), which shows that the Sb enter in the matrix properly up to 4% doping concentration. The local structure of U is found to remain unchanged on Sb doping indicating clearly that Sb dopants preferably replace Bi atoms.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  2. Probing cation antisite disorder in Gd2 Ti2 O7 pyrochlore by site-specific near-edge x-ray-absorption fine structure and x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Nachimuthu, P.; Thevuthasan, S.; Engelhard, M. H.; Weber, W. J.; Shuh, D. K.; Hamdan, N. M.; Mun, B. S.; Adams, E. M.; McCready, D. E.; Shutthanandan, V.; Lindle, D. W.; Balakrishnan, G.; Paul, D. M.; Gullikson, E. M.; Perera, R. C. C.; Lian, J.; Wang, L. M.; Ewing, R. C.

    2004-09-01

    Disorder in Gd2Ti2O7 is investigated by near-edge x-ray-absorption fine structure (NEXAFS) and x-ray photoelectron spectroscopy (XPS). NEXAFS shows Ti4+ ions occupy octahedral sites with a tetragonal distortion induced by vacant oxygen sites. O1s XPS spectra obtained with a charge neutralization system from Gd2Ti2O7(100) and the Gd2Ti2O7 pyrochlore used by Chen [Phys. Rev. Lett. 88, 105901 (2002)], both yielded a single peak, unlike the previous result on the latter that found two peaks. The current results give no evidence for an anisotropic distribution of Ti and O. The extra features reported in the aforementioned communication resulted from charging effects and incomplete surface cleaning. Thus, a result confirming the direct observation of simultaneous cation-anion antisite disordering and lending credence to the split vacancy model has been clarified.

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

    SciTech Connect

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

    2009-10-21

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

  4. Effects of strain relaxation in Pr0.67Sr0.33MnO3 films probed by polarization dependent X-ray absorption near edge structure

    DOE PAGES

    zhang, Bangmin; Chen, Jingsheng; Venkatesan, T.; Sun, Cheng -Jun; Heald, Steve M.; Chow, Gan Moog; Yang, Ping; Chi, Xiao; Lin, Weinan

    2016-01-28

    In this study, the Mn K edge X-ray absorption near edge structure (XANES) of Pr0.67Sr0.33MnO3 films with different thicknesses on (001) LaAlO3 substrate were measured, and the effects of strain relaxation on film properties were investigated. The films experienced in-plane compressive strain and out-of-plane tensile strain. Strain relaxation evolved with the film thickness. In the polarization dependent XANES measurements, the in-plane (parallel) and out-of-plane (perpendicular) XANES spectrocopies were anisotropic with different absorption energy Er. The resonance energy Er along two directions shifted towards each other with increasing film thickness. Based on the X-ray diffraction results, it was suggested that themore » strain relaxation weakened the difference of the local environment and probability of electronic charge transfer (between Mn 3d and O 2p orbitals) along the in-plane and out-of-plane directions, which was responsible for the change of Er. XANES is a useful tool to probe the electronic structures, of which the effects on magnetic properties with the strain relaxation was also been studied.« less

  5. Cationic vacancies and anomalous spectral-weight transfer in Ti1-xTaxO2 thin films studied via polarization-dependent near-edge x-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Qi, Dong-Chen; Barman, Arkajit Roy; Debbichi, Lamjed; Dhar, S.; Santoso, Iman; Asmara, Teguh Citra; Omer, Humair; Yang, Kesong; Krüger, Peter; Wee, Andrew T. S.; Venkatesan, T.; Rusydi, Andrivo

    2013-06-01

    We report the electronic structures of Ta-doped anatase TiO2 thin films grown by pulsed laser deposition (PLD) with varying magnetization using a combination of first-principles calculations and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. The roles of Ta doping and Ti vacancies are clarified, and the observed room-temperature ferromagnetism is attributed to the localized magnetic moments at Ti vacancy sites ferromagnetically ordered by electron charge carriers. O K-edge spectra exhibit significant polarization dependence which is discussed and supported by first-principles calculations in relation to both the crystal symmetry and the formation of defects. In particular, anomalous spectral-weight transfer across the entire O K edge for the ferromagnetic thin film is associated exclusively with the occurrence of Ti vacancies and strong correlation effects, which result in the enhancement of the direct interaction between oxygen sites and of the anisotropy of the eg-pσ hybridizations in the out-of-plane component. Our results show that O K-edge NEXAFS spectra can provide reliable experimental probes capable of revealing cationic defects that are intimately related to the ferromagnetism in transition metal oxides.

  6. 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.

  7. Chemical forms of sulfur in geological and archeological asphaltenes from Middle East, France, and Spain determined by sulfur K- and L-edge X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Sarret, Géraldine; Connan, Jacques; Kasrai, Masoud; Bancroft, G. Michael; Charrié-Duhaut, Armelle; Lemoine, Sylvie; Adam, Pierre; Albrecht, Pierre; Eybert-Bérard, Laurent

    1999-11-01

    Asphaltene samples extracted from archeological and geological bitumens from the Middle East, France, and Spain were studied by sulfur K- and L-edge X-ray absorption near-edge structure (XANES) spectroscopy in combination with isotopic analyses (δ 13C and δD). Within each series, the samples were genetically related by their δ 13C values. The gross and elemental composition and the δD values were used to characterize the weathering state of the samples. Sulfur K- and L-edge XANES results show that in all the samples, dibenzothiophenes are the dominant forms of sulfur. In the least oxidized asphaltenes, minor species include disulfides, alkyl and aryl sulfides, and sulfoxides. With increasing alteration the proportion of oxidized sulfur (sulfoxides, sulfones, sulfonates and sulfates) increases, whereas the disulfide and sulfide content decreases. This evolution is observed in all the series, regardless of the origin of the asphaltenes. This work illustrates the advantages of XANES spectroscopy as a selective probe for determining sulfur speciation in natural samples. It also shows that S K- and L-edge XANES spectroscopy are complementary for identifying the oxidized and reduced forms of sulfur, respectively.

  8. Effect of heat treatment on the activity and stability of PtCo/C catalyst and application of in-situ X-ray absorption near edge structure for proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Lin, Rui; Zhao, Tiantian; Shang, Mingfeng; Wang, Jianqiang; Tang, Wenchao; Guterman, Vladimir E.; Ma, Jianxin

    2015-10-01

    For the purpose of reducing the cost and improving the performance of the proton exchange membrane fuel cell (PEMFC), some low-Pt or non-Pt catalysts have been studied in recent years. PtCo/C electrocatalysts are synthesized by a two-step reduction approach followed by the heat treatment. PtCo metal particles are uniformly dispersed on the surface of XC-72 carbon support, with a uniform particle size distribution. The PtCo/C catalyst after 400 °C heat treatment has the best electrochemical performance among the as-prepared catalysts, even superior to the commercial Pt/C catalyst. In the durability test, PtCo/C-400 also shows excellent stability with only 6.9% decline of electrochemical surface area (ECSA) after 1000 cyclic voltammetry (CV) cycles. In-situ X-ray absorption near edge structure (XANES) technique is conducted to explore the nanostructure change of Pt during the PEMFC operation. For PtCo/C catalyst, with the fuel cell operation potential decreasing from open circuit voltage (OCV) to 0.3 V, the Pt L3 white line intensity decreases continuously, indicating the decline of Pt 5d-vacancy due to the adsorption of oxygenated species.

  9. Near-edge x-ray absorption fine-structure study of ion-beam-induced phase transformation in Gd2(Ti1-yZry)2O7

    NASA Astrophysics Data System (ADS)

    Nachimuthu, P.; Thevuthasan, S.; Shutthanandan, V.; Adams, E. M.; Weber, W. J.; Begg, B. D.; Shuh, D. K.; Lindle, D. W.; Gullikson, E. M.; Perera, R. C. C.

    2005-02-01

    The structural and electronic properties of Gd2(Ti1-yZry)2O7 (y =0-1) pyrochlores following a 2.0-MeV Au2+ ion-beam irradiation (˜5.0×1014Au2+/cm2) have been investigated by Ti2p and O1s near-edge x-ray absorption fine structure (NEXAFS). The irradiation of Gd2(Ti1-yZry)2O7 leads to the phase transformation from the ordered pyrochlore structure (Fd3m) to the defect fluorite structure (Fm3m) regardless of Zr concentration. Irradiated Gd2(Ti1-yZry)2O7 with y ⩽0.5 are amorphous, although significant short-range order is present. Contrasting to this behavior, compositions with y ⩾0.75 retain crystallinity in the defect fluorite structure following irradiation. The local structures of Zr4+ in the irradiated Gd2(Ti1-yZry)2O7 with y ⩾0.75 determined by NEXAFS are the same as in the cubic fluorite-structured yttria-stabilized zirconia (Y -ZrO2), thereby providing conclusive evidence for the phase transformation. The TiO6 octahedra present in Gd2(Ti1-yZry)2O7 are completely modified by ion-beam irradiation to TiOx polyhedra, and the Ti coordination is increased to eight with longer Ti -O bond distances. The similarity between cation sites and the degree of disorder in Gd2Zr2O7 facilitate the rearrangement and relaxation of Gd, Zr, and O ions/defects. This inhibits amorphization during the ion-beam-induced phase transition to the radiation-resistant defect fluorite structure, which is in contrast to the ordered Gd2Ti2O7.

  10. Speciation of deeply buried TiOx nanolayers with grazing-incidence x-ray fluorescence combined with a near-edge x-ray absorption fine-structure investigation

    NASA Astrophysics Data System (ADS)

    Pollakowski, Beatrix; Beckhoff, Burkhard; Reinhardt, Falk; Braun, Stefan; Gawlitza, Peter

    2008-06-01

    Nondestructive methods based on electron emission may encounter serious difficulties when probing the chemical state of deeply buried nanolayers due to restricted information depth. The purpose of the present work is to evaluate to which extent photon emission can overcome these restrictions. Grazing-incidence x-ray fluorescence combined with a near-edge x-ray absorption fine-structure investigation (GIXRF-NEXAFS) offers access to depth-resolving analysis of buried nanolayers with respect to both the chemical speciation and the layer composition. By varying the angle of incidence, the penetration depth can be tuned from a few to several hundreds of nanometers. The information depth of the emitted fluorescence radiation is in the same general range as the soft x-ray regime. Initial measurements were performed on nominally 30 nm thick titanium nanolayers oxidized to different extents and buried below 5 nm carbon layers. These layered structures were produced by means of ion beam sputtering deposition. The plane grating monochromator beamline for undulator radiation in the laboratory of the Physikalisch-Technische Bundesanstalt at the electron storage ring BESSY II provides tunable radiation of both well-known flux and high spectral purity for GIXRF-NEXAFS studies. The current results confirm that GIXRF-NEXAFS has the potential to substantially contribute to the speciation of deeply buried nanolayers. The analysis of measurements at a constant incident angle demonstrated that it is not possible to find an angle of incidence for the NEXAFS region to ensure a stable penetration depth. However, appropriate angular corrections can ensure a constant mean penetration depth, in particular, in the vicinity of absorption edges.

  11. Study on the d state of platinum in Pt/SiO sub 2 and Na/Pt/SiO sub 2 catalysts under C double bond C hydrogenation conditions by X-ray absorption near-edge structure spectroscopy

    SciTech Connect

    Yoshitake, Hideaki; Iwasawa, Yasuhiro )

    1991-09-19

    The change in the d-electron density of platinum during D{sub 2} + CH{sub 2}{double bond}CHX reactions on Pt/SiO{sub 2} and Na/Pt/SiO{sub 2} catalysts and its influence on the catalysis were studied by X-ray absorption near-edge structure (XANES) spectroscopy, kinetics and FT-IR. It was demonstrated from the change of the white lines in XANES spectra at Pt L{sub 2} and L{sub 3} edges that CH{sub 2}{double bond}CHX (X = H, CH{sub 3}, COCH{sub 3}, CF{sub 3}, and CN) is adsorbed on the Pt surface and extracts the electrons of the d state. Hence, the deuterogenation rate is reduced as the value of Hammett's {sigma}{sub P} increases. The linear free energy relationship between the reaction rate and {sigma}{sub P} was observed for the deuterogenation of CH{sub 2}{double bond}CHX. The rate of ethene deuterogenation was promoted by Na{sub 2}O addition. The electron density of unoccupied d states of pt under vacuum decreased by Na{sub 2}O addition, indicating the electron donation from Na{sub 2}O addition. The electron density of unoccupied d states of Pt under vacuum decreased by Na{sub 2}O addition, indicating the electron donation from Na{sub 2}O addition. However, most of these additional electrons were observed to move to ethene under reaction conditions. The acceptor of the electrons was suggested by di-{sigma}-ethene by the shift of {upsilon}(C-H). The kinetic parameters are discussed in relation to the change in the d state of Pt as a function of {sigma}{sub P} and Na quantity.

  12. Vanadium bisimide bonding investigated by X-ray crystallography, 51V and 13C nuclear magnetic resonance spectroscopy, and V L(3,2)-edge X-ray absorption near-edge structure spectroscopy.

    PubMed

    La Pierre, Henry S; Minasian, Stefan G; Abubekerov, Mark; Kozimor, Stosh A; Shuh, David K; Tyliszczak, Tolek; Arnold, John; Bergman, Robert G; Toste, F Dean

    2013-10-01

    Syntheses of neutral halide and aryl vanadium bisimides are described. Treatment of VCl2(NtBu)[NTMS(N(t)Bu)], 2, with PMe3, PEt3, PMe2Ph, or pyridine gave vanadium bisimides via TMSCl elimination in good yield: VCl(PMe3)2(N(t)Bu)2 3, VCl(PEt3)2(N(t)Bu)2 4, VCl(PMe2Ph)2(N(t)Bu)2 5, and VCl(Py)2(N(t)Bu)2 6. The halide series (Cl-I) was synthesized by use of TMSBr and TMSI to give VBr(PMe3)2(N(t)Bu)2 7 and VI(PMe3)2(N(t)Bu)2 8. The phenyl derivative was obtained by reaction of 3 with MgPh2 to give VPh(PMe3)2(N(t)Bu)2 9. These neutral complexes are compared to the previously reported cationic bisimides [V(PMe3)3(N(t)Bu)2][Al(PFTB)4] 10, [V(PEt3)2(N(t)Bu)2][Al(PFTB)4] 11, and [V(DMAP)(PEt3)2(N(t)Bu)2][Al(PFTB)4] 12 (DMAP = dimethylaminopyridine, PFTB = perfluoro-tert-butoxide). Characterization of the complexes by X-ray diffraction, (13)C NMR, (51)V NMR, and V L(3,2)-edge X-ray absorption near-edge structure (XANES) spectroscopy provides a description of the electronic structure in comparison to group 6 bisimides and the bent metallocene analogues. The electronic structure is dominated by π bonding to the imides, and localization of electron density at the nitrogen atoms of the imides is dictated by the cone angle and donating ability of the axial neutral supporting ligands. This phenomenon is clearly seen in the sensitivity of (51)V NMR shift, (13)C NMR Δδ(αβ), and L3-edge energy to the nature of the supporting phosphine ligand, which defines the parameters for designing cationic group 5 bisimides that would be capable of breaking stronger σ bonds. Conversely, all three methods show little dependence on the variable equatorial halide ligand. Furthermore, this analysis allows for quantification of the electronic differences between vanadium bisimides and the structurally analogous mixed Cp/imide system CpV(N(t)Bu)X2 (Cp = C5H5(1-)). PMID:24024833

  13. X-ray photoelectron spectroscopy and x-ray absorption near edge structure study of copper sites hosted at the internal surface of ZSM-5 zeolite: A comparison with quantitative and energetic data on the CO and NH3 adsorption

    NASA Astrophysics Data System (ADS)

    Bolis, V.; Maggiorini, S.; Meda, L.; D'Acapito, F.; Palomino, G. Turnes; Bordiga, S.; Lamberti, C.

    2000-11-01

    The oxidation state of Cu species dispersed in a Cu-ZSM-5 zeolite obtained by a nonconventional gas-phase CuCl exchange, and nominally containing only Cu(I) species, was studied by x-ray photoelectron spectroscopy (XPS) and x-ray absorption near edge structure (XANES) analyses. The oxidation of Cu(I) species to Cu(II) by simple exposure to the atmosphere and subsequent reduction by thermal activation in vacuo was monitored. The quantitative and energetic aspects of the formation of carbonyl-like and amino-complexes at the metallic sites was studied by means of adsorption microcalorimetry. CO and NH3 were used as probe molecules in order to assess the coordinative unsaturation of the Cu(I) cations. Adsorption heats comprised in the 130-40 kJ mol-1 interval were obtained for the formation of both type of complexes. The perturbation induced on the Cu centers and/or on the zeolite matrix by the adsorption of the probe molecules was monitored by parallel experiments of XPS, IR, and XANES. A significant fraction of CO and NH3 molecules are irreversibly held on Cu(I) sites even after outgassing at room temperature (RT) at a final dynamic vacuum of 10-5 Torr. On the contrary, no evidence of Cu(I)/CO or of Cu(I)/NH3 complexes was observed by XPS, indicating that such adducts are totally destroyed upon outgassing at 10-9 Torr. This fact implies a reconsideration of what was previously considered as a "stable adduct." XPS allowed to reveal the existence of ammonia adsorbed on defective Al(III) species, and to explain the chemical nature of species formed at the earliest stages of NH3 dosage and characterized by a heat of adsorption as high as 180 kJ mol-1. By comparing the quantitative XPS and volumetric-calorimetric data it was inferred that a significant gradient of defects amount is present in the system. Finally, from the whole set of XPS measurements here reported and from parallel blank experiments on the ZSM-5 zeolite before Cu-exchange, a calibration scale for the N(1

  14. Bonding modifications in carbon nitride films induced by thermal annealing: An x-ray absorption near edge study

    SciTech Connect

    Jimenez, I.; Tong, W.M.; Shuh, D.K.; Holloway, B.C.; Kelly, M.A.; Pianetta, P.; Terminello, L.J.; Himpsel, F.J.

    1999-05-01

    The thermal stability of nonstoichiometric carbon nitride films has been studied by x-ray absorption near edge spectroscopy. Amorphous carbon nitride thin films were annealed in vacuum up to 1150 {degree}C revealing the presence of nitrogen in different bonding configurations. Annealing to 450 {degree}C results in the loss of {approximately}50{percent} of the nitrogen. The remaining nitrogen is bonded to carbon within a graphitic framework and it evolves into a more stable configuration with increasing temperature without significant N loss up to 820 {degree}C. Beyond this temperature, nitrogen loss occurs without important structural changes. {copyright} {ital 1999 American Institute of Physics.}

  15. [Effect of Long-Term Fertilization on Organic Nitrogen Functional Groups in Black Soil as Revealed by Synchrotron-Based X-Ray Absorption Near-Edge Structure Spectroscopy].

    PubMed

    Li, Hui; Gao, Qiang; Wang, Shuai; Zhu, Ping; Zhang, Jin-jing; Zhao, Yi-dong

    2015-07-01

    Nitrogen (N) is a common limiting nutrient in crop production. The N content of soil has been used as an important soil fertility index. Organic N is the major form of N in soil. In most agricultural surface soils, more than 90% of total N occurs in organic forms. Therefore, understanding the compositional characteristics of soil organic N functional groups can provide the scientific basis for formulating the reasonable farmland management strategies. Synchrotron radiation soft X-ray absorption near-edge structure (N K-edge XANES) spectroscopy is the most powerful tool to characterize in situ organic N functional groups compositions in soil. However, to our most knowledge, no studies have been conducted to examine the organic N functional groups compositions of soil using N K-edge XANES spectroscopy under long-term fertilization practices. Based on a long-term field experiment (started in 1990) in a black soil (Gongzhuling, Northeast China), we investigated the differences in organic N functional groups compositions in bulk soil and clay-size soil fraction among fertilization patterns using synchrotron-based N K- edge XANES spectroscopy. Composite soil samples (0-20 cm) were collected in 2008. The present study included six treatments: farmland fallow (FALL), no-fertilization control (CK), chemical nitrogen, phosphorus, and potassium fertilization (NPK), NPK in combination with organic manure (NPKM), 1.5 times of NPKM (1.5 NPKM), and NPK in combination with maize straw (NPKS). The results showed that N K-edge XANES spectra of all the treatments under study exhibited characteristic absorption peaks in the ranges of 401.2-401.6 and 402.7-403.1 eV, which were assigned as amides/amine-N and pyrrole-N, respectively. These characteristic absorption peaks were more obvious in clay-size soil fraction than in bulk soil. The results obtained from the semi-quantitative analysis of N K-edge XANES spectra indicated that the relative proportion of amides/amine-N was the highest

  16. [Effect of Long-Term Fertilization on Organic Nitrogen Functional Groups in Black Soil as Revealed by Synchrotron-Based X-Ray Absorption Near-Edge Structure Spectroscopy].

    PubMed

    Li, Hui; Gao, Qiang; Wang, Shuai; Zhu, Ping; Zhang, Jin-jing; Zhao, Yi-dong

    2015-07-01

    Nitrogen (N) is a common limiting nutrient in crop production. The N content of soil has been used as an important soil fertility index. Organic N is the major form of N in soil. In most agricultural surface soils, more than 90% of total N occurs in organic forms. Therefore, understanding the compositional characteristics of soil organic N functional groups can provide the scientific basis for formulating the reasonable farmland management strategies. Synchrotron radiation soft X-ray absorption near-edge structure (N K-edge XANES) spectroscopy is the most powerful tool to characterize in situ organic N functional groups compositions in soil. However, to our most knowledge, no studies have been conducted to examine the organic N functional groups compositions of soil using N K-edge XANES spectroscopy under long-term fertilization practices. Based on a long-term field experiment (started in 1990) in a black soil (Gongzhuling, Northeast China), we investigated the differences in organic N functional groups compositions in bulk soil and clay-size soil fraction among fertilization patterns using synchrotron-based N K- edge XANES spectroscopy. Composite soil samples (0-20 cm) were collected in 2008. The present study included six treatments: farmland fallow (FALL), no-fertilization control (CK), chemical nitrogen, phosphorus, and potassium fertilization (NPK), NPK in combination with organic manure (NPKM), 1.5 times of NPKM (1.5 NPKM), and NPK in combination with maize straw (NPKS). The results showed that N K-edge XANES spectra of all the treatments under study exhibited characteristic absorption peaks in the ranges of 401.2-401.6 and 402.7-403.1 eV, which were assigned as amides/amine-N and pyrrole-N, respectively. These characteristic absorption peaks were more obvious in clay-size soil fraction than in bulk soil. The results obtained from the semi-quantitative analysis of N K-edge XANES spectra indicated that the relative proportion of amides/amine-N was the highest

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

    NASA Astrophysics Data System (ADS)

    Osorio, A. G.; Bergmann, C. P.

    2015-10-01

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

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

    PubMed

    Okumura, Toyoki; Yamaguchi, Yoichi; Kobayashi, Hironori

    2016-07-21

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

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

    PubMed

    Okumura, Toyoki; Yamaguchi, Yoichi; Kobayashi, Hironori

    2016-07-21

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

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

    PubMed

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

    2013-03-01

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

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

    PubMed

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

    2013-03-01

    This study investigates biogeochemical reductive release of arsenate from beudantite into solution in a crater area in northern Taiwan, using a combination of X-ray absorption near-edge structure (XANES) and atomic absorption spectrometry. Total arsenic (As) concentrations in the soil were more than 200 mg/kg. Over four months of laboratory experiments, less than 0.8% As was released into solution after reduction experiments. The 71% to 83% As was chemically reduced into arsenite (As(III)) and partially weathering into the soluble phase. The kinetic dissolution and re-precipitation of As, Fe, Pb and sulfate in this area of paddy soils merits further study. PMID:23923437

  2. Electron energy loss-near edge structure as a fingerprint for identifying chromium nitrides

    NASA Astrophysics Data System (ADS)

    Mitterbauer, C.; Hébert, C.; Kothleitner, G.; Hofer, F.; Schattschneider, P.; Zandbergen, H. W.

    2004-04-01

    Electron energy-loss near-edge structure data for the N K and the Cr L 2,3 edges of CrN and Cr 2N have been acquired in order to distinguish between these chromium nitride modifications. The N K edge spectra of these compounds have been modelled using both band structure and multiple scattering methods. We compare the results of these calculations with the experimental edges which have been recorded using a conventional transmission electron microscope (TEM) as well as a monochromated TEM (Wien filter).

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  4. Diffraction anomalous near-edge structure in ordered GaInP

    NASA Astrophysics Data System (ADS)

    Alagna, L.; Prosperi, T.; Turchini, S.; Ferrari, C.; Francesio, L.; Franzosi, P.

    1998-04-01

    We report the diffraction anomalous near-edge structure (DANES) of a nominally lattice matched GaxIn1-xP/GaAs (x=0.51) heteroepitaxial layer, grown by metal organic chemical vapor deposition, which shows long range ordering in the cationic sublattice along the <111> direction. DANES spectra, originating from the 004 reflections of the substrate and of the epi-layer and that from the "forbidden" -5/2 5/2 -5/2 reflection of the superstructure, have been recorded at the Ga K edge. A full theoretical simulation, based on the kinematic formalism, largely agrees with the experimental data.

  5. Near-edge x-ray absorption spectroscopy of RT/sub 2/Si/sub 2/ and RT/sub 2/Ge/sub 2/ compounds

    SciTech Connect

    Ansari, P.H.; Qi, B.; Liang, G.; Perez, I.; Lu, F.; Croft, M.

    1988-04-15

    X-ray absorption near-edge spectroscopy (XANES) measurements on 1:2:2 compounds of the form RT/sub 2/X/sub 2/ with R = Ce and Eu, T = a transition metal, and X = Si or Ge are presented. XANES measurements on each of the three sublattices are used to elucidate elements of the electronic structure of these compounds. In particular, the evidence for the strongly bonded T-X planes, the coupling of the Ce valence-state stability to the T-X planes, and the response of the X-p orbitals to varying transition-metal components are discussed.

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

    SciTech Connect

    Levy, A.; Dorchies, F.; Fourment, C.; Harmand, M.; Hulin, S.; Santos, J. J.; Descamps, D.; Petit, S.; Bouillaud, R.

    2010-06-15

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

  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. C-C bond unsaturation degree in monosubstituted ferrocenes for molecular electronics investigated by a combined near-edge x-ray absorption fine structure, x-ray photoemission spectroscopy, and density functional theory approach

    SciTech Connect

    Boccia, A.; Lanzilotto, V.; Marrani, A. G.; Zanoni, R.; Stranges, S.; Alagia, M.; Fronzoni, G.; Decleva, P.

    2012-04-07

    We present the results of an experimental and theoretical investigation of monosubstituted ethyl-, vinyl-, and ethynyl-ferrocene (EtFC, VFC, and EFC) free molecules, obtained by means of synchrotron-radiation based C 1s photoabsorption (NEXAFS) and photoemission (C 1s XPS) spectroscopies, and density functional theory (DFT) calculations. Such a combined study is aimed at elucidating the role played by the C-C bond unsaturation degree of the substituent on the electronic structure of the ferrocene derivatives. Such substituents are required for molecular chemical anchoring onto relevant surfaces when ferrocenes are used for molecular electronics hybrid devices. The high resolution C 1s NEXAFS spectra exhibit distinctive features that depend on the degree of unsaturation of the hydrocarbon substituent. The theoretical approach to consider the NEXAFS spectrum made of three parts allowed to disentangle the specific contribution of the substituent group to the experimental spectrum as a function of its unsaturation degree. C 1s IEs were derived from the experimental data analysis based on the DFT calculated IE values for the different carbon atoms of the substituent and cyclopentadienyl (Cp) rings. Distinctive trends of chemical shifts were observed for the substituent carbon atoms and the substituted atom of the Cp ring along the series of ferrocenes. The calculated IE pattern was rationalized in terms of initial and final state effects influencing the IE value, with special regard to the different mechanism of electron conjugation between the Cp ring and the substituent, namely the {sigma}/{pi} hyperconjugation in EtFC and the {pi}-conjugation in VFC and EFC.

  9. C-C bond unsaturation degree in monosubstituted ferrocenes for molecular electronics investigated by a combined near-edge x-ray absorption fine structure, x-ray photoemission spectroscopy, and density functional theory approach

    NASA Astrophysics Data System (ADS)

    Boccia, A.; Lanzilotto, V.; Marrani, A. G.; Stranges, S.; Zanoni, R.; Alagia, M.; Fronzoni, G.; Decleva, P.

    2012-04-01

    We present the results of an experimental and theoretical investigation of monosubstituted ethyl-, vinyl-, and ethynyl-ferrocene (EtFC, VFC, and EFC) free molecules, obtained by means of synchrotron-radiation based C 1s photoabsorption (NEXAFS) and photoemission (C 1s XPS) spectroscopies, and density functional theory (DFT) calculations. Such a combined study is aimed at elucidating the role played by the C-C bond unsaturation degree of the substituent on the electronic structure of the ferrocene derivatives. Such substituents are required for molecular chemical anchoring onto relevant surfaces when ferrocenes are used for molecular electronics hybrid devices. The high resolution C 1s NEXAFS spectra exhibit distinctive features that depend on the degree of unsaturation of the hydrocarbon substituent. The theoretical approach to consider the NEXAFS spectrum made of three parts allowed to disentangle the specific contribution of the substituent group to the experimental spectrum as a function of its unsaturation degree. C 1s IEs were derived from the experimental data analysis based on the DFT calculated IE values for the different carbon atoms of the substituent and cyclopentadienyl (Cp) rings. Distinctive trends of chemical shifts were observed for the substituent carbon atoms and the substituted atom of the Cp ring along the series of ferrocenes. The calculated IE pattern was rationalized in terms of initial and final state effects influencing the IE value, with special regard to the different mechanism of electron conjugation between the Cp ring and the substituent, namely the σ/π hyperconjugation in EtFC and the π-conjugation in VFC and EFC.

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

    SciTech Connect

    Dorchies, F. Fedorov, N.; Lecherbourg, L.

    2015-07-15

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

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

    PubMed

    Dorchies, F; Fedorov, N; Lecherbourg, L

    2015-07-01

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

  12. 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.

  13. General Method for Determination of the Surface Composition in Bimetallic Nanoparticle Catalysts from the L Edge X-ray Absorption Near-Edge Spectra

    SciTech Connect

    Wu, Tiapin; Childers, David; Gomez, Carolina; Karim, Ayman M.; Schweitzer, Neil; Kropf, Arthur; Wang, Hui; Bolin, Trudy B.; Hu, Yongfeng; Kovarik, Libor; Meyer, Randall; Miller, Jeffrey T.

    2012-10-08

    Bimetallic PtPd on silica nano-particle catalysts have been synthesized and their average structure determined by Pt L3 and Pd K-edge extended X-ray absorption finestructure (EXAFS) spectroscopy. The bimetallic structure is confirmed from elemental line scans by STEM for the individual 1-2 nm sized particles. A general method is described to determine the surface composition in bimetallic nanoparticles even when both metals adsorb, for example, CO. By measuring the change in the L3 X-ray absorption near-edge structure (XANES) spectra with and without CO in bimetallic particles and comparing these changes to those in monometallic particles of known size the fraction of surface atoms can be determined. The turnover rates (TOR) and neopentane hydrogenolysis and isomerization selectivities based on the surface composition suggest that the catalytic and spectroscopic properties are different from those in monometallic nano-particle catalysts. At the same neo-pentane conversion, the isomerization selectivity is higher for the PtPd catalyst while the TOR is lower than that of both Pt and Pd. As with the catalytic performance, the infrared spectra of adsorbed CO are not a linear combination of the spectra on monometallic catalysts. Density functional theory calculations indicate that the Pt-CO adsorption enthalpy increases while the Pd-CO bond energy decreases. The ability to determine the surface composition allows for a better understanding of the spectroscopic and catalytic properties of bimetallic nanoparticle catalysts.

  14. Electron energy-loss near-edge structures of 3d transition metal oxides recorded at high-energy resolution.

    PubMed

    Mitterbauer, C; Kothleitner, G; Grogger, W; Zandbergen, H; Freitag, B; Tiemeijer, P; Hofer, F

    2003-09-01

    Near-edge fine structures of the metal L(2,3) and O K-edges in transition metal-oxides have been studied with a transmission electron microscope equipped with a monochromator and a high-resolution imaging filter. This system enables the recording of EELS spectra with an energy resolution of 0.1eV thus providing new near-edge fine structure details which could not be observed previously by EELS in conventional TEM instruments. EELS-spectra from well-defined oxides like titanium oxide (TiO(2)), vanadium oxide (V(2)O(5)), chromium oxide (Cr(2)O(3)), iron oxide (Fe(2)O(3)), cobalt oxide (CoO) and nickel oxide (NiO) have been measured with the new system. These spectra are compared with EELS data obtained from a conventional microscope and the main spectral features are interpreted. Additionally, the use of monochromised TEMs is discussed in view of the natural line widths of K and L(2,3) edges. PMID:12871809

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

    SciTech Connect

    Yang, Mino; Baik, Hionsuck; Ivanovskaya, Viktoria; Colliex, Christian; Benayad, Anass

    2011-03-01

    The present paper reports the energy loss near-edge structure (ELNES) study of monoclinic HfO{sub 2} (m-HfO{sub 2}) and tantalum doped m-HfO{sub 2} (Ta{sub 0.1}Hf{sub 0.9}O{sub 2}) thin films prepared by radio frequency magnetron co-sputtering method. A change in the O K-ELNES spectra was observed as the amount of dopant increases. In order to precise the common features and the differences as a function of Ta defect nature (substitutional or interstitial) in HfO{sub 2}, the O K-ELNES were commented with respect to density functional theory calculations implemented in Vienna ab initio simulation package code. The calculated Ta doped HfO{sub 2} band structure showed that substitutional tantalum is the dominant defect and the spectral differences between doped and non-doped HfO{sub 2} are mainly originated from the change in the local cation distribution around the oxygen atoms.

  16. Predicting Near Edge X-ray Absorption Spectra with the Spin-Free Exact-Two-Component Hamiltonian and Orthogonality Constrained Density Functional Theory.

    PubMed

    Verma, Prakash; Derricotte, Wallace D; Evangelista, Francesco A

    2016-01-12

    Orthogonality constrained density functional theory (OCDFT) provides near-edge X-ray absorption (NEXAS) spectra of first-row elements within one electronvolt from experimental values. However, with increasing atomic number, scalar relativistic effects become the dominant source of error in a nonrelativistic OCDFT treatment of core-valence excitations. In this work we report a novel implementation of the spin-free exact-two-component (X2C) one-electron treatment of scalar relativistic effects and its combination with a recently developed OCDFT approach to compute a manifold of core-valence excited states. The inclusion of scalar relativistic effects in OCDFT reduces the mean absolute error of second-row elements core-valence excitations from 10.3 to 2.3 eV. For all the excitations considered, the results from X2C calculations are also found to be in excellent agreement with those from low-order spin-free Douglas-Kroll-Hess relativistic Hamiltonians. The X2C-OCDFT NEXAS spectra of three organotitanium complexes (TiCl4, TiCpCl3, TiCp2Cl2) are in very good agreement with unshifted experimental results and show a maximum absolute error of 5-6 eV. In addition, a decomposition of the total transition dipole moment into partial atomic contributions is proposed and applied to analyze the nature of the Ti pre-edge transitions in the three organotitanium complexes.

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

    PubMed

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

    2014-10-22

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

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

    PubMed

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

    2014-10-22

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

  19. Synchrotron-based X-ray absorption near-edge spectroscopy imaging for laterally resolved speciation of selenium in fresh roots and leaves of wheat and rice

    PubMed Central

    Wang, Peng; Menzies, Neal W.; Lombi, Enzo; McKenna, Brigid A.; James, Simon; Tang, Caixian; Kopittke, Peter M.

    2015-01-01

    Knowledge of the distribution of selenium (Se) species within plant tissues will assist in understanding the mechanisms of Se uptake and translocation, but in situ analysis of fresh and highly hydrated plant tissues is challenging. Using synchrotron-based fluorescence X-ray absorption near-edge spectroscopy (XANES) imaging to provide laterally resolved data, the speciation of Se in fresh roots and leaves of wheat (Triticum aestivum L.) and rice (Oryza sativa L.) supplied with 1 μM of either selenate or selenite was investigated. For plant roots exposed to selenate, the majority of the Se was efficiently converted to C-Se-C compounds (i.e. methylselenocysteine or selenomethionine) as selenate was transported radially through the root cylinder. Indeed, even in the rhizodermis which is exposed directly to the bulk solution, only 12–31% of the Se was present as uncomplexed selenate. The C-Se-C compounds were probably sequestered within the roots, whilst much of the remaining uncomplexed Se was translocated to the leaves—selenate accounting for 52–56% of the total Se in the leaves. In a similar manner, for plants exposed to selenite, the Se was efficiently converted to C-Se-C compounds within the roots, with only a small proportion of uncomplexed selenite observed within the outer root tissues. This resulted in a substantial decrease in translocation of Se from the roots to leaves of selenite-exposed plants. This study provides important information for understanding the mechanisms responsible for the uptake and subsequent transformation of Se in plants. PMID:26019258

  20. [Effects of long-term fertilization on organic carbon functional groups in black soil as revealed by synchrotron radiation soft X-ray near-edge absorption spectroscopy].

    PubMed

    Wang, Nan; Wang, Shuai; Wang, Qing-He; Dong, Pei-Bo; Li, Cui-Lan; Zhang, Jin-Jing; Gao, Qiang; Zhao, Yi-Dong

    2012-10-01

    A 20 years (1984-2004) stationary field experiment was conducted to evaluate the effects of long-term application of chemical fertilizers (N or NPK) alone or in combination with low (0.125 kg x hm(-2)) or high dose of corn stalk (0.25 kg x hm(-2)) on organic carbon functional groups in black soil using synchrotron radiation soft X-ray near-edge absorption spectroscopy (C-1s NEXAFS). Compared with the control (CK) treatment, the aromatic C and the carboxyl C of soil increased, whereas the aliphatic C, the carbonyl C and the aliphatic C/aromatic C ratio decreased after the application of chemical fertilizer alone. After the application of chemical fertilizations in combined with corn stalk, the aromatic C decreased while the aliphatic C and the aliphatic C/aromatic C ratio increased as compared to N or NPK fertilizer treatment. And the change tendency was more obvious with the increase in the dose of corn stalk applied. Regardless of corn stalk application, the aromatic C, the aliphatic C, and the aliphatic C/aromatic C ratio were all higher for NPK than for N fertilizer treatment. The above results indicated that, compared with the no-fertilizer control treatment, the application of chemical fertilizers alone resulted in the relative proportion of aromatic compounds increased whereas that of aliphatic hydrocarbon compounds decreased. On the other hand, the relative proportion of the aliphatic hydrocarbon compounds was higher after the application of chemical fertilizers with than without corn stalk, with high than with low dose of corn stalk, and with NPK than with N fertilization. C-1s NEXAFS spectroscopy could characterize in situ the changes of organic carbon functional groups in soil under long-term stationary fertilization.

  1. Synchrotron-based X-ray absorption near-edge spectroscopy imaging for laterally resolved speciation of selenium in fresh roots and leaves of wheat and rice.

    PubMed

    Wang, Peng; Menzies, Neal W; Lombi, Enzo; McKenna, Brigid A; James, Simon; Tang, Caixian; Kopittke, Peter M

    2015-08-01

    Knowledge of the distribution of selenium (Se) species within plant tissues will assist in understanding the mechanisms of Se uptake and translocation, but in situ analysis of fresh and highly hydrated plant tissues is challenging. Using synchrotron-based fluorescence X-ray absorption near-edge spectroscopy (XANES) imaging to provide laterally resolved data, the speciation of Se in fresh roots and leaves of wheat (Triticum aestivum L.) and rice (Oryza sativa L.) supplied with 1 μM of either selenate or selenite was investigated. For plant roots exposed to selenate, the majority of the Se was efficiently converted to C-Se-C compounds (i.e. methylselenocysteine or selenomethionine) as selenate was transported radially through the root cylinder. Indeed, even in the rhizodermis which is exposed directly to the bulk solution, only 12-31% of the Se was present as uncomplexed selenate. The C-Se-C compounds were probably sequestered within the roots, whilst much of the remaining uncomplexed Se was translocated to the leaves-selenate accounting for 52-56% of the total Se in the leaves. In a similar manner, for plants exposed to selenite, the Se was efficiently converted to C-Se-C compounds within the roots, with only a small proportion of uncomplexed selenite observed within the outer root tissues. This resulted in a substantial decrease in translocation of Se from the roots to leaves of selenite-exposed plants. This study provides important information for understanding the mechanisms responsible for the uptake and subsequent transformation of Se in plants.

  2. Micro-X-ray absorption near edge structure as a suitable probe to monitor live organisms

    NASA Astrophysics Data System (ADS)

    Oger, Phil M.; Daniel, I.; Simionovici, A.; Picard, A.

    2008-04-01

    X-ray spectroscopies are very powerful tools to determine the chemistry of complex dilute solutes in abiotic and biotic systems. We have assayed their suitability to monitor the chemistry of complex solutions in a live biotic system. The impact of the probe on cells was quantified for 4 different cellular organisms differing in their resistance level to environmental stresses. We show that none of the organisms tested can survive the radiation doses needed for the acquisition of meaningful spectroscopic data. Therefore, on one hand, X-ray spectroscopy cannot be applied to the monitoring of single cells, and cellular damages have to be taken into account in the interpretation of the evolution of such systems. On the other hand, due to the limited extension of X-ray induced cellular damages in the culture volume, it is possible to probe a population of live cells provided that the culture to beam probe ratio is large enough to minimize the impact of mortality on the evolution of the biological system. Our results suggest that it could be possible to probe the volume in the close vicinity of a cell without affecting its activity. Using this setup we could monitor the reduction of selenite by the X-ray sensitive bacterium, Agrobacterium tumefaciens strain C58, for 24 h. This method has a great potential to monitor the respiration of various metals, such as iron, manganese and arsenic, in situ under relevant environmental conditions by live microorganisms.

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

    SciTech Connect

    Wu, Yuntao Luo, Jialiang; Ren, Guohao; Nikl, Martin

    2014-01-01

    In the recent successful improvement of scintillation efficiency in Lu{sub 3}Al{sub 5}O{sub 12}:Ce driven by Ga{sup 3+} and Gd{sup 3+} admixture, the “band-gap engineering” and energy level positioning have been considered the valid strategies so far. This study revealed that this improvement was also associated with the cerium valence instability along with the changes of chemical composition. By utilizing X-ray absorption near edge spectroscopy technique, tuning the Ce{sup 3+}/Ce{sup 4+} ratio by Ga{sup 3+} admixture was evidenced, while it was kept nearly stable with the Gd{sup 3+} admixture. Ce valence instability and Ce{sup 3+}/Ce{sup 4+} ratio in multicomponent garnets can be driven by the energy separation between 4f ground state of Ce{sup 3+} and Fermi level.

  4. X-ray absorption near edge studies of cytochrome P-450-CAM, chloroperoxidase, and myoglobin. Direct evidence for the electron releasing character of a cysteine thiolate proximal ligand.

    PubMed

    Liu, H I; Sono, M; Kadkhodayan, S; Hager, L P; Hedman, B; Hodgson, K O; Dawson, J H

    1995-05-01

    The low spin ferric and low and high spin ferrous forms of myoglobin, bacterial cytochrome P-450-CAM, and chloroperoxidase have been examined by Fe-K x-ray absorption edge spectroscopy. The positions of the absorption edge and the shapes of preedge and edge regions of imidazole adducts of ferric P-450-CAM and chloroperoxidase are essentially the same when compared with thiolate-ligated ferric myoglobin. As these three protein derivatives all have six-coordinate, low spin, ferric hemes with axial imidazole and thiolate ligands, the superposition of x-ray absorption edge spectral properties demonstrates that the protein environment does not effect the spectra, provided one compares heme iron centers with identical coordination numbers, spin and oxidation states, and ligand sets. In contrast, a 0.96 eV difference is observed in the energy of the absorption edge for imidazole- and thiolate-ligated ferric myoglobin with the latter shifted to lower energy as observed for ferrous myoglobin states. Similarly, in the low spin ferric-imidazole and ferrous-CO states, the energies of the absorption edge for chloroperoxidase and P-450-CAM are shifted in the direction of the ferrous state (to lower energy) when compared with those for analogous myoglobin derivatives. In the deoxyferrous high spin state, comparison of the edge spectra of chloroperoxidase with analogous data for cytochrome P-450-CAM suggests that the electron density at the iron is similar for these two protein states. The shifts observed in the energies of the x-ray absorption edge for the thiolate-ligated states of these proteins relative to derivatives lacking a thiolate ligand provide a direct measure of the electron releasing character of a thiolate axial ligand. These results therefore support the suggested role of the cysteinate proximal ligand of P-450 as a strong internal electron donor to promote O-O bond cleavage in the putative ferric-peroxide intermediate to generate the proposed ferryl-oxo "active

  5. The effect of nanocrystallite size in monoclinic HfO{sub 2} films on lattice expansion and near-edge optical absorption

    SciTech Connect

    Cisneros-Morales, M. C.; Aita, C. R.

    2010-05-10

    Nanocrystalline monoclinic HfO{sub 2} films were sputter deposited on fused silica substrates, air annealed at 573 to 1273 K to affect crystallite growth, and analyzed by x-ray diffraction and spectrophotometry. Lattice expansion occurs with diminishing crystallite size. O 2p->Hf 5d interband absorption dominates the optical edge at energy E>=6.24 eV, with an optical band gap, E{sub o}=5.48+-0.023, which is independent of crystallite size. However, the strength of a localized resonant band, with onset at 5.65 eV and maximum at 5.94 eV, is affected by crystallite size. Its polaronic origin in a perfect HfO{sub 2} lattice is discussed.

  6. Parameters Influencing Sulfur Speciation in Environmental Samples Using Sulfur K-Edge X-Ray Absorption Near-Edge Structure

    PubMed Central

    Pongpiachan, Siwatt; Thumanu, Kanjana; Kositanont, Charnwit; Schwarzer, Klaus; Prietzel, Jörg; Hirunyatrakul, Phoosak; Kittikoon, Itthipon

    2012-01-01

    This paper aims to enhance the credibility of applying the sulfur K-edge XANES spectroscopy as an innovative “fingerprint” for characterizing environmental samples. The sensitivities of sulfur K-edge XANES spectra of ten sulfur compound standards detected by two different detectors, namely, Lytle detector (LyD) and Germanium detector (GeD), were studied and compared. Further investigation on “self-absorption” effect revealed that the maximum sensitivities of sulfur K-edge XANES spectra were achieved when diluting sulfur compound standards with boron nitride (BN) at the mixing ratio of 0.1%. The “particle-size” effect on sulfur K-edge XANES spectrum sensitivities was examined by comparing signal-to-noise ratios of total suspended particles (TSP) and particulate matter of less than 10 millionths of a meter (PM10) collected at three major cities of Thailand. The analytical results have demonstrated that the signal-to-noise ratios of sulfur K-edge XANES spectra were positively correlated with sulfate content in aerosols and negatively connected with particle sizes. The combination of hierarchical cluster analysis (HCA) and principal component analysis (PCA) has proved that sulfur K-edge XANES spectrum can be used to characterize German terrestrial soils and Andaman coastal sediments. In addition, this study highlighted the capability of sulfur K-edge XANES spectra as an innovative “fingerprint” to distinguish tsunami backwash deposits (TBD) from typical marine sediments (TMS). PMID:23193498

  7. Sulfur Poisoning Mechanism of Steam Reforming Catalysts: an X-ray Absorption Near Edge Structure (XANES) Spectroscopic Study

    SciTech Connect

    Chen, Y.; Xie, C; Li, Y; Song, C; Bolin, T

    2010-01-01

    The present XANES study aims at elucidating the roles of carbon deposits and metal sulfides in the catalyst deactivation in steam reforming reactions with the presence of sulfur. CeO{sub 2}-Al{sub 2}O{sub 3}-supported Ni and Rh-based catalysts were tested in steam reforming of liquid hydrocarbon fuel containing 350 ppm sulfur for H{sub 2} production at 800 C. The Rhcatalyst demonstrated much better sulfur tolerance than the Nicatalyst. XANES revealed that there are various sulfur species (metal sulfide, sulfonate, sulfate and organic sulfide) on the used Ni and Rhcatalysts. Metal sulfide and organic sulfide are the dominant sulfur species on the Nicatalyst whereas sulfonate and sulfate predominate on the Rhcatalyst. Meanwhile organic sulfide and sulfate are also observed on the support alone. Furthermore, there are more carbon deposits formed in the presence of sulfur on both catalysts. More carboxylgroups occur on the carbon deposits formed on the same catalyst when there is no sulfur in the fuel. From correlation analysis of the amounts of nickel sulfide and carbon deposits along with the relative catalytic activity loss, we conclude that sulfur causes the initial deactivation of the Nicatalyst by metal sulfide formation in the first few hours while build-up of carbon deposits contributes mainly to the subsequent deactivation.

  8. 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.

  9. Sulfur poisoning mechanism of steam reforming catalysts : an X-ray absorption near edge structure (XANES) spectroscopic study.

    SciTech Connect

    Chen, Y.; Xie, C.; Li, Y.; Song, C.; Bolin, T.; X-Ray Science Division; Pennsylvania State Univ.

    2010-04-29

    The present XANES study aims at elucidating the roles of carbon deposits and metal sulfides in the catalyst deactivation in steam reforming reactions with the presence of sulfur. CeO{sub 2}-Al{sub 2}O{sub 3}-supported Ni and Rh-based catalysts were tested in steam reforming of liquid hydrocarbon fuel containing 350 ppm sulfur for H{sub 2} production at 800 C. The Rh catalyst demonstrated much better sulfur tolerance than the Ni catalyst. XANES revealed that there are various sulfur species (metal sulfide, sulfonate, sulfate and organic sulfide) on the used Ni and Rh catalysts. Metal sulfide and organic sulfide are the dominant sulfur species on the Ni catalyst whereas sulfonate and sulfate predominate on the Rh catalyst. Meanwhile organic sulfide and sulfate are also observed on the support alone. Furthermore, there are more carbon deposits formed in the presence of sulfur on both catalysts. More carboxyl groups occur on the carbon deposits formed on the same catalyst when there is no sulfur in the fuel. From correlation analysis of the amounts of nickel sulfide and carbon deposits along with the relative catalytic activity loss, we conclude that sulfur causes the initial deactivation of the Ni catalyst by metal sulfide formation in the first few hours while build-up of carbon deposits contributes mainly to the subsequent deactivation.

  10. Sulfur poisoning mechanism of steam reforming catalysts: an X-ray absorption near edge structure (XANES) spectroscopic study.

    PubMed

    Chen, Yongsheng; Xie, Chao; Li, Yan; Song, Chunshan; Bolin, Trudy B

    2010-06-01

    The present XANES study aims at elucidating the roles of carbon deposits and metal sulfides in the catalyst deactivation in steam reforming reactions with the presence of sulfur. CeO(2)-Al(2)O(3)-supported Ni and Rh-based catalysts were tested in steam reforming of liquid hydrocarbon fuel containing 350 ppm sulfur for H(2) production at 800 degrees C. The Rh catalyst demonstrated much better sulfur tolerance than the Ni catalyst. XANES revealed that there are various sulfur species (metal sulfide, sulfonate, sulfate and organic sulfide) on the used Ni and Rh catalysts. Metal sulfide and organic sulfide are the dominant sulfur species on the Ni catalyst whereas sulfonate and sulfate predominate on the Rh catalyst. Meanwhile organic sulfide and sulfate are also observed on the support alone. Furthermore, there are more carbon deposits formed in the presence of sulfur on both catalysts. More carboxyl groups occur on the carbon deposits formed on the same catalyst when there is no sulfur in the fuel. From correlation analysis of the amounts of nickel sulfide and carbon deposits along with the relative catalytic activity loss, we conclude that sulfur causes the initial deactivation of the Ni catalyst by metal sulfide formation in the first few hours while build-up of carbon deposits contributes mainly to the subsequent deactivation. PMID:20431820

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

    PubMed

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

    2015-11-01

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

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

    NASA Astrophysics Data System (ADS)

    Zhang, Yubo; Zhang, Jiawei; Gao, Weiwei; Abtew, Tesfaye A.; Wang, Youwei; Zhang, Peihong; Zhang, Wenqing

    2013-11-01

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

  13. Near-edge elastic photon scattering in amorphous systems

    NASA Astrophysics Data System (ADS)

    Hugtenburg, R. P.; England, D. W.; Bradley, D. A.

    2007-10-01

    The structure of valence and unoccupied electron orbitals and the neighbouring electron density distribution of atoms and ions in amorphous systems can be examined through use of resonance in the elastic photon scattering-cross-section in the vicinity of core atomic orbital energies. So-called anomalous X-ray scattering (AXS) is a mode of analysis that offers similar information to that of EXAFS but can be obtained concurrently with diffraction mode imaging. Of interest is whether the dilute-ion aqueous system provides an environment suitable for testing independent particle approximation (IPA) predictions. With the aqueous environment as the reference system for calibrating relative cross-sections, particular challenges include photons scattered by the medium being subsequently absorbed by the ion, limiting the thickness of the attenuating medium and motivating use of bright synchrotron photon sources where tunable X-rays are obtained at sub-eV resolution using a Si 111 monochromator. Measured scattering intensities and fluorescent yields were compared and shown to agree qualitatively with Monte Carlo calculations utilising amplitudes calculated from modified form-factors with anomalous scatter factors at a resolution of several eV determined from the Dirac-Slater exchange potential. Experimentally determined form-factors for pure water were used to calibrate fluorescent yield and elastic scattering intensities for measurement of the energy dependent variation of these quantities near edge and XRF imaging of the Zn concentration in wax mounted, formalin fixed, breast tumour samples. Results indicate the distribution of Zn at higher resolution than sampling dimensions used in previous studies. Shifts in the position and profile of K-edge absorption and elastic scattering features in aqeuous Zn, Zn doped sol-gel glass and Zn in tissue are shown to reflect changes in the atomic charge state and environment and offer support for the presence of non-nutrient Zn bearing

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

    PubMed

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

    2015-09-01

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

  15. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using x-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  16. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using X-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  17. Probing the orientation of electrostatically immobilized Protein G B1 by time-of-flight secondary ion spectrometry, sum frequency generation, and near-edge X-ray adsorption fine structure spectroscopy.

    PubMed

    Baio, Joe E; Weidner, Tobias; Baugh, Loren; Gamble, Lara J; Stayton, Patrick S; Castner, David G

    2012-01-31

    To fully develop techniques that provide an accurate description of protein structure at a surface, we must start with a relatively simple model system before moving to increasingly complex systems. In this study, X-ray photoelectron spectroscopy (XPS), sum frequency generation spectroscopy (SFG), near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to probe the orientation of Protein G B1 (6 kDa) immobilized onto both amine (NH(3)(+)) and carboxyl (COO(-)) functionalized gold. Previously, we have shown that we could successfully control orientation of a similar Protein G fragment via a cysteine-maleimide bond. In this investigation, to induce opposite end-on orientations, a charge distribution was created within the Protein G B1 fragment by first substituting specific negatively charged amino acids with neutral amino acids and then immobilizing the protein onto two oppositely charged self-assembled monolayer (SAM) surfaces (NH(3)(+) and COO(-)). Protein coverage, on both surfaces, was monitored by the change in the atomic % N, as determined by XPS. Spectral features within the SFG spectra, acquired for the protein adsorbed onto a NH(3)(+)-SAM surface, indicates that this electrostatic interaction does induce the protein to form an oriented monolayer on the SAM substrate. This corresponded to the polarization dependence of the spectral feature related to the NEXAFS N(1s)-to-π* transition of the β-sheet peptide bonds within the protein layer. ToF-SIMS data demonstrated a clear separation between the two samples based on the intensity differences of secondary ions stemming from amino acids located asymmetrically within Protein G B1 (methionine: 62 and 105 m/z; tyrosine: 107 and 137 m/z; leucine: 86 m/z). For a more quantitative examination of orientation, we developed a ratio comparing the sum of the intensities of secondary-ions stemming from the amino acid residues at either end

  18. Examination of the local structure in composite and lowdimensional semiconductor by X-ray Absorption Spectroscopy

    SciTech Connect

    Lawniczak-Jablonska, K.; Demchenko, I.N.; Piskorska, E.; Wolska,A.; Talik, E.; Zakharov, D.N.; Liliental-Weber, Z.

    2006-09-25

    X-ray absorption methods have been successfully used to obtain quantitative information about local atomic composition of two different materials. X-ray Absorption Near Edge Structure analysis and X-Ray Photoelectron Spectroscopy allowed us to determine seven chemical compounds and their concentrations in c-BN composite. Use of Extended X-ray Absorption Fine Structure in combination with Transmission Electron Microscopy enabled us to determine the composition and size of buried Ge quantum dots. It was found that the quantum dots consisted out of pure Ge core covered by 1-2 monolayers of a layer rich in Si.

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

    SciTech Connect

    Reitsma, G.; Deuzeman, M. J.; Hoekstra, R.; Schlathölter, T.; Boschman, L.; Hoekstra, S.

    2015-01-14

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

  20. Speciation and Long- and Short-term Molecular-level Dynamics of Soil Organic Sulfur Studied by X-ray Absorption Near-Edge Structure Spectroscopy

    SciTech Connect

    D Solomon; J Lehmann; K Knoth de Zarruk; J Dathe; J Kinyangi; B Liang; S Machado

    2011-12-31

    We investigated speciation, oxidative state changes, and long- and short-term molecular-level dynamics of organic S after 365 d of aerobic incubation with and without the addition of sugarcane residue using XANES spectroscopy. Soil samples were collected from the upper 15 cm of undisturbed grasslands since 1880, from undisturbed grasslands since 1931, and from cultivated fields since 1880 in the western United States. We found three distinct groups of organosulfur compounds in these grassland-derived soils: (i) strongly reduced (S{sup 0} to S{sup 1+}) organic S that encompasses thiols, monosulfides, disulfides, polysulfides, and thiophenes; (ii) organic S in intermediate oxidation (S{sup 2+} to S{sup 5+}) states, which include sulfoxides and sulfonates; and (iii) strongly oxidized (S{sup 6+}) organic S, which comprises ester-SO{sub 4}-S. The first two groups represent S directly linked to C and accounted for 80% of the total organic S detected by XANES from the undisturbed soils. Aerobic incubation without the addition of sugarcane residue led to a 21% decline in organanosulfur compounds directly linked to C and to up to an 82% increase inorganic S directly bonded to O. Among the C-bonded S compounds, low-valence thiols, sulfides, thiophenic S, and intermediate-valence sulfoxide S seem to be highly susceptible to microbial attack and may represent the most reactive components of organic S pool in these grassland soils. Sulfonate S exhibited a much lower short-term reactivity. The incorporation of sugarcane residue resulted in an increase in organosulfur compounds directly bonded to C at the early stage of incubation. However, similar to soils incubated without residue addition, the proportion of organic S directly linked to C continued to decline with increasing duration of aerobic incubation, whereas the proportion of organic S directly bonded to O showed a steady rise.

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

    PubMed Central

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

    2012-01-01

    This paper focuses on providing new results relating to the impacts of Diurnal variation, Vertical distribution, and Emission source on sulfur K-edge XANES spectrum of aerosol samples. All aerosol samples used in the diurnal variation experiment were preserved using anoxic preservation stainless cylinders (APSCs) and pressure-controlled glove boxes (PCGBs), which were specially designed to prevent oxidation of the sulfur states in PM10. Further investigation of sulfur K-edge XANES spectra revealed that PM10 samples were dominated by S(VI), even when preserved in anoxic conditions. The “Emission source effect” on the sulfur oxidation state of PM10 was examined by comparing sulfur K-edge XANES spectra collected from various emission sources in southern Thailand, while “Vertical distribution effects” on the sulfur oxidation state of PM10 were made with samples collected from three different altitudes from rooftops of the highest buildings in three major cities in Thailand. The analytical results have demonstrated that neither “Emission source” nor “Vertical distribution” appreciably contribute to the characteristic fingerprint of sulfur K-edge XANES spectrum in PM10. PMID:22988545

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

    SciTech Connect

    Kim, Do Heui; Szanyi, Janos; Kwak, Ja Hun; Wang, Xianqin; Hanson, Jonathan C.; Engelhard, Mark H.; Peden, Charles HF

    2009-04-03

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

  3. Combined use of synchrotron radiation based micro-X-ray fluorescence, micro-X-ray diffraction, micro-X-ray absorption near-edge, and micro-fourier transform infrared spectroscopies for revealing an alternative degradation pathway of the pigment cadmium yellow in a painting by Van Gogh.

    PubMed

    Van der Snickt, Geert; Janssens, Koen; Dik, Joris; De Nolf, Wout; Vanmeert, Frederik; Jaroszewicz, Jacub; Cotte, Marine; Falkenberg, Gerald; Van der Loeff, Luuk

    2012-12-01

    Over the past years a number of studies have described the instability of the pigment cadmium yellow (CdS). In a previous paper we have shown how cadmium sulfide on paintings by James Ensor oxidizes to CdSO(4)·H(2)O. The degradation process gives rise to the fading of the bright yellow color and the formation of disfiguring white crystals that are present on the paint surface in approximately 50 μm sized globular agglomerations. Here, we study cadmium yellow in the painting "Flowers in a blue vase" by Vincent van Gogh. This painting differs from the Ensor case in the fact that (a) a varnish was superimposed onto the degraded paint surface and (b) the CdS paint area is entirely covered with an opaque crust. The latter obscures the yellow color completely and thus presents a seemingly more advanced state of degradation. Analysis of a cross-sectioned and a crushed sample by combining scanning microscopic X-ray diffraction (μ-XRD), microscopic X-ray absorption near-edge spectroscopy (μ-XANES), microscopic X-ray fluorescence (μ-XRF) based chemical state mapping and scanning microscopic Fourier transform infrared (μ-FT-IR) spectrometry allowed unravelling the complex alteration pathway. Although no crystalline CdSO(4) compounds were identified on the Van Gogh paint samples, we conclude that the observed degradation was initially caused by oxidation of the original CdS pigment, similar as for the previous Ensor case. However, due to the presence of an overlying varnish containing lead-based driers and oxalate ions, secondary reactions took place. In particular, it appears that upon the photoinduced oxidation of its sulfidic counterion, the Cd(2+) ions reprecipitated at the paint/varnish interface after having formed a complex with oxalate ions that themselves are considered to be degradation products of the resin and/or oil in the varnish. The SO(4)(2-) anions, for their part, found a suitable reaction partner in Pb(2+) ions stemming from a dissolved lead

  4. Combined use of synchrotron radiation based micro-X-ray fluorescence, micro-X-ray diffraction, micro-X-ray absorption near-edge, and micro-fourier transform infrared spectroscopies for revealing an alternative degradation pathway of the pigment cadmium yellow in a painting by Van Gogh.

    PubMed

    Van der Snickt, Geert; Janssens, Koen; Dik, Joris; De Nolf, Wout; Vanmeert, Frederik; Jaroszewicz, Jacub; Cotte, Marine; Falkenberg, Gerald; Van der Loeff, Luuk

    2012-12-01

    Over the past years a number of studies have described the instability of the pigment cadmium yellow (CdS). In a previous paper we have shown how cadmium sulfide on paintings by James Ensor oxidizes to CdSO(4)·H(2)O. The degradation process gives rise to the fading of the bright yellow color and the formation of disfiguring white crystals that are present on the paint surface in approximately 50 μm sized globular agglomerations. Here, we study cadmium yellow in the painting "Flowers in a blue vase" by Vincent van Gogh. This painting differs from the Ensor case in the fact that (a) a varnish was superimposed onto the degraded paint surface and (b) the CdS paint area is entirely covered with an opaque crust. The latter obscures the yellow color completely and thus presents a seemingly more advanced state of degradation. Analysis of a cross-sectioned and a crushed sample by combining scanning microscopic X-ray diffraction (μ-XRD), microscopic X-ray absorption near-edge spectroscopy (μ-XANES), microscopic X-ray fluorescence (μ-XRF) based chemical state mapping and scanning microscopic Fourier transform infrared (μ-FT-IR) spectrometry allowed unravelling the complex alteration pathway. Although no crystalline CdSO(4) compounds were identified on the Van Gogh paint samples, we conclude that the observed degradation was initially caused by oxidation of the original CdS pigment, similar as for the previous Ensor case. However, due to the presence of an overlying varnish containing lead-based driers and oxalate ions, secondary reactions took place. In particular, it appears that upon the photoinduced oxidation of its sulfidic counterion, the Cd(2+) ions reprecipitated at the paint/varnish interface after having formed a complex with oxalate ions that themselves are considered to be degradation products of the resin and/or oil in the varnish. The SO(4)(2-) anions, for their part, found a suitable reaction partner in Pb(2+) ions stemming from a dissolved lead

  5. Electronic structure investigation of highly compressed aluminum with K edge absorption spectroscopy.

    PubMed

    Benuzzi-Mounaix, A; Dorchies, F; Recoules, V; Festa, F; Peyrusse, O; Levy, A; Ravasio, A; Hall, T; Koenig, M; Amadou, N; Brambrink, E; Mazevet, S

    2011-10-14

    The electronic structure evolution of highly compressed aluminum has been investigated using time resolved K edge x-ray absorption spectroscopy. A long laser pulse (500 ps, I(L)≈8×10(13) W/cm(2)) was used to create a uniform shock. A second ps pulse (I(L)≈10(17)  W/cm(2)) generated an ultrashort broadband x-ray source near the Al K edge. The main target was designed to probe aluminum at reshocked conditions up to now unexplored (3 times the solid density and temperatures around 8 eV). The hydrodynamical conditions were obtained using rear side visible diagnostics. Data were compared to ab initio and dense plasma calculations, indicating potential improvements in either description. This comparison shows that x-ray-absorption near-edge structure measurements provide a unique capability to probe matter at these extreme conditions and severally constrains theoretical approaches currently used. PMID:22107398

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

    PubMed

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

    2016-07-28

    Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, and a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (-0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions. PMID:27475372

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  8. Trichroism in energy-loss near-edge structure spectroscopy: Polarization dependence of near-edge fine structures

    SciTech Connect

    Le Bosse, Jean-Claude; Epicier, Thierry; Chermette, Henry

    2007-08-15

    The goal of this paper is to relate the current of inelastically scattered electrons collected in a transmission electron microscope (TEM) to the double differential electron energy-loss cross section. Up to now, this relationship, which depends on the point symmetry around the probed atom site, has been essentially studied in a situation called dichroism. This situation can be encountered when a principal threefold, fourfold, or sixfold rotation axis through the probed atom site exists. The electron energy-loss cross section is then a linear combination of longitudinal and transversal cross sections, and the weights of these components are cos{sup 2} {theta}{sub q} and sin{sup 2} {theta}{sub q}, where {theta}{sub q} is the angle between the scattering wave vector q and the principal rotation axis. The first aim of this paper is to find the dependence on q of the cross section in all other cases, that is to say, when the symmetry around the probed atom site is described with one of the eight low symmetry point groups C{sub 1}, S{sub 2}, C{sub 1h}, C{sub 2}, C{sub 2h}, C{sub 2v}, D{sub 2}, and D{sub 2h}. In these eight cases of low symmetry, three distinct situations called trichroism can be distinguished. In these situations, the cross section is expressed in terms of the cross sections obtained for six, four, or three particular orientations of the scattering wave vector. The second aim of this paper is to provide an expression of the inelastically scattered electron current collected in a TEM for these three situations of trichroism. This current is expressed in terms of experimental parameters, such as the incident beam convergence, the collector acceptance, the electron beam kinetic energy, and the sample orientation. As in the case of dichroism, magic conditions can be found, for which the collected current becomes independent of the single-crystal sample orientation. The case of the C K edge in the nonstoichiometric V{sub 6}C{sub 5} metallic carbide with a trigonal symmetry is given as an illustration.

  9. 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.

  10. 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

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

    PubMed

    Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

    2015-11-01

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

  12. 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.

  13. Electronic and chemical state of aluminum from the single- (K) and double-electron excitation (KLII&III, KLI) x-ray absorption near-edge spectra of α-alumina, sodium aluminate, aqueous Al³⁺•(H₂O)₆, and aqueous Al(OH)₄⁻

    SciTech Connect

    Fulton, John L.; Govind, Niranjan; Huthwelker, Thomas; Bylaska, Eric J.; Vjunov, Aleksei; Pin, Sonia; Smurthwaite, Tricia D.

    2015-07-02

    We probe, at high energy resolution, the double electron excitation (KLII&II) x-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of α-alumina and sodium aluminate. The two solid standards, α-alumina (octahedral) and sodium aluminate (tetrahedral) are compared to aqueous species that have the same Al coordination symmetries, Al³⁺•6H₂O (octahedral) and Al(OH)₄⁻ (tetrahedral). For the octahedral species, the edge height of the KLII&III-edge is approximately 10% of the main K-edge however the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the α-alumina and aqueous Al³⁺•6H₂O the KLII&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KLII&III-edge feature interferes with an important region of the extended-XAFS region of the spectra for the K-edge of the crystalline and aqueous standards. The K-edge spectra and K-edge positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge XANES spectra reproduce the observed transitions in the experimental spectra of the four Al species. The KLII&III and KLI onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (ΔSCF) method. Research by JLF, NG, EJB, AV, TDS was supported by U.S. Department of Energy’s (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. NG thanks Amity Andersen for help with the α-Al₂O₃ and tetrahedral sodium aluminate (NaAlO₂) clusters. All the calculations were performed using the Molecular Science Computing Capability at EMSL, a national scientific user facility sponsored by the U.S. Department of Energy’s Office of Biological and Environmental Research and located at

  14. 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

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

    SciTech Connect

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

    2014-06-16

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

  16. 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.

  17. Electrically Active and Inactive B Lattice Sites in Ultrahighly B Doped Si(001): An X-Ray Near-Edge Absorption Fine-Structure and High-Resolution Diffraction Study

    SciTech Connect

    Vailionis, A.; Glass, G.; Desjardins, P.; Cahill, D.G.; Greene, J.E.

    1999-05-01

    B lattice positions are determined as a function of B concentration C{sub B} in ultrahighly doped Si(001):B layers grown by gas-source molecular beam epitaxy from B{sub 2}H {sub 6}/Si{sub 2}H{sub 6} . For C{sub B}{le}2.5{times}10{sup 20} cm{sup {minus}3} , all B atoms reside on tetrahedrally bonded electrically active substitutional Si sites. At higher C{sub B} , inactive B is incorporated as B pairs located on single Si sites and oriented primarily along in-plane [100] and [010] directions. The B pairs are sp{sup 2} bonded with trigonal coordination while substitutional single B atoms are sp{sup 3} . A surface reaction path leading to inactive B incorporation is proposed. {copyright} {ital 1999} {ital The American Physical Society}

  18. 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.

  19. Structure and Composition of Cu Doped CdSe Nanocrystals Using Soft X-ray Absorption Spectroscopy

    SciTech Connect

    Meulenberg, R W; van Buuren, T; Hanif, K M; Willey, T M; Strouse, G F; Terminello, L J

    2004-06-04

    The local structure and composition of Cu ions dispersed in CdSe nanocrystals is examined using soft x-ray absorption near edge spectroscopy (XANES). Using Cu L-edge XANES and X-ray photoelectron measurements (XPS), we find that the Cu ions exist in the Cu(I) oxidation state. We also find that the observed Cu L-edge XANES signal is directly proportional to the molar percent of Cu present in our final material. Se L-edge XANES indicates changes in the Se density of states with Cu doping, due to a chemical bonding effect, and supports a statistical doping mechanism. Photoluminescence (PL) measurements indicate the Cu ions may act as deep electron traps. We show that XANES, XPS, and PL are a powerful combination of methods to study the electronic and chemical structure of dopants in nanostructured materials.

  20. Effects of backlight structure on absorption experiments

    SciTech Connect

    Iglesias, C A

    2004-11-08

    The impact of spectral details in the backlight of absorption spectroscopy experiments is considered. It is shown that experimentally unresolved structure in the backlight spectrum can introduce significant errors in the inferred transmission. Furthermore, it is shown that a valuable experimental procedure previously used to test the accuracy of the data fails to reveal these errors.

  1. Enhanced absorption in silicon metamaterials waveguide structure

    NASA Astrophysics Data System (ADS)

    Hamouche, Houria; Shabat, Mohammed M.

    2016-07-01

    Metamaterial waveguide structures for silicon solar cells are a novel approach to antireflection coating structures that can be used for the achievement of high absorption in silicon solar cells. This paper investigates numerically the possibility of improving the performance of a planar waveguide silicon solar cell by incorporating a pair of silicon nitride/metamaterial layer between a semi-infinite glass cover layer and a semi-infinite silicon substrate layer. The optimized layer thicknesses of the pair are determined under the solar spectrum AM1.5 by the effective average reflectance method. The transmission and reflection coefficients are derived by the transfer matrix method for values of metamaterial's refractive index in visible and near-infrared radiation. In addition, the absorption coefficient is examined for several angles of incidence of the transverse electric polarized (TE), transverse magnetic polarized (TM) and the total (TE&TM) guided waves. Numerical results provide an extremely high absorption. The absorptivity of the structure achieves greater than 98 %.

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

    SciTech Connect

    Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th.; Heimann, P. A.; Dorchies, F.

    2014-04-17

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

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

    DOE PAGES

    Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; et al

    2014-04-17

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

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

    NASA Astrophysics Data System (ADS)

    Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th; Heimann, P. A.; Dorchies, F.

    2014-04-01

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

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

    PubMed

    Gaudin, J; Fourment, C; Cho, B I; Engelhorn, K; Galtier, E; Harmand, M; Leguay, P M; Lee, H J; Nagler, B; Nakatsutsumi, M; Ozkan, C; Störmer, M; Toleikis, S; Tschentscher, Th; Heimann, P A; Dorchies, F

    2014-04-17

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

  6. Characterizing the Solvated Structure of Photoexcited [Os(terpy)₂](2+) with X-ray Transient Absorption Spectroscopy and DFT Calculations.

    PubMed

    Zhang, Xiaoyi; Pápai, Mátyás; Møller, Klaus B; Zhang, Jianxin; Canton, Sophie E

    2016-01-01

    Characterizing the geometric and electronic structures of individual photoexcited dye molecules in solution is an important step towards understanding the interfacial properties of photo-active electrodes. The broad family of "red sensitizers" based on osmium(II) polypyridyl compounds often undergoes small photo-induced structural changes which are challenging to characterize. In this work, X-ray transient absorption spectroscopy with picosecond temporal resolution is employed to determine the geometric and electronic structures of the photoexcited triplet state of [Os(terpy)₂](2+) (terpy: 2,2':6',2″-terpyridine) solvated in methanol. From the EXAFS analysis, the structural changes can be characterized by a slight overall expansion of the first coordination shell [OsN₆]. DFT calculations supports the XTA results. They also provide additional information about the nature of the molecular orbitals that contribute to the optical spectrum (with TD-DFT) and the near-edge region of the X-ray spectra. PMID:26907233

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

    NASA Astrophysics Data System (ADS)

    Liu, Shanshan

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

  8. Thermally detected optical absorption in sophisticated nitride structures

    NASA Astrophysics Data System (ADS)

    Vasson, A.; Shubina, T. V.; Leymarie, J.

    2005-02-01

    The thermally detected optical absorption (TDOA) is applied to elucidate peculiarities of absorption in nitride structures of unusual morphology like GaN nanocolumns or InN layers with various imperfections. A study of GaN structures permits us to establish position of an absorption edge in TDOA spectra. We demonstrate that the absorption edge is different in GaN regions of opposite polarities. In InN with metallic In inclusions, this technique enable separation of InN interband absorption and extinction related to the Mie resonances, if the latter are below the principal absorption edge.

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

    PubMed

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

    2010-01-01

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

  10. X-ray absorption spectroscopy by full-field X-ray microscopy of a thin graphite flake: Imaging and electronic structure via the carbon K-edge

    PubMed Central

    Hitchock, Adam P; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Ewels, Chris P; Guttmann, Peter

    2012-01-01

    Summary We demonstrate that near-edge X-ray-absorption fine-structure spectra combined with full-field transmission X-ray microscopy can be used to study the electronic structure of graphite flakes consisting of a few graphene layers. The flake was produced by exfoliation using sodium cholate and then isolated by means of density-gradient ultracentrifugation. An image sequence around the carbon K-edge, analyzed by using reference spectra for the in-plane and out-of-plane regions of the sample, is used to map and spectrally characterize the flat and folded regions of the flake. Additional spectral features in both π and σ regions are observed, which may be related to the presence of topological defects. Doping by metal impurities that were present in the original exfoliated graphite is indicated by the presence of a pre-edge signal at 284.2 eV. PMID:23016137

  11. Metal induced gap states at LiCl Cu(0 0 1) interface studied by X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Kiguchi, Manabu; Katayama, Masao; Yoshikawa, Genki; Saiki, Koichiro; Koma, Atushi

    2003-05-01

    A single crystalline LiCl film grows heteroepitaxially on Cu(0 0 1) in a layer-by-layer fashion at 300 K. The LiCl-Cu(0 0 1) system provides a well-defined insulator-metal interface. Electronic structure of the LiCl film grown on Cu(0 0 1) was studied using Cl K-edge near edge X-ray absorption fine structure (NEXAFS). A pre-peak was observed on the bulk edge onset for the thin LiCl films. The pre-peak showed formation of metal-induced gap states (MIGS) in the band gap of LiCl. The characteristic decay length of the MIGS was determined to be 2.6 Å by analyzing the thickness dependence on the intensity of the pre-peak. The present result has revealed the MIGS at the well-defined insulator-metal interface for the first time.

  12. Documentation and Search for Missing Near Edge L-mode Transport

    NASA Astrophysics Data System (ADS)

    Waltz, R. E.; Holland, C.

    2011-10-01

    While GYRO simulations of the core (0 < r / a < 0 . 7) in typical DIII-D L-modes seems to be in good agreement with experiment, local GYRO simulated low- k (kθρs < 1) transport and turbulence intensity is about 5-fold lower than experimentally inferred levels in the near edge L-mode (r / a = 0 . 7 - 0 . 95) DIII-D shot 128913. Global slice GYRO simulations of this and other well-studied discharges are presented here to further document the shortfall. TGLF transport simulations over a large L-mode database indicate this short fall is not atypical and L-modes easily transit to H-like profiles. High edge e-i collisionality stabilizes the TEM modes so that χɛ decreases like T7/2 / n to the cold edge. The very high magnetic shear stabilizes the ITG despite the very high temperature gradient drive and high q. High- k ETG can make up for the shortfall in the electron but not the ion channel. Near edge L-mode transport is highly local. Artificially large edge damping of the zonal flows/GAMs helps only somewhat. Work supported by US DOE under DE-FG02-95ER54309 and DE-FG02-07ER54917.

  13. Electronic structures and bonding properties of chlorine-treated nitrogenated carbon nanotubes: X-ray absorption and scanning photoelectron microscopy studies

    SciTech Connect

    Ray, S. C.; Pao, C. W.; Tsai, H. M.; Chiou, J. W.; Pong, W. F.; Chen, C. W.; Tsai, M.-H.; Papakonstantinou, P.; Chen, L. C.; Chen, K. H.; Graham, W. G.

    2007-05-07

    The electronic and bonding properties of nitrogenated carbon nanotubes (N-CNTs) exposed to chlorine plasma were investigated using C and N K-edge x-ray absorption near-edge structure (XANES) and scanning photoelectron microscopy (SPEM). The C and N K-edge XANES spectra of chlorine-treated N-CNTs consistently reveal the formation of pyridinelike N-CNTs by the observation of 1s{yields}{pi}*(e{sub 2u}) antibonding and 1s{yields}{pi}*(b{sub 2g}) bonding states. The valence-band photoemission spectra obtained from SPEM images indicate that chlorination of the nanotubes enhances the C-N bonding. First-principles calculations of the partial densities of states in conjunction with C K-edge XANES data identify the presence of C-Cl bonding in chlorine treated N-CNTs.

  14. ATOMIC AND MOLECULAR PHYSICS: X-ray absorption near the edge structure and X-ray photoelectron spectroscopy studies on pyrite prepared by thermally sulfurizing iron films

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Liu, Ying-Shu; Wang, Bao-Yi; Wei, Long; Kui, Re-Xi; Qian, Hai-Jie

    2009-07-01

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

  15. Simple algorithm to determine the near-edge smoke boundaries with scanning lidar.

    PubMed

    Kovalev, Vladimir A; Newton, Jenny; Wold, Cyle; Hao, Wei Min

    2005-03-20

    We propose a modified algorithm for the gradient method to determine the near-edge smoke plume boundaries using backscatter signals of a scanning lidar. The running derivative of the ratio of the signal standard deviation (STD) to the accumulated sum of the STD is calculated, and the location of the global maximum of this function is found. No empirical criteria are required to determine smoke boundaries; thus the algorithm can be used without a priori selection of threshold values. The modified gradient method is not sensitive to the signal random noise at the far end of the lidar measurement range. Experimental data obtained with the Fire Sciences Laboratory lidar during routine prescribed fires in Montana were used to test the algorithm. Analysis results are presented that demonstrate the robustness of this algorithm. PMID:15813280

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

    SciTech Connect

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

    1998-02-15

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

  17. In situ extended X-ray absorption fine structure study during selective alcohol oxidation over Pd/Al2O3 in supercritical carbon dioxide.

    PubMed

    Grunwaldt, Jan-Dierk; Caravati, Matteo; Baiker, Alfons

    2006-05-25

    High-pressure in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data are reported during the selective oxidation of benzyl alcohol to benzaldehyde in supercritical carbon dioxide over a Pd/Al(2)O(3) catalyst (shell impregnated). For this purpose, a continuous-flow system with a spectroscopic cell suitable for in situ X-ray absorption studies on heterogeneous catalysts up to 200 degrees C and 200 bar has been developed. Due to the high contribution of the dense fluid to the overall X-ray absorption, high stability of the process pressure is mandatory, particularly when recording EXAFS spectra. According to EXAFS and XANES results, the palladium particles were fully reduced after exposure to benzyl alcohol in scCO(2). In contrast to Pd-catalyzed liquid-phase oxidation, a higher oxygen tolerance of the catalyst was observed. Palladium was partially oxidized on the surface under typical reaction conditions (0.9 mol % benzyl alcohol/0.5 mol % O(2) in carbon dioxide), which gradually increased when the concentration of oxygen in the feed was raised. Both XANES and EXAFS data uncovered that palladium is mainly oxidized on the surface or within the outermost layers. These results are in accordance with simulations of the XANES data using the FEFF8.20 code (program for ab initio calculations on multiple scattering XAS) and EXAFS data fitting/simulation. PMID:16706447

  18. Optimal design of porous structures for the fastest liquid absorption.

    PubMed

    Shou, Dahua; Ye, Lin; Fan, Jintu; Fu, Kunkun

    2014-01-14

    Porous materials engineered for rapid liquid absorption are useful in many applications, including oil recovery, spacecraft life-support systems, moisture management fabrics, medical wound dressings, and microfluidic devices. Dynamic absorption in capillary tubes and porous media is driven by the capillary pressure, which is inversely proportional to the pore size. On the other hand, the permeability of porous materials scales with the square of the pore size. The dynamic competition between these two superimposed mechanisms for liquid absorption through a heterogeneous porous structure may lead to an overall minimum absorption time. In this work, we explore liquid absorption in two different heterogeneous porous structures [three-dimensional (3D) circular tubes and porous layers], which are composed of two sections with variations in radius/porosity and height. The absorption time to fill the voids of porous constructs is expressed as a function of radius/porosity and height of local sections, and the absorption process does not follow the classic Washburn's law. Under given height and void volume, these two-section structures with a negative gradient of radius/porosity against the absorption direction are shown to have faster absorption rates than control samples with uniform radius/porosity. In particular, optimal structural parameters, including radius/porosity and height, are found that account for the minimum absorption time. The liquid absorption in the optimized porous structure is up to 38% faster than in a control sample. The results obtained can be used a priori for the design of porous structures with excellent liquid management property in various fields.

  19. Monopeptide versus Monopeptoid: Insights on Structure and Hydration of Aqueous Alanine and Sarcosine via X-ray Absorption Spectroscopy

    SciTech Connect

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

    2009-11-19

    Despite the obvious significance, the aqueous interactions of peptides remain incompletely understood. Their synthetic analogues called peptoids (poly-N-substituted glycines), have recently emerged as a promising biomimetic material, particularly due to their robust secondary structure and resistance to denaturation. We describe comparative near-edge x-ray absorption fine structure (NEXAFS) spectroscopy studies of aqueous sarcosine, the simplest peptoid, and alanine, its peptide isomer, interpreted by density functional theory calculations. The sarcosine nitrogen K-edge spectrum is blue-shifted with respect to that of alanine, in agreement with our calculations; we conclude that this shift results primarily from the methyl group substitution on the nitrogen of sarcosine. Our calculations indicate that the nitrogen K-edge spectrum of alanine differs significantly between dehydrated and hydrated scenarios, while that of the sarcosine zwitterion is less affected by hydration. In contrast, the computed sarcosine spectrum is greatly impacted by conformational variations, while the alanine spectrum is not. This relates to a predicted solvent dependence for alanine, as compared to sarcosine. Additionally, we show the theoretical nitrogen K-edge spectra to be sensitive to the degree of hydration, indicating that experimental X-ray spectroscopy may be able to distinguish between bulk and partial hydration, such as found in confined environments near proteins and in reverse micelles.

  20. 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.

  1. X-ray absorption studies of the local structure and f-level occupancy in CeIr(1-x)Rh(x)In(5)

    SciTech Connect

    Daniel, M.; Han, S.-W.; Booth, C.H.; Cornelius, A.L.; Pagliuso, P.G.; Sarrao, J.L.; Thompson, J.D.

    2004-04-15

    The CeIr{sub 1-x}Rh{sub x}In{sub 5} series exhibits a range of interesting phenomena, including heavy-fermion superconductivity, non-Fermi liquid behavior, and concomitant antiferromagnetism (AF) and superconductivity (SC). In the low-Rh concentration range (0.1 {ge} x {ge} 0.5), specific heat measurements show a broad anomaly, suggestive of gross phase separation. We have performed x-ray absorption experiments at the Ce L{sub III}, Ir L{sub III}, and Rh K-edges as a function of Rh concentration and temperature. X-ray absorption near-edge structure (XANES) measurements indicate that cerium is close to trivalent in this system, with no measurable change with temperature from 20-300 K, consistent with a heavy-fermion material. Extended x-ray absorption fine structure (EXAFS) measurements as a function of temperature from all measured edges indicate the local crystal structure of all samples is well ordered, with no gross phase separation observed, even for samples with x = 0.125 and x = 0.25. These results therefore suggest that the anomalous specific heat behavior in the 0.1 {ge} x {ge} 0.5 range have some other explanation, and some possibilities are discussed.

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

    SciTech Connect

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

    1996-12-31

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

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

    SciTech Connect

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  5. Structure of epitaxial (Fe,N) codoped rutile TiO2 thin films by x-ray absorption

    NASA Astrophysics Data System (ADS)

    Kaspar, T. C.; Ney, A.; Mangham, A. N.; Heald, S. M.; Joly, Y.; Ney, V.; Wilhelm, F.; Rogalev, A.; Yakou, F.; Chambers, S. A.

    2012-07-01

    Homoepitaxial thin films of Fe:TiO2 and (Fe,N):TiO2 were deposited on rutile(110) by molecular beam epitaxy. X-ray absorption near edge spectroscopy (XANES) spectra were collected at the Ti L-edge, Fe L-edge, Ti K-edge, O K-edge, and N K-edge. No evidence of structural disorder associated with a high concentration of oxygen vacancies is observed. Substitution of Fe for Ti could be inferred, and secondary phases such as Fe2O3, Fe3O4, and FeTiO3 can be ruled out. The similarity of the N K-edge spectra to O, and the presence of a strong x-ray linear dichroism signal for the N K-edge, indicates that N is substitutional for O in the rutile lattice and is not present as a secondary phase such as TiN. Simulations of the XANES spectra confirm substitution, although N appears to be present in more than one local environment. Neither Fe:TiO2 nor (Fe,N):TiO2 exhibit intrinsic room temperature ferromagnetism, despite the presence of mixed valent Fe(II)/Fe(III) in the reduced (Fe,N):TiO2 film.

  6. Quasi-static energy absorption of hollow microlattice structures

    SciTech Connect

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

    2014-12-01

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

  7. Electronic structure and optic absorption of phosphorene under strain

    NASA Astrophysics Data System (ADS)

    Duan, Houjian; Yang, Mou; Wang, Ruiqiang

    2016-07-01

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

  8. Iron absorption and phenolic compounds: importance of different phenolic structures.

    PubMed

    Brune, M; Rossander, L; Hallberg, L

    1989-08-01

    The phenolic compounds (phenolic monomers, polyphenols, tannins) are considered to interfere with iron absorption by complex formation with iron in the gastro-intestinal lumen, making the iron less available for absorption. Very little is known about the extent to which different types of phenolic compounds of different size and chemical structure inhibit iron absorption. The relationship between iron absorption and the amount and type of phenolic compounds was studied by the extrinsic tag method. The aims of the studies were as follows: (i) To study the effect of small phenolic compounds with different hydroxylation patterns (gallic acid, catechin, chlorogenic acid) on iron absorption, (ii) To study the effect of different amounts of a hydrolysable tannin containing ten gallic acid residues (tannic acid) on iron absorption. (iii) To study the degree of inhibition of iron absorption by some foods and beverages (oregano, spinach, coffee and tea) in relation to their respective content of iron-binding phenolic groups, measured by a newly developed method. The inhibition of iron absorption by tannic acid was strongly dose-related. The smallest amount (5 mg) inhibited absorption by 20 per cent, 25 mg by 67 per cent and 100 mg by 88 per cent. Gallic acid inhibited iron absorption to the same extent as tannic acid, per mol galloyl groups, whereas no inhibition was observed when catechin was added to the test meal. Chlorogenic acid inhibited iron absorption to a lesser extent. Oregano and tea inhibited iron absorption in proportion to their respective content of galloyl groups, whereas the inhibitory effect of spinach was less marked. The inhibiting effect of coffee was explained mainly by its content of galloyl groups, but also by some other factor, probably chlorogenic acid. It is concluded that the content of iron-binding galloyl groups might be a major determinant of the inhibitory effect of phenolic compounds on iron absorption from the diet, whereas the phenolic

  9. In situ surface extended x-ray absorption fine structure spectroscopy of a lead monolayer at a silver(111) electrode/electrolyte interface

    SciTech Connect

    Samant, M.G.; Borges, G.L.; Gordon J.G. II; Melroy, O.R.; Blum, L.

    1987-09-30

    With use of fluorescence detection and grazing incidence excitation, the X-ray absorption spectrum was obtained, at the PbL/sub III/ edge, of a monoatomic adlayer of lead on a silver (111) electrode immersed in solution. The adlayer was produced by under potential deposition from aqueous lead acetate/sodium acetate electrolyte. The edge position and the near-edge structure confirm that the lead is fully reduced to the zerovalent state. The extended X-ray absorption fine structure (EXAFS) contains no detectable contribution from lead-silver scattering, either because the lead layer is incommensurate with the underlying silver lattice or because there is large thermal motion of the lead atoms. Instead, the fine structure is due to scattering from a single type of light atom, most likely oxygen. This oxygen must arise from adsorbed water molecules or acetate ions. The lead-oxygen distance changes with the electrode potential from 2.33 +/- 0.02 A at -0.53 V to 2.38 +/- 0.02 A at -1 V (vs. Ag/AgCl, 3 M KCl).

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

    SciTech Connect

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

    2013-08-15

    Polycrystalline Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+δ} ceramics (x=0, 0.01, 0.03, 0.05) were fabricated using a simple thermal hydro-decomposition method and a spark plasma sintering technique. Thermoelectric property measurements showed that increasing Fe concentration resulted in a decrease in electrical resistivity, thermopower and thermal conductivity, leading to an improvement in the dimensionless figure-of-merit, >35% for x=0.05 at 1073 K. An X-ray absorption spectroscopy technique was used to investigate the local structure of Fe ions in the Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+δ} structure for the first time. By fitting data from the extended X-ray absorption fine structure (EXAFS) spectra and analyzing the X-ray absorption near-edge structure (XANES) spectra incorporated with first principle simulation, it was shown that Fe was substituted for Co in the the Ca{sub 2}CoO{sub 3} (rocksalt, RS) layer rather than in the CoO{sub 2} layer. Variation in the thermoelectric properties as a function of Fe concentration was attributed to charge transfer between the CoO{sub 2} and the RS layers. The origin of the preferential Fe substitution site was investigated considering the ionic radii of Co and Fe and the total energy of the system. - Graphical abstract: The Fe K-edge XANES spectra of: (a) experimental result in comparison to the simulated spectra when Fe atoms were substituted in the RS layer; (b) with magnetic moment; (c) without magnetic moment, and in the CoO{sub 2} layer; (d) with magnetic moment and (e) without magnetic moment. Highlights: • Synthesis, structural studies, and thermoelectric properties of Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+δ}. • Direct evidence for the local structure of the Fe ions in the Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+δ} using XAS analysis. • EXAFS and XANES analysis showed that Fe was likely to be situated in the RS layer structure. • Changes in TE property with Fe content was due to charge transfer between

  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. Dynamic energy absorption characteristics of hollow microlattice structures

    SciTech Connect

    Liu, YL; Schaedler, TA; Chen, X

    2014-10-01

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

  13. Absorption-reduced waveguide structure for efficient terahertz generation

    SciTech Connect

    Pálfalvi, L.; Fülöp, J. A.; Hebling, J.

    2015-12-07

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

  14. Energy absorption characteristics of nano-composite conical structures

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

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

  15. X-ray absorption spectroscopy of Ru-doped relaxor ferroelectrics with a perovskite-type structure

    NASA Astrophysics Data System (ADS)

    Vitova, T.; Mangold, S.; Paulmann, C.; Gospodinov, M.; Marinova, V.; Mihailova, B.

    2014-04-01

    X-ray absorption near-edge structure and extended x-ray absorption fine structure spectroscopy at the Ru K edge of Ru-doped PbSc0.5Ta0.5O3 (PST-Ru), PbSc0.5Nb0.5O3 (PSN-Ru), and 0.9PbZn1/3Nb2/3O3-0.1PbTiO3 (PZN-0.1PT-Ru) as well as at the Ta L3 edge of PST-Ru and the Nb K edge of PSN-Ru was applied to study the short- and intermediate-range atomic arrangements in perovskite-type (ABO3) relaxor ferroelectrics. The compounds were also analyzed by complementary Raman scattering, visible/near-visible absorption spectroscopy, and synchrotron x-ray single-crystal diffraction. The results show that Ru is octahedrally coordinated in all three relaxor host matrices but the average oxidation state of Ru in PST-Ru and PSN-Ru is ˜4.4, whereas it is ˜3.8 in PZN-0.1PT-Ru. In PbSc0.5B''0.5O3 (B'' = Ta, Nb) Ru substitutes for the B'' cations in the form of isolated point defects, while in PZN-0.1PT-Ru Ru replaces adjacent A and B sites, forming a chainlike structural species of face-sharing elongated octahedra. Chemical 1:1 B-site order as well as dynamic BO6 tilting is observed around both the Ru dopant and the major B'' cation in PST-Ru and PSN-Ru regardless of the fact that according to x-ray diffraction at ambient conditions, the average structure is cubic with weak or no long-range chemical order. Pb cations are off-center displaced from the prototypic cubic A site for all three compounds and in Ru-doped PbSc0.5B''0.5O3 the BO6 tilt angle correlates with the degree of coherent B-Pb distances.

  16. 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})

  17. Thin resonant structures for angle and polarization independent microwave absorption

    NASA Astrophysics Data System (ADS)

    Lockyear, Matthew J.; Hibbins, Alastair P.; Sambles, J. Roy; Hobson, Peter A.; Lawrence, Christopher R.

    2009-01-01

    We present a microwave absorbing structure comprised of an array of subwavelength radius copper disks, closely spaced from a ground plane by a low loss dielectric. Experiments and accompanying modeling demonstrate that this structure supports electromagnetic standing wave resonances associated with a cylindrical cavity formed by the volume immediately beneath each metal disk. Microwave absorption on resonance of these modes, at wavelengths much greater than the thickness of the structure, is dictated almost entirely by the radius of the disk and permittivity of the dielectric, being largely independent of the incident angle and polarization.

  18. 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.

  19. 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.

  20. Sound absorption by subwavelength membrane structures: A geometric perspective

    NASA Astrophysics Data System (ADS)

    Yang, Min; Li, Yong; Meng, Chong; Fu, Caixing; Mei, Jun; Yang, Zhiyu; Sheng, Ping

    2015-12-01

    Decorated membranes comprising a thin layer of elastic film with small rigid platelets fixed on top have been found to be efficient absorbers of low-frequency sound. In this work we consider the problem of sound absorption from a perspective aimed at deriving upper bounds under different scenarios, i.e., whether the sound is incident from one side only or from both sides, and whether there is a reflecting surface on the back side of the membrane. By considering the negligible thickness of the membrane, usually on the order of a fraction of one millimeter, we derive a relation showing that the sum of the incoming sound waves' (complex) pressure amplitudes, averaged over the area of the membrane, must be equal to that of the outgoing waves. By using this relation, and without going to any details of the wave solutions, it is shown that the maximum absorption achievable from one-sided incidence is 50%, while the maximum absorption with a back-reflecting surface can reach 100%. The latter was attained by the hybridized resonances. All the results are shown to be in excellent agreement with the experiments. This generalized perspective, when used together with the Green function's formalism, can be useful in gaining insights into the constraints on what are achievable in scatterings and absorption by thin film structures and delineating them.

  1. X-ray absorption spectroscopy of strongly disordered glasses: Local structure around Ag ions in g-Ag{sub 2}O{center_dot}nB{sub 2}O{sub 3}

    SciTech Connect

    Kuzmin, A.; Dalba, G.; Fornasini, P.; Rocca, F.; Sipr, O.

    2006-05-01

    The local structure around Ag ions in silver borate glasses g-Ag{sub 2}O{center_dot}nB{sub 2}O{sub 3} (n=2,4) was studied by x-ray absorption spectroscopy at the Ag K edge for temperatures from 77 to 450 K. Extended x-ray absorption fine structure (EXAFS) analysis based on cumulant expansion or multishell Gaussian model fails for these systems. Therefore, the radial distribution functions (RDFs) around Ag ions were reconstructed using a method based on the direct inversion of the EXAFS expression. The RDFs consist of about eight atoms (oxygens and borons), exhibit a relatively weak temperature dependence, and indicate the presence of strong static disorder. Two main components can be identified in RDFs, located at about 2.3-2.4 A and 2.5-3.4 A, respectively. The chemical types of atoms contributing to the RDF were determined via a simulation of configurationally averaged x-ray absorption near-edge structure (XANES) and EXAFS signals. The immediate neighborhood of Ag contains mostly oxygens while borons dominate at larger distances. The combination of EXAFS and XANES techniques allowed us to determine a more complete structural model than would be possible by relying solely on either EXAFS or XANES alone.

  2. Differential near-edge coherent diffractive imaging using a femtosecond high-harmonic XUV light source.

    PubMed

    Weise, Fabian; Neumark, Daniel M; Leone, Stephen R; Gessner, Oliver

    2012-11-19

    Element-specific contrast enhancement in tabletop coherent diffractive imaging (CDI) is demonstrated by employing an ultrafast extreme ultraviolet (XUV) light source with tunable photon energy. By combining two measurements performed at energies below and above the Al L(2,3) absorption edge, the spatial autocorrelation function of a micron-scale double pinhole in a 300 nm thick aluminum foil is retrieved despite a dominant background signal from directly transmitted light across the entire range of detectable diffraction angles. The fringe visibility in the diffraction patterns is 0 below the Al L(2,3) edge, 0.53 ± 0.06 above the edge, and 0.73 ± 0.08 in the differential image that combines the two measurements. The proof-of-principle experiment demonstrates that the variations of XUV optical constants in the vicinity of an inner-shell absorption edge can be utilized to improve the chemical sensitivity and image reconstruction quality of laboratory-based ultrafast imaging experiments.

  3. Structure- and dose-absorption relationships of coffee polyphenols.

    PubMed

    Erk, Thomas; Hauser, Johanna; Williamson, Gary; Renouf, Mathieu; Steiling, Heike; Dionisi, Fabiola; Richling, Elke

    2014-01-01

    Chlorogenic acids (CGAs) from coffee have biological effects related to human health. Thus, specific data on their bioavailability in the upper gastrointestinal tract are of high interest, since some molecules are absorbed here and so are not metabolized by colonic microflora. Up to now, no data on structure-absorption relationships for CGAs have been published, despite this being the most consumed group of polyphenols in the western diet. To address this gap, we performed ex vivo absorption experiments with pig jejunal mucosa using the Ussing chamber model (a model simulating the mucosa and its luminal/apical side). The main coffee polyphenols, caffeoylquinic acid (CQA), feruloylquinic acid (FQA), caffeic acid (CA), dicaffeoylquinic acid (diCQA), and D-(-)-quinic acid (QA), were incubated in individual experiments equivalent to gut lumen physiologically achievable concentrations (0.2-3.5 mM). Identification and quantification were performed with HPLC-diode array detection and HPLC-MS/MS. Additionally, the presence of ABC-efflux transporters was determined by Western blot analysis. The percentages of initially applied CGAs that were absorbed through the jejunal pig mucosa were, in increasing order: diCQA, trace; CQA, ≈ 1%; CA, ≈ 1.5%; FQA, ≈ 2%; and QA, ≈ 4%. No differences were observed within the CGA subgroups. Dose-absorption experiments with 5-CQA suggested a passive diffusion (nonsaturable absorption and a linear dose-flux relationship) and its secretion was affected by NaN3 , indicating an active efflux. The ABC-efflux transporters MDR 1 and MRP 2 were identified in pig jejunal mucosa for the first time. We conclude that active efflux plays a significant role in CGA bioavailability and, further, that the mechanism of CGA absorption in the jejunum is governed by their physicochemical properties.

  4. Tunable many-body interactions in semiconducting graphene: Giant excitonic effect and strong optical absorption

    NASA Astrophysics Data System (ADS)

    Dvorak, Marc; Wu, Zhigang

    2015-07-01

    Electronic and optical properties of graphene depend strongly on many-body interactions. Employing the highly accurate many-body perturbation approach based on Green's functions, we find a large renormalization over independent particle methods of the fundamental band gaps of semiconducting graphene structures with periodic defects. Additionally, their exciton binding energies are larger than 0.4 eV, suggesting significantly strengthened electron-electron and electron-hole interactions. Their absorption spectra show two strong peaks whose positions are sensitive to the defect fraction and distribution. The strong near-edge optical absorption and excellent tunability make these two-dimensional materials promising for optoelectronic applications.

  5. Incorporation of Pertechnetate and Perrhenate into Corroded Steel Surfaces Studied by X-ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Heald, Steve M.; Krupka, Kenneth M.; Brown, Christopher F.

    2012-04-01

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

  6. Energy absorption characteristics of lightweight structural member by stacking conditions

    NASA Astrophysics Data System (ADS)

    Choi, Juho; Yang, Yongjun; Hwang, Woochae; Pyeon, Seokbeom; Min, Hanki; Yeo, Ingoo; Yang, Inyoung

    2012-04-01

    The recent trend in vehicle design is aimed at improving crash safety and environmental-friendliness. To solve these issues, the needs for lighter vehicle to limit exhaust gas and improve fuel economy has been requested for environmental-friendliness. Automobile design should be made for reduced weight once the safety of vehicle is maintained. In this study, composite structural members were manufactured using carbon fiber reinforced plastic (CFRP) which are representative lightweight structural materials. Carbon fiber has been researched as alternative to metals for lightweight vehicle and better fuel economy. CFRP is an anisotropic material which is the most widely adapted lightweight structural member because of their inherent design flexibility and high specific strength and stiffness. Also, variation of CFRP interface number is important to increase the energy absorption capacity. In this study, one type of circular shaped composite tube was used, combined with reinforcing foam. The stacking condition was selected to investigate the effect of the fiber orientation angle and interface number. The crashworthy behavior of circular composite material tubes subjected to static axial compression under same conditions is reported. The axial static collapse tests were carried out for each section member. The collapse modes and the energy absorption capability of the members were analyzed.

  7. Energy absorption characteristics of lightweight structural member by stacking conditions

    NASA Astrophysics Data System (ADS)

    Choi, Juho; Yang, Yongjun; Hwang, Woochae; Pyeon, Seokbeom; Min, Hanki; Yeo, Ingoo; Yang, Inyoung

    2011-11-01

    The recent trend in vehicle design is aimed at improving crash safety and environmental-friendliness. To solve these issues, the needs for lighter vehicle to limit exhaust gas and improve fuel economy has been requested for environmental-friendliness. Automobile design should be made for reduced weight once the safety of vehicle is maintained. In this study, composite structural members were manufactured using carbon fiber reinforced plastic (CFRP) which are representative lightweight structural materials. Carbon fiber has been researched as alternative to metals for lightweight vehicle and better fuel economy. CFRP is an anisotropic material which is the most widely adapted lightweight structural member because of their inherent design flexibility and high specific strength and stiffness. Also, variation of CFRP interface number is important to increase the energy absorption capacity. In this study, one type of circular shaped composite tube was used, combined with reinforcing foam. The stacking condition was selected to investigate the effect of the fiber orientation angle and interface number. The crashworthy behavior of circular composite material tubes subjected to static axial compression under same conditions is reported. The axial static collapse tests were carried out for each section member. The collapse modes and the energy absorption capability of the members were analyzed.

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

    SciTech Connect

    Zhang, Chu; Gustafson, Johan; Merte, Lindsay R.; Evertsson, Jonas; Norén, Katarina; Carlson, Stefan; Svensson, Håkan; Carlsson, Per-Anders

    2015-03-15

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

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

    NASA Astrophysics Data System (ADS)

    Zhang, Chu; Gustafson, Johan; Merte, Lindsay R.; Evertsson, Jonas; Norén, Katarina; Carlson, Stefan; Svensson, Hâkan; Carlsson, Per-Anders

    2015-03-01

    An easy-to-use sample environment reaction cell for X-ray based in situ studies of powders and small structured samples, e.g., powder, pellet, and monolith catalysts, is described. The design of the cell allows for flexible use of appropriate X-ray transparent windows, shielding the sample from ambient conditions, such that incident X-ray energies as low as 3 keV can be used. Thus, in situ X-ray absorption spectroscopy (XAS) measurements in either transmission or fluorescence mode are facilitated. Total gas flows up to about 500 mln/min can be fed while the sample temperature is accurately controlled (at least) in the range of 25-500 °C. The gas feed is composed by a versatile gas-mixing system and the effluent gas flow composition is monitored with mass spectrometry (MS). These systems are described briefly. Results from simultaneous XAS/MS measurements during oxidation of carbon monoxide over a 4% Pt/Al2O3 powder catalyst are used to illustrate the system performance in terms of transmission XAS. Also, 2.2% Pd/Al2O3 and 2% Ag - Al2O3 powder catalysts have been used to demonstrate X-ray absorption near-edge structure (XANES) spectroscopy in fluorescence mode. Further, a 2% Pt/Al2O3 monolith catalyst was used ex situ for transmission XANES. The reaction cell opens for facile studies of structure-function relationships for model as well as realistic catalysts both in the form of powders, small pellets, and coated or extruded monoliths at near realistic conditions. The applicability of the cell for X-ray diffraction measurements is discussed.

  10. Characterization of protein immobilization at silver surfaces bynear edge x-ray absorption fine structure spectroscopy

    SciTech Connect

    Liu, X.; Jang, C.-H.; Zheng, F.; J rgensen, A.; Denlinger, J.D.; Dickson, K.A.; Raines, R.T.; Abbott, N.L.; Himpsel, F.J.

    2006-06-21

    Ribonuclease A (RNase A) is immobilized on silver surfacesin oriented and random form via self-assembled monolayers (SAMs) ofalkanethiols. The immobilization process is characterized step-by-stepusing chemically selective near-edge X-ray absorption fine structurespectroscopy (NEXAFS) at the C, N, and S K-edges. Causes of imperfectimmobilization are pinpointed, such as oxidation and partial desorptionof the alkanethiol SAMs and incomplete coverage. The orientation of theprotein layer manifests itself in an 18 percent polarization dependenceof the NEXAFS signal from the N 1s to pi* transition of the peptide bond,which is not seen for a random orientation. The S 1s to C-S sigma*transition exhibits an even larger polarization dependence of 41 percent,which is reduced to 5 percent for a random orientation. A quantitativemodel is developed that explains the sign and magnitude of thepolarization dependence at both edges. The results demonstrate thatNEXAFS is able to characterize surface reactions during theimmobilization of proteins and to provide insight into their orientationson surfaces.

  11. X-ray absorption spectroscopy of metalloproteins.

    PubMed

    Ward, Jesse; Ollmann, Emily; Maxey, Evan; Finney, Lydia A

    2014-01-01

    Metalloproteins are enormously important in biology. While a variety of techniques exist for studying metals in biology, X-ray absorption spectroscopy is particularly useful in that it can determine the local electronic and physical structure around the metal center, and is one of the few avenues for studying "spectroscopically silent" metal ions like Zn(II) and Cu(I) that have completely filled valence bands. While X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) are useful for studying metalloprotein structure, they suffer the limitation that the detected signal is an average of all the various metal centers in the sample, which limits its usefulness for studying metal centers in situ or in cell lysates. It would be desirable to be able to separate the various proteins in a mixture prior to performing X-ray absorption studies, so that the derived signal is from one species only. Here we describe a method for performing X-ray absorption spectroscopy on protein bands following electrophoretic separation and western blotting.

  12. Ab initio X-Ray Absorption Fine Structure Cumulants

    NASA Astrophysics Data System (ADS)

    Vila, F.; Rehr, J. J.; Rossner, H. H.; Krappe, H. J.

    2006-03-01

    Theoretical calculations of vibrational effects in x-ray absorption spectra typically employ semi-phenomenological models, e.g. empirical force constants or correlated Debye or Einstein models. Instead we introduce an efficient and generally applicable ab initio approach based on electronic structure calculations of the dynamical matrix together with the Lanczos recursion algorithm [1] and relations between the cumulants. The approach yields 1) the thermal expansion coefficients (first cumulant of the vibrational distribution function); 2) correlated Debye-Waller factors (second cumulants) and 3) anharmonic contributions (third cumulants). Results are presented for crystalline (Cu, Au, Ge, GaAs) and molecular (GeCl4, C6H6) systems. Our results for the Debye-Waller factors agree well with experiment. [1]H.J. Krappe and H.H. Rossner, Phys. Rev. B70, 104102 (2004).

  13. Molecular structures and protonation state of 2-Mercaptopyridine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Eckert, S.; Miedema, P. S.; Quevedo, W.; O'Cinneide, B.; Fondell, M.; Beye, M.; Pietzsch, A.; Ross, M.; Khalil, M.; Föhlisch, A.

    2016-03-01

    The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms.

  14. Electronic structure of the organic semiconductor copper phthalocyanine: experiment and theory.

    PubMed

    Aristov, V Yu; Molodtsova, O V; Maslyuk, V V; Vyalikh, D V; Zhilin, V M; Ossipyan, Yu A; Bredow, T; Mertig, I; Knupfer, M

    2008-01-21

    The electronic structure of the organic semiconductor copper-phthalocyanine (CuPc) has been determined by a combination of conventional and resonant photoemission, near-edge x-ray absorption, as well as by the first-principles calculations. The experimentally obtained electronic valence band structure of CuPc is in very good agreement with the calculated density of states results, allowing the derivation of detailed site specific information.

  15. Omnidirectional light absorption of disordered nano-hole structure inspired from Papilio ulysses.

    PubMed

    Wang, Wanlin; Zhang, Wang; Fang, Xiaotian; Huang, Yiqiao; Liu, Qinglei; Bai, Mingwen; Zhang, Di

    2014-07-15

    Butterflies routinely produce nanostructured surfaces with useful properties. Here, we report a disordered nano-hole structure with ridges inspired by Papilio ulysses that produce omnidirectional light absorption compared with the common ordered structure. The result shows that the omnidirectional light absorption is affected by polarization, the incident angle, and the wavelength. Using the finite-difference time-domain (FDTD) method, the stable omnidirectional light absorption is achieved in the structure inspired from the Papilio ulysses over a wide incident angle range and with various wavelengths. This explains some of the mysteries of the structure of the Papilio ulysses butterfly. These conclusions can guide the design of omnidirectional absorption materials. PMID:25121688

  16. Omnidirectional light absorption of disordered nano-hole structure inspired from Papilio ulysses.

    PubMed

    Wang, Wanlin; Zhang, Wang; Fang, Xiaotian; Huang, Yiqiao; Liu, Qinglei; Bai, Mingwen; Zhang, Di

    2014-07-15

    Butterflies routinely produce nanostructured surfaces with useful properties. Here, we report a disordered nano-hole structure with ridges inspired by Papilio ulysses that produce omnidirectional light absorption compared with the common ordered structure. The result shows that the omnidirectional light absorption is affected by polarization, the incident angle, and the wavelength. Using the finite-difference time-domain (FDTD) method, the stable omnidirectional light absorption is achieved in the structure inspired from the Papilio ulysses over a wide incident angle range and with various wavelengths. This explains some of the mysteries of the structure of the Papilio ulysses butterfly. These conclusions can guide the design of omnidirectional absorption materials.

  17. Predictions of the near edge transport shortfall in DIII-D L-mode plasmas using the trapped gyro-Landau-fluid model

    SciTech Connect

    Kinsey, J. E.; Staebler, G. M.; Candy, J.; Petty, C. C.; Waltz, R. E.; Rhodes, T. L.

    2015-01-15

    Previous studies of DIII-D L-mode plasmas have shown that a transport shortfall exists in that our current models of turbulent transport can significantly underestimate the energy transport in the near edge region. In this paper, the Trapped Gyro-Landau-Fluid (TGLF) drift wave transport model is used to simulate the near edge transport in a DIII-D L-mode experiment designed to explore the impact of varying the safety factor on the shortfall. We find that the shortfall systematically increases with increasing safety factor and is more pronounced for the electrons than for the ions. Within the shortfall dataset, a single high current case has been found where no transport shortfall is predicted. Reduced neutral beam injection power has been identified as the key parameter separating this discharge from other discharges exhibiting a shortfall. Further analysis shows that the energy transport in the L-mode near edge region is not stiff according to TGLF. Unlike the H-mode core region, the predicted temperature profiles are relatively more responsive to changes in auxiliary heating power. In testing the fidelity of TGLF for the near edge region, we find that a recalibration of the collision model is warranted. A recalibration improves agreement between TGLF and nonlinear gyrokinetic simulations performed using the GYRO code with electron-ion collisions. The recalibration only slightly impacts the predicted shortfall.

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

    SciTech Connect

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

    1989-09-19

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

  19. Micro Structure of Nickel in Spin Coated Thin Film Magnets

    NASA Astrophysics Data System (ADS)

    Vides, Katherine; Dahanayake, Rasika; Samarasekara, Pubudu; Dehipawala, Sunil

    2014-03-01

    Micro-Structure of Nickel compounds in thin film magnets was investigated using Extended X ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES). These thin film magnets were prepared by spin coating several layers of precursor containing iron and Nickel on a glass substrate. Thickness of the films was controlled by spin rate. Several magnets were prepared with different thicknesses and each film was annealed to either 200C or 350c in air. Variation of oxidation state and nearest neighbor bond lengths of each magnet was measured to characterize Ni in the film.

  20. Correction method for the self-absorption effects in fluorescence extended X-ray absorption fine structure on multilayer samples.

    PubMed

    Li, Wen Bin; Yang, Xiao Yue; Zhu, Jing Tao; Tu, Yu Chun; Mu, Bao Zhong; Yu, Hai Sheng; Wei, Xiang Jun; Huang, Yu Ying; Wang, Zhan Shan

    2014-05-01

    A novel correction method for self-absorption effects is proposed for extended X-ray absorption fine structure (EXAFS) detected in the fluorescence mode on multilayer samples. The effects of refraction and multiple reflection at the interfaces are fully considered in this correction method. The correction is performed in k-space before any further data analysis, and it can be applied to single-layer or multilayer samples with flat surfaces and without thickness limit when the model parameters for the samples are known. The validity of this method is verified by the fluorescence EXAFS data collected for a Cr/C multilayer sample measured at different experimental geometries. PMID:24763646

  1. Fabrication of multi-layered absorption structure for high quantum efficiency photon detectors

    SciTech Connect

    Fujii, Go; Fukuda, Daiji; Numata, Takayuki; Yoshizawa, Akio; Tsuchida, Hidemi; Fujino, Hidetoshi; Ishii, Hiroyuki; Itatani, Taro; Zama, Tatsuya; Inoue, Shuichiro

    2009-12-16

    We report on some efforts to improve a quantum efficiency of titanium-based optical superconducting transition edge sensors using the multi-layered absorption structure for maximizing photon absorption in the Ti layer. Using complex refractive index values of each film measured by a Spectroscopic Ellipsometry, we designed and optimized by a simulation code. An absorption measurement of fabricated structure was in good agreement with the design and was higher than 99% at optimized wavelength of 1550 nm.

  2. KEMP: A program script for automated biological x-ray absorption spectroscopy data reduction

    SciTech Connect

    Korbas, Malgorzata; Fulla Marsa, Daniel; Meyer-Klaucke, Wolfram

    2006-06-15

    Automation of x-ray absorption spectroscopic (XAS) data reduction is essential to cope with high-throughput data collection becoming available at an increasing number of synchrotron radiation centers. A flexible script called KEMP has been developed and implemented at the XAS beamline at EMBL Hamburg. It automatically processes fluorescence XAS data. The pipeline includes dead time correction, energy calibration, selection of fluorescence detector channels, as well as the extraction of x-ray absorption near-edge structure and extended x-ray-absorption fine structure. The output is quickly available and thus can be included in the design of further experiments, which results in a more efficient use of the beam time.

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

    PubMed Central

    2015-01-01

    The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide–metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp2-derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network. PMID:25152800

  4. X-ray absorption studies of battery materials

    SciTech Connect

    McBreen, J.

    1996-10-01

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

  5. The tunable electronic structure and optic absorption properties of phosphorene by a normally applied electric field

    NASA Astrophysics Data System (ADS)

    Yang, Mou; Duan, Hou-Jian; Wang, Rui-Qiang

    2016-10-01

    We studied the electronic structure and optical absorption properties of phosphorene (a monolayer black phosphorus) under a normally applied electric field. The electric field enlarges the energy gap, weakens the effective mass anisotropy, and increases the effective mass component along the armchair direction (x-direction) for both conduction and valence bands but provides little change to the component along the zigzag direction (y-direction). The band edge optical absorption is completely polarized in the x-direction, and decreases when increasing the electric field. If the exciting frequency is beyond the energy gap, the absorption for the y-polarized light becomes nonzero, but the absorption is still highly polarized.

  6. First principles calculation of oxygen K edge absorption spectrum of acetic acid: Relationship between the spectrum and molecular dynamics

    NASA Astrophysics Data System (ADS)

    Matsui, Yoshiki; Mizoguchi, Teruyasu

    2016-04-01

    First principles calculation of the oxygen K-edge absorption near-edge structure of liquid acetic acid was performed to investigate the relationship between the spectrum and the molecular dynamics in a liquid. The single and double bonded oxygens gave strong peaks at different energies. A liquid model constructed using a molecular dynamics simulation reproduced the experimental spectrum. We revealed that the effect of the dynamic behavior of molecules in a liquid clearly appears in the particular peak from a single-bond oxygen. The relationship between the bonding nature and the dynamic information of a molecule in a spectrum was determined and presented.

  7. Improved diamond surfaces following lift-off and plasma treatments as observed by x-ray absorption spectroscopy

    SciTech Connect

    Stacey, Alastair; Drumm, Virginia S.; Fairchild, Barbara A.; Ganesan, Kumar; Prawer, Steven; Rubanov, Sergey; Kalish, Rafi; Cowie, Bruce C. C.; Hoffman, Alon

    2011-05-02

    We have investigated the nature of the residual damage in diamond crystals following the ion implantation/graphitization ''lift-off'' process, using near-edge x-ray absorption fine structure spectroscopy and transmission electron microscopy. A defective but crystalline interface is found, which displays dense pre-edge unoccupied states and an almost complete loss of the core-level C 1s exciton signature. This residual crystalline damage is resistant to standard chemical etching, however a hydrogen plasma treatment is found to completely recover a pristine diamond surface. Analysis and removal of residual ion-induced damage is considered crucial to the performance of many diamond device architectures.

  8. 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

  9. 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

  10. 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.

  11. Mode manipulation and near-THz absorptions in binary grating-graphene layer structures

    PubMed Central

    2014-01-01

    The excitation and absorption properties of grating coupled graphene surface plasmons were studied. It was found that whether a mode can be excited is mainly determined by the frequency of incident light and the duty ratio of gratings. In the structure consisting graphene bilayer, a blueshift of the excitation frequency existed when the distance between neighbor graphene layer were decreased gradually. In graphene-grating multilayer structures, a strong absorption (approximately 90% at maximum) was found in near-THz range. PMID:24559407

  12. Acid-site characterization of water-oxidized alumina films by near-edge x-ray absorption and soft x-ray photoemission

    SciTech Connect

    O`Hagan, P.J.; Merrill, R.P.; Rhodin, T.N.; Woronick, S.W.; Shinn, N.D.; Woolery, G.L.; Chester, A.W.

    1994-12-01

    Hydroxylated alumina films have been synthesized by water oxidation of single crystal Al(110) surfaces. Thermal dehydroxylation results in anion vacancies which produce an Al(3s) defect state 3.5 eV below the conduction band edge. A maximum in the defect-DOS occurs for oxides heated to 350 to 400C, which is where the materials exhibit maximum Lewis acidity with respect to C{sub 2}H{sub 4}. Adsorbed C{sub 2}H{sub 4} produces thermally active C{sub 2} species which interact covalently with the defect-DOS and nonbonding O(2p) from the top of the valence band. C(1s) binding energies suggest significant charge transfer which is consistent with a carbenium ion. Ni evaporated onto the surface, however, transfers charge directly to Al species and does not interact with O atoms at the defect site. The defect-DOS is regenerated when the C{sub 2} species decomposes or when Ni migrates thermally through the oxide layer.

  13. Omnidirectional polarization insensitive tunable absorption in graphene metamaterial of nanodisk structure

    NASA Astrophysics Data System (ADS)

    Ning, Renxia; Bao, Jie; Jiao, Zheng; Xu, Yuan

    2015-11-01

    Tunable absorption based on graphene metamaterial with nanodisk structure at near-infrared frequency was investigated using the finite difference time domain method. The absorption of the nanodisk structure which consisting of Au-MgF2-graphene-Au-polyimide (from bottom to top) can be tuned by the chemical potential of graphene at certain diameter of nanodisk. The permittivity of graphene is discussed with different chemical potential to obtain tunable absorption. It is shown that the increased value of the chemical potential of graphene can lead to blue-shifted of the absorption peaks and the values decreased. Moreover, dual-band and triple-band absorption can be achieved for resonance frequencies at normal incidence. Compared with diameter of nanodisks, the multilayer structure shows multi-band absorber, and an omnidirectional absorption at 195.25 THz is insensitive to TE/TM polarization. This omnidirectional polarization insensitive absorption may be applied by optical communications such as optical absorber, near infrared stealth, and filter.

  14. Biomimetic cellular metals-using hierarchical structuring for energy absorption.

    PubMed

    Bührig-Polaczek, A; Fleck, C; Speck, T; Schüler, P; Fischer, S F; Caliaro, M; Thielen, M

    2016-07-19

    Fruit walls as well as nut and seed shells typically perform a multitude of functions. One of the biologically most important functions consists in the direct or indirect protection of the seeds from mechanical damage or other negative environmental influences. This qualifies such biological structures as role models for the development of new materials and components that protect commodities and/or persons from damage caused for example by impacts due to rough handling or crashes. We were able to show how the mechanical properties of metal foam based components can be improved by altering their structure on various hierarchical levels inspired by features and principles important for the impact and/or puncture resistance of the biological role models, rather than by tuning the properties of the bulk material. For this various investigation methods have been established which combine mechanical testing with different imaging methods, as well as with in situ and ex situ mechanical testing methods. Different structural hierarchies especially important for the mechanical deformation and failure behaviour of the biological role models, pomelo fruit (Citrus maxima) and Macadamia integrifolia, were identified. They were abstracted and transferred into corresponding structural principles and thus hierarchically structured bio-inspired metal foams have been designed. A production route for metal based bio-inspired structures by investment casting was successfully established. This allows the production of complex and reliable structures, by implementing and combining different hierarchical structural elements found in the biological concept generators, such as strut design and integration of fibres, as well as by minimising casting defects. To evaluate the structural effects, similar investigation methods and mechanical tests were applied to both the biological role models and the metallic foams. As a result an even deeper quantitative understanding of the form-structure

  15. Biomimetic cellular metals-using hierarchical structuring for energy absorption.

    PubMed

    Bührig-Polaczek, A; Fleck, C; Speck, T; Schüler, P; Fischer, S F; Caliaro, M; Thielen, M

    2016-01-01

    Fruit walls as well as nut and seed shells typically perform a multitude of functions. One of the biologically most important functions consists in the direct or indirect protection of the seeds from mechanical damage or other negative environmental influences. This qualifies such biological structures as role models for the development of new materials and components that protect commodities and/or persons from damage caused for example by impacts due to rough handling or crashes. We were able to show how the mechanical properties of metal foam based components can be improved by altering their structure on various hierarchical levels inspired by features and principles important for the impact and/or puncture resistance of the biological role models, rather than by tuning the properties of the bulk material. For this various investigation methods have been established which combine mechanical testing with different imaging methods, as well as with in situ and ex situ mechanical testing methods. Different structural hierarchies especially important for the mechanical deformation and failure behaviour of the biological role models, pomelo fruit (Citrus maxima) and Macadamia integrifolia, were identified. They were abstracted and transferred into corresponding structural principles and thus hierarchically structured bio-inspired metal foams have been designed. A production route for metal based bio-inspired structures by investment casting was successfully established. This allows the production of complex and reliable structures, by implementing and combining different hierarchical structural elements found in the biological concept generators, such as strut design and integration of fibres, as well as by minimising casting defects. To evaluate the structural effects, similar investigation methods and mechanical tests were applied to both the biological role models and the metallic foams. As a result an even deeper quantitative understanding of the form-structure

  16. Local environment of metal ions in phthalocyanines: K-edge X-ray absorption spectra.

    PubMed

    Rossi, G; d'Acapito, F; Amidani, L; Boscherini, F; Pedio, M

    2016-09-14

    We report a detailed study of the K-edge X-ray absorption spectra of four transition metal phthalocyanines (MPc, M = Fe, Co, Cu and Zn). We identify the important single and multiple scattering contributions to the spectra in the extended energy range and provide a robust treatment of thermal damping; thus, a generally applicable model for the interpretation of X-ray absorption fine structure spectra is proposed. Consistent variations of bond lengths and Debye Waller factors are found as a function of atomic number of the metal ion, indicating a variation of the metal-ligand bond strength which correlates with the spatial arrangement and occupation of molecular orbitals. We also provide an interpretation of the near edge spectral features in the framework of a full potential real space multiple scattering approach and provide a connection to the local electronic structure. PMID:27510989

  17. Local environment of metal ions in phthalocyanines: K-edge X-ray absorption spectra.

    PubMed

    Rossi, G; d'Acapito, F; Amidani, L; Boscherini, F; Pedio, M

    2016-09-14

    We report a detailed study of the K-edge X-ray absorption spectra of four transition metal phthalocyanines (MPc, M = Fe, Co, Cu and Zn). We identify the important single and multiple scattering contributions to the spectra in the extended energy range and provide a robust treatment of thermal damping; thus, a generally applicable model for the interpretation of X-ray absorption fine structure spectra is proposed. Consistent variations of bond lengths and Debye Waller factors are found as a function of atomic number of the metal ion, indicating a variation of the metal-ligand bond strength which correlates with the spatial arrangement and occupation of molecular orbitals. We also provide an interpretation of the near edge spectral features in the framework of a full potential real space multiple scattering approach and provide a connection to the local electronic structure.

  18. Molecular structures and absorption spectra assignment of corrole NH tautomers.

    PubMed

    Beenken, Wichard; Presselt, Martin; Ngo, Thien H; Dehaen, Wim; Maes, Wouter; Kruk, Mikalai

    2014-02-01

    The individual absorption spectra of the two NH tautomers of 10-(4,6-dichloropyrimidin-5-yl)-5,15-dimesitylcorrole are assigned on the basis of the Gouterman four-orbital model and a quantum chemical TD-DFT study. The assignment indicates that the red-shifted T1 tautomer is the one with protonated pyrrole nitrogen atoms N(21), N(22) and N(23), whereas the blue-shifted T2 tautomer has pyrrole nitrogen atoms N(21), N(22) and N(24) protonated. A wave-like nonplanar distortion of the macrocycle in the ground state is found for both NH tautomers, with the wave axis going through the pyrroles containing N(22) and N(24). The 7C plane determined by the least-squares distances to the carbon atoms C1, C4, C5, C6, C9, C16, and C19 is suggested as a mean corrole macrocycle plane for the analysis of out-of-plane distortions. The magnitude of these distortions is distinctly different for the two NH tautomers, leading to substantial perturbations of their acid-base properties, which are rationalized by the interplay of the degree of out-of-plane distortion of the macrocycle as a whole and the tendency of the pyrrole nitrogen atoms toward pyramidalization, with the former leading to a basicity increase whereas the latter enhances the acidity.

  19. Enhanced absorption of graphene strips with a multilayer subwavelength grating structure

    SciTech Connect

    Hu, Jin-Hua; Huang, Yong-Qing Duan, Xiao-Feng; Wang, Qi; Zhang, Xia; Wang, Jun; Ren, Xiao-Min

    2014-12-01

    The optical absorption of graphene strips covered on a multilayer subwavelength grating (MSG) surface is theoretically investigated. The absorption of graphene strips with MSG is enhanced in the wavelength range of 1500 nm to 1600 nm by critical coupling, which is associated with the combined effects of a guided resonance of MSG and its photonic band gap effect. The critical coupling of the graphene strips can be controlled by adjusting the incident angle without changing the structural parameters of MSG. The absorption of graphene strips can also be tuned by varying key parameters, such as grating period, strip width, and incident angle.

  20. Structural transformations of stacking fault tetrahedra upon the absorption of point defects

    NASA Astrophysics Data System (ADS)

    Poletaev, G. M.; Starostenkov, M. D.

    2009-01-01

    Mechanisms of the structural modification of stacking fault tetrahedra (SFTs) upon the absorption of point defects have been studied by the method of molecular dynamics. The sequential absorption of vacancies by a perfect SFT is accompanied by the following transformations: (i) the formation of a step on one of the SFT faces, (ii) a change in the step sign upon reaching the middle of the face, (iii) the formation of an SFT with truncated vertex, and (iv) the formation of the perfect SFT. Upon the absorption of interstitial atoms, the stages of SFT transformation follow the reverse order.

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

    NASA Astrophysics Data System (ADS)

    Saikia, Dip

    2008-04-01

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

  2. Designing photonic structures of nanosphere arrays on reflectors for total absorption

    NASA Astrophysics Data System (ADS)

    Almpanis, E.; Papanikolaou, N.

    2013-08-01

    By means of full electrodynamic simulations, we investigate structures that can totally absorb light minimizing all reflections. Such efficient absorbers of visible and infrared light are useful in photovoltaic and sensor applications. Our study provides a simple and transparent analysis of the optical properties of structures comprising a resonant cavity and a reflector, which are the basic ingredients of a resonant absorber, based on general principles of scattering theory. We concentrate on periodic arrays of metallic or dielectric spherical particles in front of metallic or dielectric mirrors and show that tuning the material absorption could turn resonances in the structures into total absorption bands. Perfect absorption is predicted in metallic sphere arrays but also for Si spheres on a metallic substrate, moreover, by replacing the substrate below the Si spheres with a lossless dielectric Bragg mirror an all-dielectric-perfect-absorber is designed.

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

    SciTech Connect

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

    2015-11-15

    A set of r.f. sputter deposited ZnO thin films prepared with different Mn doping concentrations have been characterised by Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Spectroscopy (XANES) measurements at Zn, Mn and O K edges and at Mn L{sub 2,3} edges apart from long range structural characterisation by Grazing Incident X-ray Diffraction (GIXRD) technique. Magnetic measurements show room temperature ferromagnetism in samples with lower Mn doping which is however, gets destroyed at higher Mn doping concentration. The results of the magnetic measurements have been explained using the local structure information obtained from EXAFS and XANES measurements.

  4. Measurements of photon interference X-ray absorption fine structure (piXAFS).

    PubMed

    Tröger, L; Kappen, P; Nishino, Y; Haack, N; Materlik, G

    2001-03-01

    Experimental data are presented which demonstrate the existence of a fine structure in extended X-ray absorption spectra due to interference effects in the initial photon state (piXAFS). Interference occurs between the incident electromagnetic wave and its coherently scattered waves from neighboring atoms. Using fine platinum and tungsten powders as well as polycrystalline platinum foil, piXAFS was measured in high-precision absorption experiments at beamline X1 at HASYLAB/DESY over a wide energy range. piXAFS is observed below and above absorption-edge positions in both transmission and total-electron-yield detection. Based on experimental data it is shown that piXAFS is sensitive to geometric atomic structure. Fourier-transformed piXAFS data carry information, comparable with that of EXAFS, about the short-range-order structure of the sample. Sharp structures occur in piXAFS when a Bragg backscattering condition of the incident X-rays is fulfilled. They allow precise measurement of long-range-order structural information. Measured data are compared with simulations based on piXAFS theory. Although piXAFS structures are similarly observed in two detection techniques, the importance of scattering off the sample for the measurements needs to be investigated further. Disentangling piXAFS, multielectron photoexcitations and atomic XAFS in high-precision measurements close to absorption edges poses a challenge for future studies.

  5. Structure-property Relationships for Methyl-terminated Alkyl Self-assembled Monolayers

    SciTech Connect

    F DelRio; D Rampulla; C Jaye; G Stan; R Gates; D Fischer; R Cook

    2011-12-31

    Structure-property relationships for methyl-terminated alkyl self-assembled monolayers (SAMs) are developed using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and atomic force microscopy (AFM). NEXAFS C K-edge spectra are used to compute the dichroic ratio, which provides a quantitative measure of the molecular structure. AFM data are analyzed with an elastic adhesive contact model, modified by a first-order elastic perturbation method to include substrate effects, to extract the monolayer mechanical properties. Using this approach, the measured mechanical properties are not influenced by the substrate, which allows universal structure-property relationships to be developed for methyl-terminated alkyl SAMs.

  6. Electronic structure of bacterial surface protein layers

    SciTech Connect

    Maslyuk, Volodymyr V.; Mertig, Ingrid; Bredow, Thomas; Mertig, Michael; Vyalikh, Denis V.; Molodtsov, Serguei L.

    2008-01-15

    We report an approach for the calculation of the electronic density of states of the dried two-dimensional crystalline surface protein layer (S layer) of the bacterium Bacillus sphaericus NCTC 9602. The proposed model is based on the consideration of individual amino acids in the corresponding conformation of the peptide chain which additively contribute to the electronic structure of the entire protein complex. The derived results agree well with the experimental data obtained by means of photoemission (PE), resonant PE, and near-edge x-ray absorption spectroscopy.

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

    PubMed

    Qu, Xiao-ying; Li, Yu-jin

    2010-11-01

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

  8. Ab initio self-consistent x-ray absorption fine structure analysis for metalloproteins.

    PubMed

    Dimakis, Nicholas; Bunker, Grant

    2006-12-01

    X-ray absorption fine structure is a powerful tool for probing the structures of metals in proteins in both crystalline and noncrystalline environments. Until recently, a fundamental problem in biological XAFS has been that ad hoc assumptions must be made concerning the vibrational properties of the amino acid residues that are coordinated to the metal to fit the data. Here, an automatic procedure for accurate structural determination of active sites of metalloproteins is presented. It is based on direct multiple-scattering simulation of experimental X-ray absorption fine structure spectra combining electron multiple scattering calculations with density functional theory calculations of vibrational modes of amino acid residues and the genetic algorithm differential evolution to determine a global minimum in the space of fitting parameters. Structure determination of the metalloprotein active site is obtained through a self-consistent iterative procedure with only minimal initial information.

  9. Structural Characterization of Bimetallic Nanomaterials with Overlapping X-ray Absorption Edges

    SciTech Connect

    Menard, L.; Wang, Q; Kang, J; Sealey, A; Girolami, G; Teng, X; Frenkel, A; Nuzzo, R

    2009-01-01

    We describe a data analysis method for extended x-ray absorption fine structure spectroscopy suitable for use with compounds of diverse form that contain overlapping absorption edges. This method employs direct concurrent analysis of the data-demonstrated here for cases involving two interfering metal edges-and does not utilize subtractive or data filtering strategies that have been previously used to address this challenge. Its generality and precision are demonstrated in analyses made on two model nanoscale samples: (1) a Ir-Pt nanoparticle system supported on ?-Al2O3 and (2) a hybrid system of Pt nanowires on which Au nanoparticles have been nucleated and grown at the nanowire tips, stacking faults, and twinning boundaries. The results obtained demonstrate the unique compositional and structural qualities of these two systems as well as the broader utility of the new x-ray absorption spectroscopy based protocol used to characterize them.

  10. Electronic structure and luminescence center of blue luminescent carbon nanocrystals

    NASA Astrophysics Data System (ADS)

    Zhou, Jigang; Zhou, Xingtai; Li, Ruying; Sun, Xueliang; Ding, Zhifeng; Cutler, Jeffrey; Sham, Tsun-Kong

    2009-06-01

    The electronic structure and the origin of luminescence from blue luminescent carbon nanocrystals (CNC) have been investigated with X-ray absorption near-edge structures (XANES) and X-ray excited optical luminescence (XEOL). XANES shows that nitrogen has been incorporated into the carbon nanocrystals matrix (dominated by sp 2 carbon). XEOL from CNC is compared with that from natural diamond and previously reported CVD nanodiamond containing N impurities. The results reveal that N doping is almost certainly responsible for the blue luminescence in carbon nanocrystals. The implication of the results is discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  12. Enhancing sound absorption and transmission through flexible multi-layer micro-perforated structures.

    PubMed

    Bravo, Teresa; Maury, Cédric; Pinhède, Cédric

    2013-11-01

    Theoretical and experimental results are presented into the sound absorption and transmission properties of multi-layer structures made up of thin micro-perforated panels (ML-MPPs). The objective is to improve both the absorption and insulation performances of ML-MPPs through impedance boundary optimization. A fully coupled modal formulation is introduced that predicts the effect of the structural resonances onto the normal incidence absorption coefficient and transmission loss of ML-MPPs. This model is assessed against standing wave tube measurements and simulations based on impedance translation method for two double-layer MPP configurations of relevance in building acoustics and aeronautics. Optimal impedance relationships are proposed that ensure simultaneous maximization of both the absorption and the transmission loss under normal incidence. Exhaustive optimization of the double-layer MPPs is performed to assess the absorption and/or transmission performances with respect to the impedance criterion. It is investigated how the panel volumetric resonances modify the excess dissipation that can be achieved from non-modal optimization of ML-MPPs. PMID:24180777

  13. Acoustic contributions of a sound absorbing blanket placed in a double panel structure: absorption versus transmission.

    PubMed

    Doutres, Olivier; Atalla, Noureddine

    2010-08-01

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

  14. Atomic structure of machined semiconducting chips: An x-ray absorption spectroscopy study

    SciTech Connect

    Paesler, M.; Sayers, D.

    1988-12-01

    X-ray absorption spectroscopy (XAS) has been used to examine the atomic structure of chips of germanium that were produced by single point diamond machining. It is demonstrated that although the local (nearest neighbor) atomic structure is experimentally quite similar to that of single crystal specimens information from more distant atoms indicates the presence of considerable stress. An outline of the technique is given and the strength of XAS in studying the machining process is demonstrated.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  16. Structural and electrical properties of In-implanted Ge

    SciTech Connect

    Feng, R. Kremer, F.; Mirzaei, S.; Medling, S. A.; Ridgway, M. C.; Sprouster, D. J.; Decoster, S.; Glover, C. J.; Russo, S. P.

    2015-10-28

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

  17. Coupling continuous damage and debris fragmentation for energy absorption prediction by cfrp structures during crushing

    NASA Astrophysics Data System (ADS)

    Espinosa, Christine; Lachaud, Frédéric; Limido, Jérome; Lacome, Jean-Luc; Bisson, Antoine; Charlotte, Miguel

    2015-05-01

    Energy absorption during crushing is evaluated using a thermodynamic based continuum damage model inspired from the Matzenmiller-Lubliner-Taylors model. It was found that for crash-worthiness applications, it is necessary to couple the progressive ruin of the material to a representation of the matter openings and debris generation. Element kill technique (erosion) and/or cohesive elements are efficient but not predictive. A technique switching finite elements into discrete particles at rupture is used to create debris and accumulated mater during the crushing of the structure. Switching criteria are evaluated using the contribution of the different ruin modes in the damage evolution, energy absorption, and reaction force generation.

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

    NASA Astrophysics Data System (ADS)

    Zheng, Li-Yang; Wu, Ying; Zhang, Xiao-Liu; Ni, Xu; Chen, Ze-Guo; Lu, Ming-Hui; Chen, Yan-Feng

    2013-10-01

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

  19. First-principles calculation of electronic structure and optical absorption of BN ZnO

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao; Schleife, Andre

    2015-03-01

    The α-BN structure of ZnO, a nonequilibrium phase with a transition pressure of 25 GPa, has been found in nano structures of ZnO. The structural difference between the BN structure and the equilibrium wurtzite structure can play an important role for applications of nanostructured ZnO. In order to understand the difference, first principles calculations have been performed on both phases. The electronic structure is computed using the GW method based on Density Functional Theory and HSE hybrid functional calculations. The GW method includes the quasiparticle effects due to the screened electron-electron interaction which gives an accurate description of the electronic band structure and density of states. After that, by solving the Bethe-Salpeter Equation for the optical polarization function, which take excitonic effects into account, we have achieved an accurate description of optical absorption spectra for both structures. We find a good agreement with experimental and previous computational results for WZ structure, and predict the absorption for the BN structure. The BN structure shows a larger band gap and we found a very large optical anisotropy: The gap for extraordinary light polarization is almost 0.7eV larger than that for ordinary light polarization.

  20. Electronic Structure of the Organic Semiconductor Copper Tetraphenylporphyrin (CuTPP)

    SciTech Connect

    Reid, I.; Zhang, Y; Demasi, A; Blueser, A; Piper, L; Downes, J; Matsuura, A; Hughes, G; Smith, K

    2009-01-01

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

  1. A study on collapse behavior and energy absorption capability of Al/CFRP hybrid structural member

    NASA Astrophysics Data System (ADS)

    Hwang, Woo-Chae; Lee, Kil-Sung; Yang, Yong-Jun; Choi, Ju-Ho; Jung, Jong-An; Cha, Cheon-Seok; Yang, In-Young

    2012-04-01

    In vehicle industry, the design of vehicle should be inclined towards the safety performance aspect, at the same time; it also should have weight loss of a vehicles structural member. In this study, experimental investigations are performed for Al/CFRP Hybrid structural members. They are cured by heating to the appropriate curing temperature (130°C) by means of a heater at the vacuum bag of the autoclave. Because the CFRP is an anisotropic material whose mechanical properties, such as strength and elasticity, change with its stacking condition, special attention was given to the effects of the stacking condition on the collapse behavior evaluation of the Al/CFRP Hybrid structural members. The collapse mode and energy absorption capability of the Al/CFRP Hybrid structural members was analyzed with change of the fiber orientation. The stacking condition were selected to investigate the effect of the fiber orientation angle (+/-15°, +/-45°, 90°, 0°/90°and 90°/0° where 0°direction coincides with axis of the member)on the energy absorption of the Al/CFRP Hybrid structural members. The collapse mode and energy absorption capability of Al/CFRP Hybrid structural members was analyzed with change of the fiber orientation of CFRP.

  2. A study on collapse behavior and energy absorption capability of Al/CFRP hybrid structural member

    NASA Astrophysics Data System (ADS)

    Hwang, Woo-Chae; Lee, Kil-Sung; Yang, Yong-Jun; Choi, Ju-Ho; Jung, Jong-An; Cha, Cheon-Seok; Yang, In-Young

    2011-11-01

    In vehicle industry, the design of vehicle should be inclined towards the safety performance aspect, at the same time; it also should have weight loss of a vehicles structural member. In this study, experimental investigations are performed for Al/CFRP Hybrid structural members. They are cured by heating to the appropriate curing temperature (130°C) by means of a heater at the vacuum bag of the autoclave. Because the CFRP is an anisotropic material whose mechanical properties, such as strength and elasticity, change with its stacking condition, special attention was given to the effects of the stacking condition on the collapse behavior evaluation of the Al/CFRP Hybrid structural members. The collapse mode and energy absorption capability of the Al/CFRP Hybrid structural members was analyzed with change of the fiber orientation. The stacking condition were selected to investigate the effect of the fiber orientation angle (+/-15°, +/-45°, 90°, 0°/90°and 90°/0° where 0°direction coincides with axis of the member)on the energy absorption of the Al/CFRP Hybrid structural members. The collapse mode and energy absorption capability of Al/CFRP Hybrid structural members was analyzed with change of the fiber orientation of CFRP.

  3. Microwave-Absorption Properties of Three Kinds of Structured Cu/C Composites.

    PubMed

    Jiang, Linwen; Wang, Zhenhua; Li, Da; Geng, Dianyu; Wang, Yu; An, Jing; He, Jun; Liu, Wei; Zhang, Zhidong

    2016-06-01

    The microwave-absorption properties of three kinds of (core-shell, uniform-mixing and double-layer structured) Cu/C composites are investigated in the 2-18 GHz frequency range. The results show that the Cu/C composites with core-shell structure are favorable to obtain higher relative permittivity and better microwave-absorption properties in comparison with other Cu/C composites. The reflection loss (RL) values exceeding -10 dB are obtained in 13.0-17.2 GHz at the absorber thickness of 1.6 mm for the core-shell structured Cu/C nanoparticles, which cover most of Ku-band (12-18 GHz). The excellent microwave-absorption properties may result from synergetic effects induced by the tightly-connected core-shell interfaces. The synergetic effects are explained by a simulated physical model, wherein both the interfacial polarizations and interfacial multiple reflections are responsible to the excellent microwave-absorption performances.

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

    SciTech Connect

    Wang, Ke-Fan; Shao, Hezhu; Liu, Kong; Qu, Shengchun E-mail: wangyx@henu.edu.cn; Wang, Zhanguo; Wang, Yuanxu E-mail: wangyx@henu.edu.cn

    2015-09-14

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

  5. X-ray absorption study of the electronic structure of Mn-doped amorphous Si

    SciTech Connect

    Arenholz, Elke; Zeng, Li; Huegel, A.; Helgren, E.; Hellman, F.; Piamonteze, C.; Arenholz, E.

    2008-03-08

    The electronic structure of Mn in amorphous Si (a-Mn{sub x}Si{sub 1?x}) is studied by X-ray absorption spectroscopy at the Mn L{sub 3,2} edges for x = 0.005-0.18. Except the x = 0.005 sample, which shows a slight signature of Mn{sup 2+} atomic multiplets associated with a local Mn moment, all samples have broad and featureless L{sub 3,2} absorption peaks, corresponding to an itinerant state for all 3d electrons. The broad X-ray absorption spectra exclude the possibility of a localized 3d moment and explain the unexpectedly quenched Mn moment in this magnetically-doped amorphous semiconductor. Such a fully delocalized d state of Mn dopant in Si has not been previously suggested.

  6. Plane-wave DFT-LDA calculation of the electronic structure and absorption spectrum of copper

    NASA Astrophysics Data System (ADS)

    Marini, Andrea; Onida, Giovanni; del Sole, Rodolfo

    2001-11-01

    We present an accurate, first-principles study of the electronic structure and absorption spectrum of bulk copper within density functional theory in the local density approximation, including the study of intraband transitions. We construct norm-conserving pseudopotentials (PP's) including the 3d shell (and optionally the underlying 3s and 3p shells) in the valence and requiring a relatively small plane-wave basis (60 and 140 Ry cutoff, respectively). As a consequence, these PP's are strongly nonlocal, yielding macroscopically wrong results in the absorption spectrum when momentum matrix elements are computed naively. Our results are compared with experimental photoemission, absorption, and electron energy loss data, and suggest nontrivial self-energy effects in the quasiparticle spectrum of Cu.

  7. 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.

  8. Improvement of infrared single-photon detectors absorptance by integrated plasmonic structures

    PubMed Central

    Csete, Mária; Sipos, Áron; Szalai, Anikó; Najafi, Faraz; Szabó, Gábor; Berggren, Karl K.

    2013-01-01

    Plasmonic structures open novel avenues in photodetector development. Optimized illumination configurations are reported to improve p-polarized light absorptance in superconducting-nanowire single-photon detectors (SNSPDs) comprising short- and long-periodic niobium-nitride (NbN) stripe-patterns. In OC-SNSPDs consisting of ~quarter-wavelength dielectric layer closed by a gold reflector the highest absorptance is attainable at perpendicular incidence onto NbN patterns in P-orientation due to E-field concentration at the bottom of nano-cavities. In NCAI-SNSPDs integrated with nano-cavity-arrays consisting of vertical and horizontal gold segments off-axis illumination in S-orientation results in polar-angle-independent perfect absorptance via collective resonances in short-periodic design, while in long-periodic NCAI-SNSPDs grating-coupled surface waves promote EM-field transportation to the NbN stripes and result in local absorptance maxima. In NCDAI-SNSPDs integrated with nano-cavity-deflector-array consisting of longer vertical gold segments large absorptance maxima appear in 3p-periodic designs due to E-field enhancement via grating-coupled surface waves synchronized with the NbN stripes in S-orientation, which enable to compensate fill-factor-related retrogression. PMID:23934331

  9. 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.

  10. Structural color printing based on plasmonic metasurfaces of perfect light absorption

    PubMed Central

    Cheng, Fei; Gao, Jie; Luk, Ting S.; Yang, Xiaodong

    2015-01-01

    Subwavelength structural color filtering and printing technologies employing plasmonic nanostructures have recently been recognized as an important and beneficial complement to the traditional colorant-based pigmentation. However, the color saturation, brightness and incident angle tolerance of structural color printing need to be improved to meet the application requirement. Here we demonstrate a structural color printing method based on plasmonic metasurfaces of perfect light absorption to improve color performances such as saturation and brightness. Thin-layer perfect absorbers with periodic hole arrays are designed at visible frequencies and the absorption peaks are tuned by simply adjusting the hole size and periodicity. Near perfect light absorption with high quality factors are obtained to realize high-resolution, angle-insensitive plasmonic color printing with high color saturation and brightness. Moreover, the fabricated metasurfaces can be protected with a protective coating for ambient use without degrading performances. The demonstrated structural color printing platform offers great potential for applications ranging from security marking to information storage. PMID:26047486

  11. Structural color printing based on plasmonic metasurfaces of perfect light absorption

    NASA Astrophysics Data System (ADS)

    Cheng, Fei; Gao, Jie; Luk, Ting S.; Yang, Xiaodong

    2015-06-01

    Subwavelength structural color filtering and printing technologies employing plasmonic nanostructures have recently been recognized as an important and beneficial complement to the traditional colorant-based pigmentation. However, the color saturation, brightness and incident angle tolerance of structural color printing need to be improved to meet the application requirement. Here we demonstrate a structural color printing method based on plasmonic metasurfaces of perfect light absorption to improve color performances such as saturation and brightness. Thin-layer perfect absorbers with periodic hole arrays are designed at visible frequencies and the absorption peaks are tuned by simply adjusting the hole size and periodicity. Near perfect light absorption with high quality factors are obtained to realize high-resolution, angle-insensitive plasmonic color printing with high color saturation and brightness. Moreover, the fabricated metasurfaces can be protected with a protective coating for ambient use without degrading performances. The demonstrated structural color printing platform offers great potential for applications ranging from security marking to information storage.

  12. Structural color printing based on plasmonic metasurfaces of perfect light absorption

    DOE PAGES

    Cheng, Fei; Gao, Jie; Luk, Ting S.; Yang, Xiaodong

    2015-06-05

    Subwavelength structural color filtering and printing technologies employing plasmonic nanostructures have recently been recognized as an important and beneficial complement to the traditional colorant-based pigmentation. However, the color saturation, brightness and incident angle tolerance of structural color printing need to be improved to meet the application requirement. Here we demonstrate a structural color printing method based on plasmonic metasurfaces of perfect light absorption to improve color performances such as saturation and brightness. Thin-layer perfect absorbers with periodic hole arrays are designed at visible frequencies and the absorption peaks are tuned by simply adjusting the hole size and periodicity. Near perfectmore » light absorption with high quality factors are obtained to realize high-resolution, angle-insensitive plasmonic color printing with high color saturation and brightness. Moreover, the fabricated metasurfaces can be protected with a protective coating for ambient use without degrading performances. The demonstrated structural color printing platform offers great potential for applications ranging from security marking to information storage.« less

  13. Structural color printing based on plasmonic metasurfaces of perfect light absorption

    SciTech Connect

    Cheng, Fei; Gao, Jie; Luk, Ting S.; Yang, Xiaodong

    2015-06-05

    Subwavelength structural color filtering and printing technologies employing plasmonic nanostructures have recently been recognized as an important and beneficial complement to the traditional colorant-based pigmentation. However, the color saturation, brightness and incident angle tolerance of structural color printing need to be improved to meet the application requirement. Here we demonstrate a structural color printing method based on plasmonic metasurfaces of perfect light absorption to improve color performances such as saturation and brightness. Thin-layer perfect absorbers with periodic hole arrays are designed at visible frequencies and the absorption peaks are tuned by simply adjusting the hole size and periodicity. Near perfect light absorption with high quality factors are obtained to realize high-resolution, angle-insensitive plasmonic color printing with high color saturation and brightness. Moreover, the fabricated metasurfaces can be protected with a protective coating for ambient use without degrading performances. The demonstrated structural color printing platform offers great potential for applications ranging from security marking to information storage.

  14. Enhancing the absorption capabilities of thin-film solar cells using sandwiched light trapping structures.

    PubMed

    Abdellatif, S; Kirah, K; Ghannam, R; Khalil, A S G; Anis, W

    2015-06-10

    A novel structure for thin-film solar cells is simulated with the purpose of maximizing the absorption of light in the active layer and of reducing the parasitic absorption in other layers. In the proposed structure, the active layer is formed from an amorphous silicon thin film sandwiched between silicon nanowires from above and photonic crystal structures from below. The upper electrical contact consists of an indium tin oxide layer, which serves also as an antireflection coating. A metal backreflector works additionally as the other contact. The simulation was done using a new reliable, efficient and generic optoelectronic approach. The suggested multiscale simulation model integrates the finite-difference time-domain algorithm used in solving Maxwell's equation in three dimensions with a commercial simulation platform based on the finite element method for carrier transport modeling. The absorption profile, the external quantum efficient, and the power conversion efficiency of the suggested solar cell are calculated. A noticeable enhancement is found in all the characteristics of the novel structure with an estimated 32% increase in the total conversion efficiency over a cell without any light trapping mechanisms. PMID:26192857

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

    SciTech Connect

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

    2006-08-15

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

  16. X-ray chemical imaging and the electronic structure of a single nanoplatelet Ni/graphene composite.

    PubMed

    Zhou, Chunyu; Wang, Jian; Szpunar, Jerzy A

    2014-03-01

    Chemical imaging and quantitative analysis of a single graphene nanoplatelet grown with Ni nanoparticles (Ni/graphene) has been performed by scanning transmission X-ray microscopy (STXM). Local electronic and chemical structure of Ni/graphene has been investigated by spatially resolved C, O K-edges and Ni L-edge X-ray absorption near edge structure (XANES) spectroscopy, revealing the covalent anchoring of Ni(0) on graphene. This study facilitates the understanding of the structure modification of host materials for hydrogen storage and offers a better understanding of interaction between Ni particles and graphene.

  17. Control of the active site structure of giant bilayer hemoglobin from the Annelid Eisenia foetida using hierarchic assemblies

    SciTech Connect

    Girasole, Marco; Arcovito, Alessandro; Marconi, Augusta; Davoli, Camilla; Congiu-Castellano, Agostina; Bellelli, Andrea; Amiconi, Gino

    2005-12-05

    The active site structure of the oxygenated derivative of the main subassemblies (whole protein, dodecamers, and trimers) of the giant haemoglobin from Eisenia foetida has been characterized by x-ray absorption near edge structure spectroscopy. The data revealed a remarkable effect of the hierarchic assemblies on the active site of the subunit. Specifically, the whole protein has the same site structure of the dodecamer, while a sharp conformational transition occurs when the dodecamer is disassembled into trimers (and monomers) revealing that constraints due to the protein matrix determine the active site geometry and, consequently, the protein function in these large complexes.

  18. Inside and Outside: X-ray Absorption Spectroscopy Mapping of Chemical Domains in Graphene Oxide.

    PubMed

    De Jesus, Luis R; Dennis, Robert V; Depner, Sean W; Jaye, Cherno; Fischer, Daniel A; Banerjee, Sarbajit

    2013-09-19

    The oxidative chemistry of graphite has been investigated for over 150 years and has attracted renewed interest given the importance of exfoliated graphene oxide as a precursor to chemically derived graphene. However, the bond connectivities, steric orientations, and spatial distribution of functional groups remain to be unequivocally determined for this highly inhomogeneous nonstoichiometric material. Here, we demonstrate the application of principal component analysis to scanning transmission X-ray microscopy data for the construction of detailed real space chemical maps of graphene oxide. These chemical maps indicate very distinct functionalization motifs at the edges and interiors and, in conjunction with angle-resolved near-edge X-ray absorption fine structure spectroscopy, enable determination of the spatial location and orientations of functional groups. Chemical imaging of graphene oxide provides experimental validation of the modified Lerf-Klinowski structural model. Specifically, we note increased contributions from carboxylic acid moieties at edge sites with epoxide and hydroxyl species dominant within the interior domains.

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

    NASA Astrophysics Data System (ADS)

    Aquilanti, G.; Trapananti, A.; Minicucci, M.; Liscio, F.; Twaróg, A.; Principi, E.; Pascarelli, S.

    2007-10-01

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

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

    PubMed

    Fan, Jian-Xin; Wang, Yu-Jun; Liu, Cun; Wang, Li-Hua; Yang, Ke; Zhou, Dong-Mei; Li, Wei; Sparks, Donald L

    2014-08-30

    The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils. PMID:25064258

  1. Quantitative Phase Composition of TiO2-Coated Nanoporous-Au Monoliths by X-ray Absorption Spectroscopy and Correlations to Catalytic

    SciTech Connect

    Bagge-Hansen, Michael; Wichmann, Andre; Wittstock, Arne; Lee, Jonathan R. I.; Ye, Jianchao; Willey, Trevor M.; Kuntz, Joshua D.; van Buuren, Tony; Biener, Juergen; Baumer, Marcus; Biener, Monika M.

    2014-02-03

    Porous titania/metal composite materials have many potential applications in the fields of green catalysis, energy harvesting, and storage in which both the overall morphology of the nanoporous host material and the crystallographic phase of the titania (TiO 2) guest determine the material’s performance. New insights into the structure–function relationships of these materials were obtained by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy that, for example, provides quantitative crystallographic phase composition from ultrathin, nanostructured titania films, including sensitivity to amorphous components. We demonstrate that crystallographic phase, morphology, and catalytic activity of TiO 2-functionalized nanoporous gold (np-Au) can be controlled by a simple annealing procedure (T < 1300 K). The material was prepared by atomic layer deposition of ~2 nm thick TiO2 on millimeter-sized samples of np-Au (40–50 nm mean ligament size) and catalytically investigated with respect to aerobic CO oxidation. Moreover, the annealing-induced changes in catalytic activity are correlated with concurrent morphology and phase changes as provided by cross-sectional scanning electron microscopy, transmission electron microscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy.

  2. Quantitative Phase Composition of TiO2-Coated Nanoporous-Au Monoliths by X-ray Absorption Spectroscopy and Correlations to Catalytic

    DOE PAGES

    Bagge-Hansen, Michael; Wichmann, Andre; Wittstock, Arne; Lee, Jonathan R. I.; Ye, Jianchao; Willey, Trevor M.; Kuntz, Joshua D.; van Buuren, Tony; Biener, Juergen; Baumer, Marcus; et al

    2014-02-03

    Porous titania/metal composite materials have many potential applications in the fields of green catalysis, energy harvesting, and storage in which both the overall morphology of the nanoporous host material and the crystallographic phase of the titania (TiO 2) guest determine the material’s performance. New insights into the structure–function relationships of these materials were obtained by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy that, for example, provides quantitative crystallographic phase composition from ultrathin, nanostructured titania films, including sensitivity to amorphous components. We demonstrate that crystallographic phase, morphology, and catalytic activity of TiO 2-functionalized nanoporous gold (np-Au) can be controlled by amore » simple annealing procedure (T < 1300 K). The material was prepared by atomic layer deposition of ~2 nm thick TiO2 on millimeter-sized samples of np-Au (40–50 nm mean ligament size) and catalytically investigated with respect to aerobic CO oxidation. Moreover, the annealing-induced changes in catalytic activity are correlated with concurrent morphology and phase changes as provided by cross-sectional scanning electron microscopy, transmission electron microscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy.« less

  3. Experimental development and control of magnetorheological damper towards smart energy absorption of composite structures

    NASA Astrophysics Data System (ADS)

    Lim, Shen Hin; Prusty, B. Gangadhara; Lee, Ann; Yeoh, Guan Heng

    2013-08-01

    Experimental investigation and efficient control of magnetorheological (MR) damper towards smart energy absorption of composite structures are presented in this paper. The evaluation of an existing MR damper based on the damping force presented in our earlier work is limited by the experiment configuration setup. Using two arms configuration, an experimental test rig is designed to overcome this limitation and enabled the MR damper to be investigated throughout its full velocity range capability. A controller is then developed based on the MR damper investigation to provide automated variable control of induced current with a set crushing force and available data of composite tube crushing force. The controller is assessed numerically and shows that MR damper is controlled to provide consistent crushing force despite oscillation from the composite tube crushing force. This, thus, shows promise of MR damper integration towards smart energy absorption of composite structures.

  4. ATOMIC AND MOLECULAR PHYSICS: Electronic Structure Analysis of USiO

    NASA Astrophysics Data System (ADS)

    Murat Özkendir, Osman

    2010-05-01

    Uranium is a member of Actinides and plays important role in nuclear science and technology. Electronic and structural investigations of actinide compounds attract major interest in science. The electronic structure and chemical bonding of coffinite USiO4 are investigated by X-ray Absorption Fine Structure spectroscopy (XAFS). U L3- edge absorption spectrum in USiO4 is compared with U L3-edge spectra in UO2 and UTe due to their different electronic and chemical structures. The study presents XANES (x-ray Absorption Near-Edge Structure) and Extended XAFS (EXAFS) calculations of USiO4 thin films. The full multiple scattering approach has been applied to the calculation of U L3 edge XANES spectra of USiO4, UO2 and UTe, based on different choices of one electron potentials according to Uranium coordinations by using the real space multiple scattering method FEFF 8.2 code.

  5. 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.

  6. Broadband superior electromagnetic absorption of a discrete-structure microwave coating

    NASA Astrophysics Data System (ADS)

    Duan, Yuping; Xi, Qun; Liu, Wei; Wang, Tongmin

    2016-10-01

    A method of improving the electromagnetic (EM) absorption property of conventional microwave absorber (CMA) is proposed here. The structural design process was mainly concerned with systematic analysis and research into the impedance matching characteristic and induced current. By processing a CMA-carbonyl-iron powder (CIP) coating into many isolated regions, the discrete-structure microwave absorber (DMA) had a much better absorption property than the corresponding CMA. When the thickness was only 2.0 mm and the component content was 33 wt%, the loss of reflection was less than -10 dB shifted from 6-7 GHz to 7-13 GHz and the loss of minimum reflection decreased from 12.5 dB lost to 32 dB lost through a discrete-structure process. The microwave absorption properties of coatings with different component contents and thicknesses were investigated. The minimum reflection peaks tended to shift towards the lower frequency region as CIP content or coating thickness increased. By adjusting these three factors, a high-performance broadband absorber was produced.

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

    SciTech Connect

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

    2009-06-30

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

  8. Theoretical study on the structures and optical absorption of Si172 nanoclusters

    NASA Astrophysics Data System (ADS)

    Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua; Zhao, Li-Zhen; Zang, Qing-Jun; Wang, C. Z.; Ho, K. M.

    2015-08-01

    The structures and optical properties of silicon nanoclusters (Si NCs) have attracted continuous interest in the last few decades. However, it is a great challenge to determine the structures of Si NCs for accurate property calculation due to the complication and competition of various structural motifs. In this work, a Si172 NC with a size of about 1.8 nm was investigated using a genetic algorithm combined with tight-binding and DFT calculations. We found that a diamond crystalline core with 50 atoms (1.2 nm) was formed in the Si172 NC. It can be expected that at a size of about 172 atoms, a diamond crystalline structure can nucleate from the center of the Si NCs. The optical properties of the pure and hydrogenated Si172 NC structures also have been studied using the TDDFT method. Compared with the pure Si172 NC, the absorption peaks of the hydrogenated Si172 NC are obviously blue-shifted.

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

    SciTech Connect

    Uehara, Y.; Underwood, J.H.; Gullikson, E.M.; Perera, R.C.C.

    1997-04-01

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

  10. Biodetection of DNA and proteins using enhanced UV absorption by structuration of the chip surface

    NASA Astrophysics Data System (ADS)

    Robin, K.; Reverchon, J. L.; Mugherli, L.; Fromant, M.; Benisty, H.

    2009-02-01

    DNA and protein absorption at 260 and 280 nm can be used to reveal theses species on a biochip UV image. A first study including the design and fabrication of UV reflective multilayer biochips designed for UV contrast enhancement (factor of 4.0) together with spectrally selective AlGaN detectors demonstrated the control of chip biological coating, or Antigen/Antibody complexation with fairly good signals for typical probe density of 4x1012 molecules/cm2. Detection of fractional monolayer molecular binding requires a higher contrast enhancement which can be obtained with structured chips. Grating structures enable, at resonance, a confinement of light at the biochip surface, and thus a large interaction between the biological molecule and the lightwave field. The highest sensitivity obtained with grating-based biochip usually concerns a resonance shift, in wavelength or diffraction angle. Diffraction efficiency is also affected by UV absorption, due to enhanced light-matter interaction, and this mechanism is equally able to produce biochip images in parallel. By adjusting grating parameters, we will see how a biochip that is highly sensitive to UV absorption at its surface can be obtained. Based on the Ewald construction and diffraction diagram, instrumental resolution and smarter experimental configurations are considered. Notably, in conjunction with the 2D UV-sensitive detectors recently developed in-house, we discuss the obtainment of large contrast and good signals in a diffraction order emerging around the sample normal.

  11. Optical absorption of polar and semipolar InGaN/GaN quantum wells for blue to green converter structures

    SciTech Connect

    Neuschl, B. Helbing, J.; Thonke, K.

    2014-11-14

    The optical absorption of indium gallium nitride (InGaN)/GaN multi quantum wells (QWs) is analyzed theoretically and experimentally. For different sample structures, either planar or three-dimensional, including QWs with different tilts relative to the (0001) plane of the wurtzite crystal, the room temperature absorption spectra were measured. We observe increasing absorption for larger indium content in the active zone and for increasing QW thickness. The semipolar structures with their reduced internal electric field are favorable with respect to the spectral absorption when compared with polar samples. Numerical k ⋅ p based simulations for quantum wells with variable thickness, indium content, and orientation are in accordance with the experimental results. By taking all QW energy eigenstates in all bands as well as the orientation dependent transition probabilities into account, the spectral absorption for arbitrary sample structures can be calculated.

  12. Electronic structure measurements of metal-organic solar cell dyes using x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, Phillip S.

    The focus of this thesis is twofold: to report the results of X-ray absorption studies of metal-organic dye molecules for dye-sensitized solar cells and to provide a basic training manual on X-ray absorption spectroscopy techniques and data analysis. The purpose of our research on solar cell dyes is to work toward an understanding of the factors influencing the electronic structure of the dye: the choice of the metal, its oxidation state, ligands, and cage structure. First we study the effect of replacing Ru in several common dye structures by Fe. First-principles calculations and X-ray absorption spectroscopy at the C 1s and N 1s edges are combined to investigate transition metal dyes in octahedral and square planar N cages. Octahedral molecules are found to have a downward shift in the N 1s-to-pi* transition energy and an upward shift in C 1s-to-pi* transition energy when Ru is replaced by Fe, explained by an extra transfer of negative charge from Fe to the N ligands compared to Ru. For the square planar molecules, the behavior is more complex because of the influence of axial ligands and oxidation state. Next the crystal field parameters for a series of phthalocyanine and porphyrins dyes are systematically determined using density functional calculations and atomic multiplet calculations with polarization-dependent X-ray absorption spectra. The polarization dependence of the spectra provides information on orbital symmetries which ensures the determination of the crystal field parameters is unique. A uniform downward scaling of the calculated crystal field parameters by 5-30% is found to be necessary to best fit the spectra. This work is a part of the ongoing effort to design and test new solar cell dyes. Replacing the rare metal Ru with abundant metals like Fe would be a significant advance for dye-sensitized solar cells. Understanding the effects of changing the metal centers in these dyes in terms of optical absorption, charge transfer, and electronic

  13. Probing the local environment of substitutional Al^{3+} in goethite using X-ray absorption spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Ducher, Manoj; Blanchard, Marc; Vantelon, Delphine; Nemausat, Ruidy; Cabaret, Delphine

    2016-03-01

    We present experimental and calculated Al K-edge X-ray absorption near-edge structure (XANES) spectra of aluminous goethite with 10-33 mol% of AlOOH and diaspore. Significant changes are observed experimentally in the near- and pre-edge regions with increasing Al concentration in goethite. First-principles calculations based on density functional theory (DFT) reproduce successfully the experimental trends. This permits to identify the electronic and structural parameters controlling the spectral features and to improve our knowledge of the local environment of {Al}^{3+} in the goethite-diaspore partial solid solution. In the near-edge region, the larger peak spacing in diaspore compared to Al-bearing goethite is related to the nature (Fe or Al) of the first cation neighbours around the absorbing Al atom (Al*). The intensity ratio of the two near-edge peaks, which decreases with Al concentration, is correlated with the average distance of the first cations around Al* and the distortion of the {AlO}_6 octahedron. Finally, the decrease in intensity of the pre-edge features with increasing Al concentration is due to the smaller number of Fe atoms in the local environment of Al since Al atoms tend to cluster. In addition, it is found that the pre-edge features of the Al K-edge XANES spectra enable to probe indirectly empty 3 d states of Fe. Energetic, structural and spectroscopic results suggest that for Al concentrations around 10 mol%, Al atoms can be considered as isolated, whereas above 25 mol%, Al clusters are more likely to occur.

  14. 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.

  15. A projective reconstruction method of underground or hidden structures using atmospheric muon absorption data

    NASA Astrophysics Data System (ADS)

    Bonechi, L.; D'Alessandro, R.; Mori, N.; Viliani, L.

    2015-02-01

    Muon absorption radiography is an imaging technique based on the analysis of the attenuation of the cosmic-ray muon flux after traversing an object under examination. While this technique is now reaching maturity in the field of volcanology for the imaging of the innermost parts of the volcanic cones, its applicability to other fields of research has not yet been proved. In this paper we present a study concerning the application of the muon absorption radiography technique to the field of archaeology, and we propose a method for the search of underground cavities and structures hidden a few metres deep in the soil (patent [1]). An original geometric treatment of the reconstructed muon tracks, based on the comparison of the measured flux with a reference simulated flux, and the preliminary results of specific simulations are discussed in details.

  16. Analysis of the structure of Saturn's magnetic field using charged particle absorption signatures

    SciTech Connect

    Chenette, D.L.; Davis, L. Jr.

    1982-07-01

    A new technique is derived for determining the structure of Saturn's magnetic field. This technique uses the observed positions of charged particle absorption signatures due to the satellites and rings of Saturn to determine the parameters of an axially symmetric, spherical harmonic model of the magnetic field using the method of least squares. Absorption signatures observed along the Pioneer 11, Voyager 1, and Voyager 2 spacecraft trajectories are used to derive values for the orientation of the magnetic symmetry axis relative to Saturn's axis of rotation, the axial displacement of the center of the magnetic dipole from the center of Saturn, and the magnitude of the external field component. Comparing these results with the magnetic field model parameters deduced from analyses of magnetometer data leads us to prefer models that incorporate a northward offset of the dipole center by about 0.05 R/sub s/.

  17. An analysis of the structure of Saturn's magnetic field using charged particle absorption signatures

    SciTech Connect

    Chenette, D.L.; Davis, L. Jr.

    1983-06-01

    A technique is derived for determining the structure of Saturn's magnetic field. This technique uses the observed positions of charged particle absorption signatures due to the satellites and rings of Saturn to determine the parameters of an axially symmetric, spherical harmonic model of the magnetic field using the method of least squares. Absorption signatures observed along the Pioneer 11, Voyager 1, and Voyager 2 spacecraft trajectories are used to derive values for the orientation of the magnetic symmetry axis relative to Saturn's axis of rotation, the axial displacement of the center of the magnetic dipole from the center of Saturn, and the magnitude of the external field component. A comparison of these results with the magnetic field model parameters deduced from analyses of magnetometer data supports models which incorporate a northward offset of the dipole center by about 0.05 R(3).

  18. Titanium-silicon oxide film structures for polarization-modulated infrared reflection absorption spectroscopy

    PubMed Central

    Dunlop, Iain E.; Zorn, Stefan; Richter, Gunther; Srot, Vesna; Kelsch, Marion; van Aken, Peter A.; Skoda, Maximilian; Gerlach, Alexander; Spatz, Joachim P.; Schreiber, Frank

    2010-01-01

    We present a titanium-silicon oxide film structure that permits polarization modulated infrared reflection absorption spectroscopy on silicon oxide surfaces. The structure consists of a ~6 nm sputtered silicon oxide film on a ~200 nm sputtered titanium film. Characterization using conventional and scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy and X-ray reflectometry is presented. We demonstrate the use of this structure to investigate a selectively protein-resistant self-assembled monolayer (SAM) consisting of silane-anchored, biotin-terminated poly(ethylene glycol) (PEG). PEG-associated IR bands were observed. Measurements of protein-characteristic band intensities showed that this SAM adsorbed streptavidin whereas it repelled bovine serum albumin, as had been expected from its structure. PMID:20418963

  19. Growth and structure characterization of EuSi2 films and nanoislands on vicinal Si(001) surface

    NASA Astrophysics Data System (ADS)

    Seiler, A.; Bauder, O.; Ibrahimkutty, S.; Pradip, R.; Prüßmann, T.; Vitova, T.; Fiederle, M.; Baumbach, T.; Stankov, S.

    2014-12-01

    Europium silicide nanoislands and films with Eu coverage in the range 0.3 ML-303 ML were grown on the vicinal Si(001) surface with 4° miscut towards [110] by molecular beam epitaxy. The nanostructures were characterized by atomic force microscopy, reflection high energy electron diffraction, in situ synchrotron radiation X-ray absorption near edge structure spectroscopy and ex situ X-ray diffraction. The analysis revealed the formation of EuSi2 with a tetragonal structure. By increasing the Eu coverage the surface morphology gradually changes from isolated islands through films with very rough surface to thick films with smoother surface.

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

    NASA Astrophysics Data System (ADS)

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

    2009-10-01

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

  1. X-ray absorption spectroscopy to probe interfacial issues in photolithography.

    SciTech Connect

    Angelopoulos, Marie (IBM, T.J. Watson Research Center, Yorktown Heights, NY); Lenhart, Joseph Ludlow; Wu, Wen-li (National Institute of Standards and Technology, Gaithersburg, MD); Sambasivan, Sharadha (National Institute of Standards and Technology, Gaithersburg, MD); Fischer, Daniel A. (National Institute of Standards and Technology, Gaithersburg, MD); Jones, Ronald L. (National Institute of Standards and Technology, Gaithersburg, MD); Soles, Christopher L. (National Institute of Standards and Technology, Gaithersburg, MD); Lin, Eric K. (National Institute of Standards and Technology, Gaithersburg, MD); Goldfarb, Dario L. (IBM, T.J. Watson Research Center, Yorktown Heights, NY)

    2003-03-01

    We utilize near edge X-ray absorption fine structure spectroscopy (NEXASFS) to provide detailed chemical insight into two interfacial problems facing sub-100 nm patterning. First, chemically amplified photo-resists are sensitive to surface phenomenon, which causes deviations in the pattern profile near the interface. Striking examples include T-topping, closure, footing, and undercutting. NEXAFS was used to examine surface segregation of a photo-acid generator at the resist/air interface and to illustrate that the surface extent of deprotection in a model resist film can be different than the bulk extent of deprotection. Second, line edge roughness becomes increasingly critical with shrinking patterns, and may be intimately related to the line edge deprotection profile. A NEXAFS technique to surface depth profile for compositional gradients is described with the potential to provide chemical information about the resist line edge.

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

    SciTech Connect

    Rai, V. N.; Rajput, Parasmani; Jha, S. N.; Bhattacharyya, D.

    2015-06-24

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

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

    SciTech Connect

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

    2009-05-29

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

  4. Tailored interphase structure for improved strength and energy absorption of composites

    NASA Astrophysics Data System (ADS)

    Gao, Xiao

    Fiber reinforced polymeric composites are lightweight, high-strength and high impact-resistant materials used widely for various applications. It has been shown that the mechanical performance of composites are dependent on the interphase, a three-dimensional region of nanometer size in the vicinity of the fiber-matrix boundary that possesses properties different from those of either the fiber reinforcement or the matrix resin and governs the load transfer from matrix to fiber. This research conducts a systematic study on glass fiber-epoxy interphase structure by tailoring adhesion between constituents and the creation of textures to control strength and energy absorption through mechanical interlocking between glass fiber and epoxy matrix. Our objective is to establish the foundation for microstructural design and optimization of the composite's structural and impact performance. Two ways of roughening the glass fiber surface have been studied to create the mechanical interlocking between fiber and resin; the first technique involves forming in-situ islands on the glass fiber surface by using silane blends of Glycidoxypropyltrimethoxy silane (GPS) and Tetraethoxy silane (TEOS); the second technique applies a silane coupling agents based sizing with the incorporation of silica nanoparticles (Ludox TMA, 22 nm) onto the fiber surface. The microdroplet test was selected to characterize the influence of adhesion and mechanical interlocking effects on interphase properties of different sizing sized glass fiber reinforced epoxy systems. A suitable data reduction scheme enables the strength and specified energy absorbed due to debonding, dynamic sliding, and quasi-static sliding to be quantified. In order to validate the effect of tailored interphase structure, which is induced by creating mechanical interlocking between fiber and resin, on macroscopic composite properties, composite panels were made from these four different sizing sized glass fibers and tested using the

  5. Alcohol absorption inhibitors from bay leaf (Laurus nobilis): structure-requirements of sesquiterpenes for the activity.

    PubMed

    Yoshikawa, M; Shimoda, H; Uemura, T; Morikawa, T; Kawahara, Y; Matsuda, H

    2000-08-01

    Through a bioassay-guided separation using inhibitory activity on blood ethanol elevation in oral ethanol-loaded rat, various sesquiterpenes having an alpha-methylene-gamma-butyrolactone moiety, costunolide (1), dehydrocostus lactone (2), zaluzanin D (3), reynosin (4), santamarine (5), 3alpha-acetoxyeudesma-1,4(15),11(13)-trien-12,6alpha-+ ++olide (6) and 3-oxoeudesma-1,4,11(13)-trien-12,6alpha-olide (7), were isolated as the active principle from the leaves of Laurus nobilis (bay leaf, laurel). In order to characterize the structure requirement for the activity, several reduction products (2a-2d) and amino acid adducts (2e, 2f) of the alpha-methylene-gamma-butyrolactone moiety were synthesized from 2 and the inhibitory activities of these sesquiterpenes, together with alpha-methylene-gamma-butyrolactone (12) and its related compounds (13-16), were examined. These results indicated that the gamma-butyrolactone or gamma-butyrolactol moiety having alpha-methylene or alpha-methyl group was essential for the inhibitory activity on ethanol absorption. Since 1, 2 and 12 showed no significant effect on glucose absorption, these sesquiterpenes appeared to selectively inhibit ethanol absorption. In addition, the acute toxicities of 1 and 2 in a single oral administration were found to be lower than that of 12.

  6. Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

    NASA Astrophysics Data System (ADS)

    Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

    2016-10-01

    We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

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

    PubMed Central

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

    2015-01-01

    Configurations capable of maximizing both the absorption component of system detection efficiency and the achievable polarization contrast were determined for 1550 nm polarized light illumination of different plasmonic structure integrated superconducting nanowire single-photon detectors (SNSPDs) consisting of p = 264 nm and P = 792 nm periodic niobium nitride (NbN) patterns on silica substrate. Global effective NbN absorptance maxima appear in case of p/s-polarized light illumination in S/P-orientation (γ = 90°/0° azimuthal angle) and the highest polarization contrast is attained in S-orientation of all devices. Common nanophotonical origin of absorptance enhancement is collective resonance on nanocavity gratings with different profiles, which is promoted by coupling between localized modes in quarter-wavelength metal-insulator-metal nanocavities and laterally synchronized Brewster-Zenneck-type surface waves in integrated SNSPDs possessing a three-quarter-wavelength-scaled periodicity. The spectral sensitivity and dispersion characteristics reveal that device design specific optimal configurations exist. PMID:25654724

  8. X-ray absorption spectroscopy from H-passivated porous Si and oxidized Si nanocrystals

    SciTech Connect

    Schuppler, S.; Marcus, M.A.; Friedman, S.L.

    1994-11-01

    Quantum confinement in nanoscale Si structures is widely believed to be responsible for the visible luminescence observed from anodically etched porous silicon (por-Si), but little is known about the actual size or shape of these structures. Extended x-ray absorption fine structure data from a wide variety of por-Si samples show significantly reduced average Si coordination numbers due to the sizable contribution of surface-coordinated H. (The IUSI ratios, as large as 1.2, were independently confirmed by ir-absorption and {alpha}-recoil measurements.) The Si coordinations imply very large surface/volume ratios, enabling the average Si structures to be identified as crystalline particles (not wires) whose dimensions are typically <15 {Angstrom}. Comparison of the size-dependent peak luminescence energies with those of oxidized Si nanocrystals, whose shapes are known, shows remarkable agreement. Furthermore, near-edge x-ray absorption fine structure measurements of the nanocrystals shows the outer oxide and interfacial suboxide layers to be constant over a wide range of nanocrystal sizes. The combination of these results effectively rules out surface species as being responsible for the observed visible luminescence in por-Si, and strongly supports quantum confinement as the dominant mechanism occurring in Si particles which are substantially smaller than previously reported or proposed.

  9. Change In The Electronic Structure And Optical Absorption Of Cuprate Delafossites Via B-site Alloying

    NASA Astrophysics Data System (ADS)

    Beesley, Ramon; Panapitiya, Gihan; Lewis, James; Lewis Group Team

    Delafossite oxides are a family of materials with the form ABO2 , where the A-site is a monovalent cation (Cu , Ag , Au) and the B-site is a trivalent cation (Ga , Al , In). Delafossites typically have a wide optical band gap, this band gap may be tuned by adding a second B-site element forming an AB(1- x) 1B(x)2O2 alloy. We investigate changes in the electronic structure of CuAlO2 , CuGaO2 , and CuInO2 when alloyed with CuFeO2 . Using the FIREBALL program to optimize the atomic structure, calculate the total and partial density of states, calculate the valence band edge for each alloy level, and investigate the clustering factor of the second B-site atom, it is found that alloying with Fe creates midgap states caused by Fe - O interactions. From the partial density of state, each type of atoms contribution to the change in the valence band edge can be seen. Observed changes to the materials include increased optical absorption in the visible range, and symmetry breaking because of the deformation in the crystal structure. The CuFeO2 alloying percentages range from 0-5%. We are synthesizing these alloys to experimentally verify the changes in the optical absorption spectra.

  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. Nonlinear optical propagation in a tandem structure comprising nonlinear absorption and scattering materials

    SciTech Connect

    Wang, Kangpeng; Ju, Yongfeng; He, Jin; Zhang, Long E-mail: lzhang@siom.ac.cn; Wang, Jun E-mail: lzhang@siom.ac.cn; Chen, Yu; Blau, Werner J.

    2014-01-13

    Laser propagation in a tandem structure comprising carbon nanotubes and phthalocyanines is studied by Z-scan method. Due to the different mechanisms of the two materials, the laser beam can be attenuated with different absorptivities, by changing the sequence of light passing through each material. Numerical simulations considering the effect of path length and the change of nonlinear coefficient within each material are conducted for understanding the distribution of laser intensity in the tandem system and hence, fitting of the asymmetric Z-scan curves. The results are helpful for the design of nonlinear optical devices comprising multiple nonlinear materials and mechanisms.

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

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  13. 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.

  14. Optical Absorption, Stability and Structure of NpO2+ Complexeswith Dicarboxylic Acids

    SciTech Connect

    Guoxin Tian; Linfeng Rao

    2006-01-04

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

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

    PubMed

    Rabuffetti, Federico A; Brutchey, Richard L

    2013-12-23

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

  16. Chemical Structure of Copper in Incineration Dry Scrubber and Bag Filter Ashes

    SciTech Connect

    Hsiao, M. C.; Wang, H. Paul; Peng, C. Y.; Huang, C. H.; Wei Yuling

    2007-02-02

    Speciation of copper in waste incineration fly ashes (dry scrubber (DS) and bag filter (BF)) has been studied by X-ray absorption near edge structural (XANES) spectroscopy in the present work. Copper species such as metallic Cu, CuO, Cu(OH)2, and a small amount of CuCO3 in the fly ashes could be distinguished by semi-quantitative analysis of the edge spectra. Interestingly, nano CuO (37%) were found in the BF fly ash, that might account for its relatively high leachability of copper.

  17. Atomic force microscopy study of erythrocyte shape and membrane structure after treatment with a dihydropyridinic drug

    NASA Astrophysics Data System (ADS)

    Girasole, M.; Cricenti, A.; Generosi, R.; Congiu-Castellano, A.; Boffi, F.; Arcovito, A.; Boumis, G.; Amiconi, G.

    2000-06-01

    The overall shape and membrane surface of human erythrocytes (RBCs) in the presence of nifedipine (a dihydropyridinic drug used in the clinical treatment of hypertension and angina pectoris) were imaged by contact-mode atomic force microscopy. Nifedipine induces in RBCs relevant morphological changes the extent of which increases as a function of drug concentration and incubation time. The modifications have been interpreted as mainly due to insertion of nifedipine into the outer layer of the RBC membrane. The potential effect of nifedipine as a hemoglobin denaturant has been ruled out by x-ray absorption near-edge structure and optical spectroscopies.

  18. GaAs and AlGaAs APDs with GaSb absorption regions in a separate absorption and multiplication structure using a hetero-lattice interface

    NASA Astrophysics Data System (ADS)

    Marshall, A. R. J.; Craig, A. P.; Reyner, C. J.; Huffaker, D. L.

    2015-05-01

    Interfacial misfit (IMF) arrays were used to create two APD structures, allowing GaSb absorption layers to be combined with wide-gap multiplication regions, grown using GaAs and Al0.8Ga0.2As, respectively. The GaAs APD represents a proof-of-principle, which is developed in the Al0.8Ga0.2As APD to achieve reduced dark currents, of 5.07 μA cm-2 at 90% of the breakdown voltage, and values for effective k = β/α below 0.2. A random-path-length (RPL) simulation was used to model the excess noise in both structures, taking into account the effects of dead space. It is envisaged that the GaSb absorption regions could be replaced with other materials from the 6.1 Å family, allowing for long-wavelength APDs with reduced dark currents and excess noise.

  19. 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

  20. The Small-Scale Structure of High-Velocity Na I Absorption Toward M81

    NASA Astrophysics Data System (ADS)

    Roth, K. C.; Meyer, D. M.; Lauroesch, J. T.

    2000-12-01

    We present high-resolution (R=20,000) integral field spectra of the Na I absorption toward the nucleus of the nearby spiral galaxy M81 (NGC 3031) obtained in April 2000 with the WIYN 3.5-m telescope and the DensePak fiber optic bundle. Our DensePak map covers the central 27 x 43 arcsec of M81 at a spatial resolution of 4 arcsec which corresponds to a projected length scale of 63 pc at the distance of the galaxy (3.25 Mpc). These data were intended to explore the spatial extent of high-velocity (v = 110-130 km/s) gas seen in Na I, Mg I and Mg II absorption toward SN 1993J by Bowen et al. (1994), which they proposed is due to tidal material associated with interactions between M81 and nearby M82 (Yun, Ho & Lo 1993). No H I gas at these velocities has been detected in 21 cm interferometry maps near the position of SN 1993J (2.6 arcmin SW of the M81 nucleus). Our Na I map of the M81 core shows no evidence of the strong absorption seen at v = 110-130 km/s toward SN 1993J. However, our map does reveal a strong Na I component at v = 220 km/s in several fibers that appears to trace a filamentary structure running from the SW to the NE across the M81 nuclear region. The origin and distance of this filament are unknown. No H I gas at v = 220 km/s has previously been detected in 21 cm studies of the core. At the location of SN 1993J, Bowen et al. measured weak Mg II absorption at this velocity but found no evidence of corresponding Na I absorption. The only known H I gas that corresponds to this velocity in the M81 group are the H I streamers found around M82 by Yun, Ho, & Lo that they interpreted as tidally disrupted M82 disk material.

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

    PubMed

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

    2016-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  3. Negative thermal expansion in CuCl: An extended x-ray absorption fine structure study

    SciTech Connect

    Vaccari, M.; Grisenti, R.; Fornasini, P.; Rocca, F.; Sanson, A.

    2007-05-01

    Extended x-ray absorption fine structure (EXAFS) has been measured from liquid helium to ambient temperature at the Cu K edge of copper chloride (CuCl) to investigate the local origin of negative thermal expansion. A quantitative analysis of the first coordination shell, performed by the cumulant method, reveals that the nearest-neighbor Cu-Cl interatomic distance undergoes a strong positive expansion, contrasting with the much weaker negative expansion of the crystallographic distance between average atomic positions below 100 K. The anisotropy of relative thermal vibrations, monitored by the ratio {gamma} between perpendicular and parallel mean square relative displacements, is considerably high, while the diffraction thermal factors are isotropic. The relative perpendicular vibrations measured by EXAFS are related to the tension mechanism and to the transverse acoustic modes, which are considered responsible for negative thermal expansion in zinc-blende structures.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  6. An ISOCAM absorption survey of the structure of pre-stellar cloud cores

    NASA Astrophysics Data System (ADS)

    Bacmann, A.; André, P.; Puget, J.-L.; Abergel, A.; Bontemps, S.; Ward-Thompson, D.

    2000-09-01

    We present the results of a mid-infrared (lambda =~ 7 mu m) imaging survey of a sample of 24 starless dense cores carried out at an angular resolution of 6arcsec with the ISOCAM camera aboard the Infrared Space Observatory (ISO). The targeted cores are believed to be pre-stellar in nature and to represent the initial conditions of low-mass, isolated star formation. In previous submillimeter dust continuum studies of such pre-stellar cores, it was found that the derived column density profiles did not follow a single power-law such as NH2 ~ bar r-1 throughout their full extent but flattened out near their centre. These submillimeter observations however could not constrain the density profiles at radii greater than ~ 10000 AU. The present absorption study uses ISOCAM's sensitivity to map these pre-stellar cores in absorption against the diffuse mid-infrared background. The goal was to determine their structure at radii that extend beyond the limits of sensitivity of the submillimeter continuum maps and at twice as good an angular resolution. Among the 24 cores observed in our survey, a majority of them show deep absorption features. The starless cores studied here all show a column density profile that flattens in the centre, which confirms the submillimeter emission results. Moreover, beyond a radius of ~ 5000-10000 AU, the typical column density profile steepens with distance from core centre and gets steeper than NH2 ~ bar r-1, until it eventually merges with the low-density ambient molecular cloud. At least three of the cores present sharp edges at R ~ 15000-30000 AU and appear to be decoupled from their parent clouds, providing finite reservoirs of mass for subsequent star formation. Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, the Netherlands and the United Kingdom) and with the participation of ISAS and NASA.

  7. Absorption spectroscopy with sub-angstrom beams: ELS in STEM

    NASA Astrophysics Data System (ADS)

    Spence, John C. H.

    2006-03-01

    Electron-energy loss spectroscopy (EELS) performed using a modern transmission scanning electron microscope (STEM) now offers sub-nanometre spatial resolution and an energy resolution down to 200 meV or less, in favourable cases. The absorption spectra, which probe empty states, cover the soft x-ray region and may be obtained under conditions of well-defined momentum transfer (angle-resolved), providing a double projection onto crystallographic site and symmetry within the density of states. By combining the very high brightness of field-emission electron sources (brighter than a synchrotron) with the high cross-section of electron scattering, together with parallel detection (not possible with scanning x-ray absorption spectroscopy), a form of spectroscopy ideally suited to the study of nanostructures, interfacial states and defects in materials is obtained with uniquely high spatial resolution. We review the basic theory, the relationship of EELS to optical properties and the dielectric response function, the removal of multiple scattering artefacts and channelling effects. We consider applications in the light of recent developments in aberration corrector and electron monochromator design. Examples are cited of inner-shell spectra obtained from individual atoms within thin crystals, of the detection of interfacial electronic states in semiconductors, of inner-shell near edge structure mapped with sub-nanometre spatial resolution in glasses and of spectra obtained from individual carbon nanotubes, amongst many others.

  8. Synthesis and electronic structure of low-density monoliths of nanoporous nanocrystalline anatase TiO2

    SciTech Connect

    Kucheyev, S O; Baumann, T F; Wang, Y M; van Buuren, T; Satcher, J H

    2004-08-13

    Monolithic nanocrystalline anatase titania aerogels are synthesized by the epoxide sol-gel method followed by thermal annealing at 550 C. These aerogels are formed by {approx}10-20 nm size anatase nanoparticles which are randomly oriented and interconnected into an open-cell solid network. Aerogel monoliths have an apparent density of {approx}6% and a surface area of {approx} 100 m{sup 2} g{sup -1}. High-resolution transmission electron microscopy and soft x-ray absorption near-edge structure spectroscopy reveal good crystallinity of the anatase nanoparticles forming the aerogel skeleton.

  9. Surface plasmon effects in the absorption enhancements of amorphous silicon solar cells with periodical metal nanowall and nanopillar structures.

    PubMed

    Lin, Hung-Yu; Kuo, Yang; Liao, Cheng-Yuan; Yang, C C; Kiang, Yean-Woei

    2012-01-01

    The authors numerically investigate the absorption enhancement of an amorphous Si solar cell, in which a periodical one-dimensional nanowall or two-dimensional nanopillar structure of the Ag back-reflector is fabricated such that a dome-shaped grating geometry is formed after Si deposition and indium-tin-oxide coating. In this investigation, the effects of surface plasmon (SP) interaction in such a metal nanostructure are of major concern. Absorption enhancement in most of the solar spectral range of significant amorphous Si absorption (320-800 nm) is observed in a grating solar cell. In the short-wavelength range of high amorphous Si absorption, the weakly wavelength-dependent absorption enhancement is mainly caused by the broadband anti-reflection effect, which is produced through the surface nano-grating structures. In the long-wavelength range of diminishing amorphous Si absorption, the highly wavelength-sensitive absorption enhancement is mainly caused by Fabry-Perot resonance and SP interaction. The SP interaction includes the contributions of surface plasmon polariton and localized surface plasmon.

  10. Using in situ X-ray absorption spectroscopy to study the local structure and oxygen ion conduction mechanism in (La{sub 0.6}Sr{sub 0.4})(Co{sub 0.2}Fe{sub 0.8})O{sub 3-{delta}}

    SciTech Connect

    Itoh, Takanori; Nakayama, Masanobu

    2012-08-15

    To study the local structure and oxygen ion conduction mechanism in (La{sub 0.6}Sr{sub 0.4})(Co{sub 0.2}Fe{sub 0.8})O{sub 3-{delta}} (LSCF) as a function of the oxygen partial pressure (P(O{sub 2})), in situ the Co and Fe K-edge X-ray absorption spectroscopy (XAS) was measured at elevated temperatures of 900 and 1000 K. The reduction of the Co and Fe valence, i.e., the oxygen content (3-{delta}) in LSCF, followed the change of P(O{sub 2}) from 1 to 10{sup -4} atm during{approx}4000 s. The quantitative analysis of the X-ray absorption near edge structure (XANES) and the extended X-ray absorption fine structure (EXAFS) indicated that the Fe valence was higher than the Co valence at oxidative condition ({delta} Almost-Equal-To 0) in LSCF. Whereas the Co valence decreased more than the Fe valence after reduction of P(O{sub 2}) at both 900 and 1000 K. From the relaxation plots of the valence and the oxygen content (3-{delta}) for Co and Fe after changing P(O{sub 2}), we successfully determined D{sub chem} and E{sub a} of an oxygen ion migration around Co and Fe in LSCF. A structural model with and without oxygen vacancies and an oxygen ion conduction mechanism for LSCF are proposed based on these results. - Graphical abstract: A structural model with and without oxygen vacancies, and the oxygen ion conduction mechanism of LSCF were speculated. In other words, oxygen vacancies would form more preferentially around Co than Fe from the results of in situ XAS analysis during reduction, and oxygen ions needs to pass through at the vicinity of Fe from the results of D{sub chem} and E{sub a}. Highlights: Black-Right-Pointing-Pointer Study of the oxygen ion conduction mechanism in (La{sub 0.6}Sr{sub 0.4})(Co{sub 0.2}Fe{sub 0.8})O{sub 3-{delta}} (LSCF). Black-Right-Pointing-Pointer Using in situ X-ray absorption for study of valence and oxygen diffusion coefficient. Black-Right-Pointing-Pointer The oxygen vacancies should be preferentially localized around Co in LSCF. Black

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

    SciTech Connect

    Stanimirovic, S.; Weisberg, J. M.; Pei, Z.; Tuttle, K.; Green, J. T.

    2010-09-01

    We present results from multi-epoch neutral hydrogen (H I) absorption observations of six bright pulsars with the Arecibo telescope. Moving through the interstellar medium (ISM) with transverse velocities of 10-150 AU yr{sup -1}, these pulsars have swept across 1-200 AU over the course of our experiment, allowing us to probe the existence and properties of the tiny-scale atomic structure (TSAS) in the cold neutral medium (CNM). While most of the observed pulsars show no significant change in their H I absorption spectra, we have identified at least two clear TSAS-induced opacity variations in the direction of B1929+10. These observations require strong spatial inhomogeneities in either the TSAS clouds' physical properties themselves or else in the clouds' galactic distribution. While TSAS is occasionally detected on spatial scales down to 10 AU, it is too rare to be characterized by a spectrum of turbulent CNM fluctuations on scales of 10{sup 1}-10{sup 3} AU, as previously suggested by some work. In the direction of B1929+10, an apparent correlation between TSAS and interstellar clouds inside the warm Local Bubble (LB) indicates that TSAS may be tracing the fragmentation of the LB wall via hydrodynamic instabilities. While similar fragmentation events occur frequently throughout the ISM, the warm medium surrounding these cold cloudlets induces a natural selection effect wherein small TSAS clouds evaporate quickly and are rare, while large clouds survive longer and become a general property of the ISM.

  12. Neutron induced damage in reactor pressure vessel steel: An X-ray absorption fine structure study

    NASA Astrophysics Data System (ADS)

    Kuri, G.; Cammelli, S.; Degueldre, C.; Bertsch, J.; Gavillet, D.

    2009-03-01

    The radiation damage produced in reactor pressure vessel (RPV) steels during neutron irradiation is a long-standing problem of considerable practical interest. In this study, an extended X-ray absorption fine structure (EXAFS) spectroscopy has been applied at Cu, Ni and Mn K-edges to systematically investigate neutron induced radiation damage to the metal-site bcc structure of RPV steels, irradiated with neutrons in the fluence range from 0.85 to 5.0 × 1019 cm-2. An overall similarity of Cu, Ni and Mn atomic environment in the iron matrix is observed. The radial distribution functions (RDFs), derived from EXAFS data have been found to evolve continuously as a function of neutron fluence describing the atomic-scale structural modifications in RPVs by neutron irradiations. From the pristine data, long range order beyond the first- and second-shell is apparent in the RDF spectra. In the irradiated specimens, all near-neighbour peaks are greatly reduced in magnitude, typical of damaged material. Prolonged annealing leads annihilation of point defects to give rise to an increase in the coordination numbers of near-neighbour atomic shells approaching values close to that of non-irradiated material, but does not suppress the formation of nano-sized Cu and/or Ni-rich-precipitates. Total amount of radiation damage under a given irradiation condition has been determined. The average structural parameters estimated from the EXAFS data are presented and discussed.

  13. Atomic Structure of Pt3Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy.

    PubMed

    Becknell, Nigel; Kang, Yijin; Chen, Chen; Resasco, Joaquin; Kornienko, Nikolay; Guo, Jinghua; Markovic, Nenad M; Somorjai, Gabor A; Stamenkovic, Vojislav R; Yang, Peidong

    2015-12-23

    Understanding the atomic structure of a catalyst is crucial to exposing the source of its performance characteristics. It is highly unlikely that a catalyst remains the same under reaction conditions when compared to as-synthesized. Hence, the ideal experiment to study the catalyst structure should be performed in situ. Here, we use X-ray absorption spectroscopy (XAS) as an in situ technique to study Pt3Ni nanoframe particles which have been proven to be an excellent electrocatalyst for the oxygen reduction reaction (ORR). The surface characteristics of the nanoframes were probed through electrochemical hydrogen underpotential deposition and carbon monoxide electrooxidation, which showed that nanoframe surfaces with different structure exhibit varying levels of binding strength to adsorbate molecules. It is well-known that Pt-skin formation on Pt-Ni catalysts will enhance ORR activity by weakening the binding energy between the surface and adsorbates. Ex situ and in situ XAS results reveal that nanoframes which bind adsorbates more strongly have a rougher Pt surface caused by insufficient segregation of Pt to the surface and consequent Ni dissolution. In contrast, nanoframes which exhibit extremely high ORR activity simultaneously demonstrate more significant segregation of Pt over Ni-rich subsurface layers, allowing better formation of the critical Pt-skin. This work demonstrates that the high ORR activity of the Pt3Ni hollow nanoframes depends on successful formation of the Pt-skin surface structure.

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

    SciTech Connect

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

    2005-01-01

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

  15. Transmission loss of orthogonally rib-stiffened double-panel structures with cavity absorption.

    PubMed

    Xin, F X; Lu, T J

    2011-04-01

    The transmission loss of sound through infinite orthogonally rib-stiffened double-panel structures having cavity-filling fibrous sound absorptive materials is theoretically investigated. The propagation of sound across the fibrous material is characterized using an equivalent fluid model, and the motions of the rib-stiffeners are described by including all possible vibrations, i.e., flexural displacements, bending, and torsional rotations. The effects of fluid-structure coupling are account for by enforcing velocity continuity conditions at fluid-panel interfaces. By taking full advantage of the periodic nature of the double-panel, the space-harmonic approach and virtual work principle are applied to solve the sets of resultant governing equations, which are eventually truncated as a finite system of simultaneous algebraic equations and numerically solved insofar as the solution converges. To validate the proposed model, a comparison between the present model predictions and existing numerical and experimental results for a simplified version of the double-panel structure is carried out, with overall agreement achieved. The model is subsequently employed to explore the influence of the fluid-structure coupling between fluid in the cavity and the two panels on sound transmission across the orthogonally rib-stiffened double-panel structure. Obtained results demonstrate that this fluid-structure coupling affects significantly sound transmission loss (STL) at low frequencies and cannot be ignored when the rib-stiffeners are sparsely distributed. As a highlight of this research, an integrated optimal algorithm toward lightweight, high-stiffness and superior sound insulation capability is proposed, based on which a preliminary optimal design of the double-panel structure is performed. PMID:21476648

  16. RE L(3) x-ray absorption study of REO(1-x)F(x)FeAs (RE = La, Pr, Nd, Sm) oxypnictides.

    PubMed

    Joseph, B; Iadecola, A; Fratini, M; Bianconi, A; Marcelli, A; Saini, N L

    2009-10-28

    Rare earth L(3)-edge x-ray absorption near-edge structure (XANES) spectroscopy has been used to study REOFeAs (RE = La, Pr, Nd, Sm) oxypnictides. The Nd L(3) XANES due to the [Formula: see text] transition shows a substantial change in both white line (WL) spectral weight and the higher energy multiple scattering resonances with the partial substitution of O by F. A systematic change in the XANES features is seen due to varying lattice parameters with ionic radius of the rare earth. On the other hand, we hardly see any change across the structural phase transition. The results provide timely information on the local atomic correlations showing the importance of the local structural chemistry of the REO spacer layer and interlayer coupling in the competing superconductivity and itinerant striped magnetic phase of the oxypnictides.

  17. Excited electronic structure of methylcyanoacetylene probed by VUV Fourier-transform absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lamarre, N.; Gans, B.; Vieira Mendes, L. A.; Gronowski, M.; Guillemin, J.-C.; De Oliveira, N.; Douin, S.; Chevalier, M.; Crépin, C.; Kołos, R.; Boyé-Péronne, S.

    2016-10-01

    High resolution photoabsorption spectrum of gas-phase methylcyanoacetylene (CH3C3 N) has been recorded from 44 500 to 130 000 cm-1 at room temperature with a vacuum ultraviolet Fourier-transform spectrometer on the DESIRS synchrotron beamline (SOLEIL). The absolute photoabsorption cross section in this range is reported for the first time. Valence shell transitions and Rydberg series converging to the ground state X˜+2E of the cation as well as series converging to electronically excited states (A˜+A21 and C˜+) are observed and assigned. Time-dependent density-functional-theory calculations have been performed to support the assignment of the experimental spectrum in the low energy range. A tentative scaling of the previously measured CH3C3N+ ion yield by Lamarre et al. [17] is proposed, based on the comparison of the absorption data above the first ionization potential with the observed autoionization structures.

  18. Possible evidence for a variable fine-structure constant from QSO absorption lines: systematic errors

    NASA Astrophysics Data System (ADS)

    Murphy, M. T.; Webb, J. K.; Flambaum, V. V.; Churchill, C. W.; Prochaska, J. X.

    2001-11-01

    Comparison of quasar (QSO) absorption spectra with laboratory spectra allows us to probe possible variations in the fundamental constants over cosmological time-scales. In a companion paper we present an analysis of Keck/HIRES spectra and report possible evidence suggesting that the fine-structure constant, α, may have been smaller in the past: [formmu2]Δα/α=(-0.72+/-0.18)×10-5 over the redshift range [formmu3]0.5

  19. Synchrotron x-ray fluorescence and extended x-ray absorption fine structure analysis

    SciTech Connect

    Chen, J.R.; Gordon, B.M.; Hanson, A.L.; Jones, K.W.; Kraner, H.W.; Chao, E.C.T.; Minkin, J.A.

    1984-01-01

    The advent of dedicated synchrotron radiation sources has led to a significant increase in activity in many areas of science dealing with the interaction of x-rays with matter. Synchrotron radiation provides intense, linearly polarized, naturally collimated, continuously tunable photon beams, which are used to determine not only the elemental composition of a complex, polyatomic, dilute material but also the chemical form of the elements with improved accuracy. Examples of the application of synchrotron radiation include experiments in synchrotron x-ray fluorescence (SXRF) analysis and extended x-ray absorption fine structure (EXAFS) analysis. New synchrotron radiation x-ray microprobes for elemental analysis in the parts per billion range are under construction at several laboratories. 76 references, 24 figures.

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

    PubMed

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

    2009-05-01

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

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

    SciTech Connect

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

    2015-05-15

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

  2. Ab initio calculation of x-ray absorption of iron up to 3 Mbar and 8000 K

    NASA Astrophysics Data System (ADS)

    Mazevet, S.; Recoules, V.; Bouchet, J.; Guyot, F.; Harmand, M.; Ravasio, A.; Benuzzi-Mounaix, A.

    2014-03-01

    Using ab initio simulations within the generalized gradient approximation, we calculate x-ray absorption near edge spectra (XANES) at the iron K edge throughout the high-pressure phase diagram and up to extreme density and temperature conditions that are representative of the Earth's inner core (up to 3 Mbar and 8000 K). We show that XANES spectra near the Fe K edge exhibit clear signatures for the different high-temperature, high-pressure phases of iron. This suggests that XANES spectroscopy might be used to resolve ongoing controversies regarding both the high-pressure melting curve of iron and the nature of the solid phases undergoing melting up to several Mbar. In contrast to diffraction measurements, it also offers a severe constraint for density functional theory predictions of the transport properties of iron by providing direct information on the electronic structure of iron at these extreme conditions.

  3. Measurement of c-axis angular orientation in calcite (CaCO3) nanocrystals using X-ray absorption spectroscopy

    PubMed Central

    Gilbert, P. U. P. A.; Young, Anthony; Coppersmith, Susan N.

    2011-01-01

    We demonstrate that the ability to manipulate the polarization of synchrotron radiation can be exploited to enhance the capabilities of X-ray absorption near-edge structure (XANES) spectroscopy, to include linear dichroism effects. By acquiring spectra at the same photon energies but different polarizations, and using a photoelectron emission spectromicroscope (PEEM), one can quantitatively determine the angular orientation of micro- and nanocrystals with a spatial resolution down to 10 nm. XANES-PEEM instruments are already present at most synchrotrons, hence these methods are readily available. The methods are demonstrated here on geologic calcite (CaCO3) and used to investigate the prismatic layer of a mollusk shell, Pinctada fucata. These XANES-PEEM data reveal multiply oriented nanocrystals within calcite prisms, previously thought to be monocrystalline. The subdivision into multiply oriented nanocrystals, spread by more than 50°, may explain the excellent mechanical properties of the prismatic layer, known for decades but never explained. PMID:21693647

  4. Three-dimensional local structure refinement using a full-potential XANES analysis

    SciTech Connect

    Smolentsev, G.; Soldatov, A. V.; Feiters, M. C.

    2007-04-01

    A technique of three-dimensional (3D) local structure refinement is proposed and demonstrated by applying it to the metal complex Ni(acacR){sub 2}. The method is based on the fitting of experimental x-ray absorption near-edge structure (XANES) using a multidimensional interpolation of spectra and full potential calculations of XANES. The low number of calculations required is the main advantage of the method, which allows a computationally time-expensive method using a non-muffin-tin potential to be applied. The possibility to determine bond angles in addition to bond lengths accessible to extended x-ray-absorption fine structure opens new perspectives of XANES as a 3D structure probe.

  5. 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.

  6. Structural models and atomic distribution of bimetallic nanoparticles as investigated by X-ray absorption spectroscopy.

    PubMed

    Hwang, Bing-Joe; Sarma, Loka Subramanyam; Chen, Jiun-Ming; Chen, Ching-Hsiang; Shih, Shou-Chu; Wang, Guo-Rung; Liu, Din-Goa; Lee, Jyh-Fu; Tang, Mau-Tsu

    2005-08-10

    In this report, we describe a general methodology to determine the extent of alloying or atomic distribution quantitatively in bimetallic nanoparticles (NPs) by X-ray absorption spectroscopy (XAS). The structural parameters determined in these studies serve as a quantitative index and provide a general route to determine the structural aspects of the bimetallic NPs. We have derived various types of possible structural models based on the extent of alloying and coordination number parameters of bimetallic NPs. We also discussed the nature of homo- and heterometallic interactions in bimetallic NPs based on the extent of alloying. Herein, we use carbon-supported platinum-ruthenium bimetallic nanoparticles to demonstrate the proposed methodology, and this can be extended further to get more insights into the alloying extent or atomic distribution of other bimetallic systems. The results demonstrated in this paper open up methods to determine the atomic distribution of bimetallic NPs, which is an extremely important parameter that strongly influences the physicochemical properties of NPs and their applications.

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

    SciTech Connect

    Vaverka, April Susan Montoya

    2008-01-01

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

  8. Pressure influence on the structural characteristics of modified absorptive glass mat separators: A standard contact porosimetry study

    NASA Astrophysics Data System (ADS)

    Burashnikova, M. M.; Khramkova, T. S.; Kazarinov, I. A.; Shmakov, S. L.

    2015-09-01

    The article presents a comparative analysis of the structural characteristics of absorptive glass mats manufactured by "Hollingsworth & Vose" (a 2.8 mm thickness) and "Bernard Dumas" (a 3.0 mm thickness) modified by impregnation with polymeric emulsions based on polyvinylidene fluoride, a polyvinylpyrrolidone styrene copolymer, and polytetrafluoroethylene, by means of standard contact porosimetry. The key study is influence of features of the porous structure on the compression properties, the rate of wicking, and the oxygen cycle efficiency in lead-acid battery mock-ups under several plate-group compression pressures. It is found that the treatment of the absorptive glass mat separators with polymeric emulsions leads to redistribution of their pores by size. An increased pressure in the electrode unit insignificantly changes the pore structure of the modified absorptive glass mat separators, and the oxygen cycle efficiency rises in comparison with unmodified separators.

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

    PubMed

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

    2007-07-15

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

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

    SciTech Connect

    Citron, Robert; Kropf, A.J.

    2008-01-01

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

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

    SciTech Connect

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

    2009-06-03

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

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

    PubMed Central

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

    2013-01-01

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

  13. 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.

  14. Determination of copper binding in Pseudomonas putida CZ1 by chemical modifications and X-ray absorption spectroscopy.

    PubMed

    Chen, XinCai; Shi, JiYan; Chen, YingXu; Xu, XiangHua; Chen, LiTao; Wang, Hui; Hu, TianDou

    2007-03-01

    Previously performed studies have shown that Pseudomonas putida CZ1 biomass can bind an appreciable amount of Cu(II) and Zn(II) ions from aqueous solutions. The mechanisms of Cu- and Zn-binding by P. putida CZ1 were ascertained by chemical modifications of the biomass followed by Fourier transform infrared and X-ray absorption spectroscopic analyses of the living or nonliving cells. A dramatic decrease in Cu(II)- and Zn(II)-binding resulted after acidic methanol esterification of the nonliving cells, indicating that carboxyl functional groups play an important role in the binding of metal to the biomaterial. X-ray absorption spectroscopy was used to determine the speciation of Cu ions bound by living and nonliving cells, as well as to elucidate which functional groups were involved in binding of the Cu ions. The X-ray absorption near-edge structure spectra analysis showed that the majority of the Cu was bound in both samples as Cu(II). The fitting results of Cu K-edge extended X-ray absorption fine structure spectra showed that N/O ligands dominated in living and nonliving cells. Therefore, by combining different techniques, our results indicate that carboxyl functional groups are the major ligands responsible for the metal binding in P. putida CZ1. PMID:17021877

  15. Predicting X-ray absorption spectra of semiconducting polymers for electronic structure and morphology characterization

    NASA Astrophysics Data System (ADS)

    Su, Gregory; Patel, Shrayesh; Pemmaraju, C. Das; Kramer, Edward; Prendergast, David; Chabinyc, Michael

    2015-03-01

    Core-level X-ray absorption spectroscopy (XAS) reveals important information on the electronic structure of materials and plays a key role in morphology characterization. Semiconducting polymers are the active component in many organic electronics. Their electronic properties are critically linked to device performance, and a proper understanding of semiconducting polymer XAS is crucial. Techniques such as resonant X-ray scattering rely on core-level transitions to gain materials contrast and probe orientational order. However, it is difficult to identify these transitions based on experiments alone, and complementary simulations are required. We show that first-principles calculations can capture the essential features of experimental XAS of semiconducting polymers, and provide insight into which molecular model, such as oligomers or periodic boundary conditions, are best suited for XAS calculations. Simulated XAS can reveal contributions from individual atoms and be used to visualize molecular orbitals. This allows for improved characterization of molecular orientation and scattering analysis. These predictions lay the groundwork for understanding how chemical makeup is linked to electronic structure, and to properly utilize experiments to characterize semiconducting polymers.

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

    SciTech Connect

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

    1993-05-19

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

  17. Extended X-ray Absorption Fine Structure (EXAFS) Analysis of Novel High Laser Media

    NASA Astrophysics Data System (ADS)

    Hemantha, Aranwela; Marasinghe, G. K.; Segre, Carlo; Brow, Richard

    2011-03-01

    Rare earth-doped phosphate glasses are useful for a variety of optical and optoelectronic applications including high energy/high power (~ 1015 watt) Lasers. Binary (R2 O3)x (P2 O5)1-x glasses can be prepared in the compositional range 0 <= x <= ~ 0.30 . Atomic-scale structure, especially the coordination environment of R3+ ions, play a major role in determining optical/physical characteristics. We have investigated the R3+ local environment of Praseodymium and Neodymium ultraphosphate and meta phosphate(REMP) glasses using extended X-ray absorption fine structure technique. For both Nd and Pr phosphate glasses, nearest neighbor (oxygen) coordination decreases with increasing RE concentration. For the first oxygen shell the RE-O distance ranges between 2.38-2.40 Å and 2.39-2.46 Å for Nd and Pr respectively. The second co-ordination shell around the RE ions consists of phosphorus ions, with RE-P distance about 3.4-3.5 Å and co-ordination numbers ranging from 1.5 to 3. There exists an Oxygen shell (third shell) about 4.1 Å from RE ion for both Nd and Pr phosphate glasses. Support was provided by the NSF (UND) and DoE (Argonne Natl. Lab).

  18. Study of the Local Structure of II-Vi Ternary Alloys by Extended X-Ray Absorption Fine Structure

    NASA Astrophysics Data System (ADS)

    Pong, Way-Faung

    Bondlengths, Debye-Waller factors, and site occupancy in the diluted magnetic semiconductors Zn_ {rm 1 - x}Mn_{ rm x}Se and Hg_{ rm 1 - x}Mn_{rm x}Te, and the narrow-gap semiconductor Hg _{rm 1 - x}Cd _{rm x}Te have been measured using extended x-ray absorption fine structure (EXAFS). The nearest-neighbor bond lengths in all of these alloys are found to be constant as a function of alloy composition within the experimental uncertainty of 0.01A. Because the average cation-cation distance changes with Mn composition, these results necessarily imply distortion of the tetrahedral bond angles. In the case of Zn_{rm 1 - x}Mn_{rm x} Se, the anion sublattice is shown to suffer the largest distortion, but the cation sublattice also exhibits some relaxation. The repercussions of these results are discussed, in terms of the amount of cation and anion sublattice distortion at low temperature and its connection to the superexchange mechanism occurring between the Mn ^{+2} ions and mediated by the intervening anion in Zn_{rm 1 - x}Mn_{rm x} Se. From the NN bond length relaxation results shown in this study and those reported elsewhere for the III -V-based and II-VI-based ternary compounds and DMS alloys, it appears that substitution of Mn^{+2 } ions into II-VI-based compounds causes greater local distortion, in general, than otherwise observed when group II cations are substituted for one another. We believe that the tetrahedral bond weakening in DMS is due to MN 3d-orbital (t_2) and anion p-orbital hybridization in DMS, leaving fewer p-orbitals available for tetrahedral bonding. This leads to the weakening of the bond force constants alpha, beta, as well as the bond becoming more ionic as Mn^{+2} is substituted into the II-VI-based compounds. Finally, the experimentally extended electron energy loss fine structure (EXELFS) technique, with modulations in the differential inelastic electron scattering cross -section above an absorption core edge, has been used in recent years to

  19. Structural transitions of mechanically alloyed Fe 100- xCu x systems studied by X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Wei, Shiqiang; Yan, Wensheng; Li, Yuzhi; Liu, Wenhan; Fan, Jiangwei; Zhang, Xinyi

    2001-11-01

    The local structures of the immiscible Fe 100- xCu x alloys ( x=0, 10, 20, 40, 60, 80 and 100) produced by mechanical alloying have been investigated by X-ray absorption fine structure technique. For the Fe 100- xCu x solid solutions with x⩾40, the local environment around the Fe atoms changes from bcc to fcc structure and the Cu atoms maintain the original coordination geometry after milling for 160 h. In contrast, the local structures around the Cu atoms in both Fe 80Cu 20 and Fe 90Cu 10 alloys exhibit a transition from fcc to bcc structure. Furthermore, we found that the coordination numbers N in the first shell of the Fe and Cu atoms were largely deviated from the stoichiometric composition for the Fe 100- xCu x solid solutions with x⩾40. The Debye-waller factor σ of the fcc Fe-Cu phase is larger than that of the bcc Fe-Cu phase, and the σ (0.099 Å) around Fe atoms is larger than that around Cu atoms (0.089 Å) in the Fe 100- xCu x solid solutions with x⩾40. This indicates that the mechanically alloyed Fe 100- xCu x supersaturated solid solutions with x⩾40 is not a homogeneous alloy, but consists of fcc Fe-rich and fcc Cu-rich regions. However, In Fe 100- xCu x solid solutions with x⩽20, the Cu atoms were almost homogeneously solved into the bcc Fe-Cu phase. A possible mechanism for bcc-to-fcc and fcc-to-bcc changes in Fe 100- xCu x solid solutions is discussed in relation to the interdiffusion and the transition induced by the ball milling.

  20. Soft X-ray induced damage in PVA-based membranes in water environment monitored by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Tzvetkov, George; Späth, Andreas; Fink, Rainer H.

    2014-10-01

    The effect of synchrotron X-ray flux in a soft X-ray scanning-transmission microspectroscope (STXM) instrument on the chemical structure of air-filled poly(vinyl alcohol) (PVA) based microbubbles and their stabilizing shell has been examined. Prolonged soft X-ray illumination of the particles in aqueous suspension leads to the breaking of the microbubbles' protective polymer shell and substantial chemical changes. The latter were clarified via a micro-spot C K-edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy with further respect to the absorbed X-ray doses. Our results revealed a continuous degradation of the PVA network associated with formation of carbonyl- and carboxyl-containing species as well as an increased content of unsaturated bonds. The observed effects must be taken into account in studies of micro- and nanostructured polymer materials utilizing X-rays.

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

    PubMed

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

    2010-10-21

    Porphyrins are widely used as dye molecules in solar cells. Knowing the energies of their frontier orbitals is crucial for optimizing the energy level structure of solar cells. We use near edge x-ray absorption fine structure (NEXAFS) spectroscopy to obtain the energy of the lowest unoccupied molecular orbital (LUMO) with respect to the N(1s) core level of the molecule. A systematic energy shift of the N(1s) to LUMO transition is found along a series of 3d metal octaethylporphyrins and explained by density functional theory. It is mainly due to a shift of the N(1s) level rather than a shift of the LUMO or a change in the electron-hole interaction of the core exciton.

  2. Interpretation of X-ray absorption spectra of As(III) in solution using Monte Carlo simulations.

    PubMed

    Canche-Tello, Jesus; Vargas, M Cristina; Hérnandez-Cobos, Jorge; Ortega-Blake, Iván; Leclercq, Amelie; Solari, Pierre Lorenzo; Den Auwer, Christophe; Mustre de Leon, José

    2014-11-20

    We performed X-ray absorption spectroscopy measurements on the arsenic K-edge of As(III) in solution under acidic conditions. Extended X-ray absorption fine structure (EXAFS) and X-ray near edge structure (XANES) spectra were compared with theoretical calculations which use local atomic structure configurations, either derived from density functional theory (DFT) energy minimization (EM) calculations or based on classical Monte Carlo (MC) simulations, for a As(OH)3 cluster surrounded by water molecules. The nearest arsenic-oxygen distances obtained from the fit of the XAFS spectra are consistent with the distances present in configurations derived from Monte Carlo simulations but not with those obtained from DFT-EM calculations. Calculations of XANES using either DFT-EM or the average configuration obtained from MC simulations do not reproduce the XANES spectra in the vicinity of the absorption edge. However, specific local atomic structural configurations of the As(OH)3 and water molecules, obtained from MC simulations, which show some ordering of water molecules up to 5 Å from the arsenic, reproduce qualitatively the experimental spectra. These results highlight the capability of XANES to yield information about hydration of ions in solution.

  3. Metalloprotein active site structure determination: synergy between X-ray absorption spectroscopy and X-ray crystallography.

    PubMed

    Cotelesage, Julien J H; Pushie, M Jake; Grochulski, Pawel; Pickering, Ingrid J; George, Graham N

    2012-10-01

    Structures of metalloprotein active sites derived from X-ray crystallography frequently contain chemical anomalies such as unexpected atomic geometries or elongated bond-lengths. Such anomalies are expected from the known errors inherent in macromolecular crystallography (ca. 0.1-0.2Å) and from the lack of appropriate restraints for metal sites which are often without precedent in the small molecule structure literature. Here we review the potential of X-ray absorption spectroscopy to provide information and perspective which could aid in improving the accuracy of metalloprotein crystal structure solutions. We also review the potential problem areas in analysis of the extended X-ray absorption fine structure (EXAFS) and discuss the use of density functional theory as another possible source of geometrical restraints for crystal structure analysis of metalloprotein active sites.

  4. Use of X-ray absorption spectroscopy in the search for the best LIGO mirror coatings

    NASA Astrophysics Data System (ADS)

    McGuire, Stephen C.

    2008-03-01

    The Laser Interferometer Gravitational-wave Observatory (LIGO) seeks to improve its sensitivity for gravity-wave detection by a factor of ten during its next phase of operation, Advanced LIGO. In order to achieve this goal it is necessary to design and fabricate test mass mirrors that help minimize the noise in the interferometers and in doing so maximize gravity-wave detection capability. In this talk we will present recent results from our program of X-ray absorption spectroscopy measurements to obtain detailed chemical composition and structure of titania (TiO2)-doped tantala (Ta2O5) multilayers fabricated via ion beam sputtering on SiO2 substrates. Our investigations focus on how the microscopic features of the coatings influence their macroscopic mechanical loss properties. Our goal is to obtain correlations between chemical impurities and/or dopants and the optical absorption and mechanical loss characteristics of these multilayer coatings. To examine our samples we use synchrotron-based X-ray absorption Spectroscopy (XAS) techniques including Extended X-ray Absorption Fine Structure (EXAFS), X-ray Absorption Near Edge Structure (XANES) and X-ray Fluorescence (XRF). We present chemical and structural data obtained at the titanium K-edge and tantalum LIII-edge as well as relative elemental distribution information (Ti/Ta, Fe/Ta, and Cr/Ta) obtained via XRF. Following a brief description of the LIGO experiment, our program of research in optical materials for use in advanced versions of the interferometer will be described.

  5. Swift heavy ion irradiation of Pt nanocrystals: II. Structural changes and H desorption

    SciTech Connect

    Giulian, R.; Araujo, L.L.; Kluth, P.; Sprouster, D.J.; Schnohr, C.S.; Byrne, A.P.; Ridgway, M.C.

    2014-09-24

    The structural properties and H desorption from embedded Pt nanocrystals (NCs) following irradiation with swift heavy ions were investigated as a function of energy and fluence. From x-ray absorption near-edge spectroscopy analysis, Pt-H bonding was identified in NCs annealed in a forming gas (95% N{sub 2} + 5% H{sub 2}) ambient. The H content decreased upon irradiation and the desorption process was NC-size dependent such that larger NCs required a higher fluence to achieve a H-free state. Pt-H bonding and NC dissolution both perturbed the NC structural parameters (coordination number, bond-length and mean-square relative displacement) as determined with extended x-ray absorption fine structure measurements.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  8. Core-hole effect on XANES and electronic structure of minor actinide dioxides with fluorite structure

    NASA Astrophysics Data System (ADS)

    Suzuki, Chikashi; Nishi, Tsuyoshi; Nakada, Masami; Akabori, Mitsuo; Hirata, Masaru; Kaji, Yoshiyuki

    2012-02-01

    The authors investigated theoretically core-hole effects on X-ray absorption near-edge structures (XANES) of Np and Am LIII in neptunium dioxide (NpO2) and americium dioxide (AmO2) with CaF2-type crystal lattices using the all-electron full-potential linearized augmented plane-wave (FP-LAPW) method. The peak creation mechanism of XANES was shown by examining the electronic structures of these oxides, which indicated that core-hole screening was more marked for AmO2 than for NpO2 because of the difference in the charge transfer between these oxides. Furthermore, the results of charge density analysis suggested that the white line was assigned to the quasi-bound state composed of the localized Np d or Am d components and O components, and that the tail structure was created as a result of delocalized standing waves between the Np or Am atoms.

  9. Absorption characteristics of lithium bromide (LiBr) solution constrained by superhydrophobic nanofibrous structures

    SciTech Connect

    Isfahani, RN; Moghaddam, S

    2013-08-01

    An experimental study on absorption characteristics of water vapor into a thin lithium bromide (LiBr) solution flow is presented. The LiBr solution flow is constrained between a superhydrophobic vapor permeable wall and a solid surface that removes the heat of absorption. As opposed to conventional falling film absorbers, in this configuration, the solution film thickness and velocity can be controlled independently to enhance the absorption rate. The effects of water vapor pressure, cooling surface temperature, solution film thickness, and solution flow velocity on the absorption rate are studied. An absorption rate of approximately 0.006 kg/m(2) s was measured at a LiBr solution channel thickness and flow velocity of 100 mu m and 5 mm/s, respectively. The absorption rate increased linearly with the water vapor driving potential at the test conditions of this study. It was demonstrated that decreasing the solution film thickness and increasing the solution velocity enhance the absorption rate. The high absorption rate and the inherently compact form of the proposed,absorber facilitate development of compact small-scale waste heat or solar-thermal driven cooling systems. Published by Elsevier Ltd.

  10. Total Absorption Study of Beta Decays Relevant for Nuclear Applications and Nuclear Structure

    SciTech Connect

    Algora, A.; Valencia, E.; Taín, J.L.; Jordan, M.D.; Agramunt, J.; Rubio, B.; Estevez, E.; Molina, F.; Montaner, A.; Guadilla, V.; Fallot, M.; Porta, A.; Zakari-Issoufou, A.-A.; Bui, V.M.; and others

    2014-06-15

    An overview is given of our activities related to the study of the beta decay of neutron rich nuclei relevant for nuclear applications. Recent results of the study of the beta decay of {sup 87,88}Br using a new segmented total absorption spectrometer are presented. The measurements were performed at the IGISOL facility using trap-assisted total absorption spectroscopy.

  11. Total Absorption Study of Beta Decays Relevant for Nuclear Applications and Nuclear Structure

    SciTech Connect

    Algora, A.; Valencia, E.; Tain, J. L.; Jordan, M. D.; Agramunt, J.; Rubio, B.; Estevez, E.; Molina, F.; Montaner, A.; Guadilla, V.; Fallot, M.; Podolyak, Zs.; Regan, P. H.; Gelletly, W.; Bowry, M.; Mason, P.; Farrelly, G. F.; Rissanen, J.; Eronen, T.; Moore, I.; Penttila, H.; Aysto, J.; Eloma, V.; Hakala, J.; Jokinen, A.; Kolkinen, V.; Reponen, M.; Sonnenschein, V.; Cano-Ott, D.; Martinez, T.; Mendoza, E.; Garcia, A. R.; Gomez-Hornillos, M. B.; Gorlychev, V.; Caballero-Folch, R.; Kondev, F. G.; Sonzogni, A. A.

    2014-06-01

    We present an overview of our activities related to the study of the beta decay of neutron rich nuclei relevant for nuclear applications. Recent results of the study of the beta decay of Br using a new segmented total absorption spectrometer are presented. Our measurements were performed at the IGISOL facility using trap-assisted total absorption spectroscopy.

  12. Total Absorption Study of Beta Decays Relevant for Nuclear Applications and Nuclear Structure

    NASA Astrophysics Data System (ADS)

    Algora, A.; Valencia, E.; Taín, J. L.; Jordan, M. D.; Agramunt, J.; Rubio, B.; Estevez, E.; Molina, F.; Montaner, A.; Guadilla, V.; Fallot, M.; Porta, A.; Zakari-Issoufou, A.-A.; Bui, V. M.; Rice, S.; Podolyák, Zs.; Regan, P. H.; Gelletly, W.; Bowry, M.; Mason, P.; Farrelly, G. F.; Rissanen, J.; Eronen, T.; Moore, I.; Penttilä, H.; Äystö, J.; Eloma, V.; Hakala, J.; Jokinen, A.; Kolkinen, V.; Reponen, M.; Sonnenschein, V.; Cano-Ott, D.; Martínez, T.; Mendoza, E.; Garcia, A. R.; Gomez-Hornillos, M. B.; Gorlychev, V.; Caballero-Folch, R.; Kondev, F. G.; Sonzogni, A. A.

    2014-06-01

    An overview is given of our activities related to the study of the beta decay of neutron rich nuclei relevant for nuclear applications. Recent results of the study of the beta decay of 87,88Br using a new segmented total absorption spectrometer are presented. The measurements were performed at the IGISOL facility using trap-assisted total absorption spectroscopy.

  13. Ultralong copper phthalocyanine nanowires with new crystal structure and broad optical absorption.

    PubMed

    Wang, Hai; Mauthoor, Soumaya; Din, Salahud; Gardener, Jules A; Chang, Rio; Warner, Marc; Aeppli, Gabriel; McComb, David W; Ryan, Mary P; Wu, Wei; Fisher, Andrew J; Stoneham, Marshall; Heutz, Sandrine

    2010-07-27

    The development of molecular nanostructures plays a major role in emerging organic electronic applications, as it leads to improved performance and is compatible with our increasing need for miniaturization. In particular, nanowires have been obtained from solution or vapor phase and have displayed high conductivity or large interfacial areas in solar cells. In all cases however, the crystal structure remains as in films or bulk, and the exploitation of wires requires extensive postgrowth manipulation as their orientations are random. Here we report copper phthalocyanine (CuPc) nanowires with diameters of 10-100 nm, high directionality, and unprecedented aspect ratios. We demonstrate that they adopt a new crystal phase, designated eta-CuPc, where the molecules stack along the long axis. The resulting high electronic overlap along the centimeter length stacks achieved in our wires mediates antiferromagnetic couplings and broadens the optical absorption spectrum. The ability to fabricate ultralong, flexible metal phthalocyanine nanowires opens new possibilities for applications of these simple molecules.

  14. Structure and microwave absorption properties of Pr-Fe-Ni alloys

    NASA Astrophysics Data System (ADS)

    Xiong, Jilei; Pan, Shunkang; Cheng, Lichun; Liu, Xing; Lin, Peihao

    2015-06-01

    The Pr2Fe17-xNix (X=0.0, 0.2, 0.6, 1.0) alloy powders were obtained by arc smelting and high energy ball milling method. The phase structure, morphology and particle size of the powders were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and laser diffraction-based particle size analyzer, respectively. The saturation magnetization and electromagnetic parameters were determined by vibrating sample magnetometer (VSM) and vector network analyzer (VNA), respectively. The results indicate that the lattice parameter and the saturation magnetization of Pr2Fe17-xNix alloys decrease with increasing Ni content. And the minimum absorption peak frequency shifts towards the higher region with increasing Ni content. Compared to the powders without heat treatment, the powders tempered at 100 °C for 2 h have better absorbing properties. The minimum reflectivity peak value of Pr2Fe16Ni alloy reaches about -23.6 dB at 2.72 GHz with the matching thickness of 3.5 mm.

  15. 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.

  16. Redox Chemisty of Tantalum Clusters on Silica Characterized by X-ray Absorption Spectroscopy

    SciTech Connect

    Nemana,S.; Gates, B.

    2006-01-01

    SiO{sub 2}-supported clusters of tantalum were synthesized from adsorbed Ta(CH{sub 2}Ph){sub 5} by treatment in H{sub 2} at 523 K. The surface species were characterized by X-ray absorption spectroscopy (extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES)) and ultraviolet-visible spectroscopy. The EXAFS data show that SiOO{sub 2}-supported tantalum clusters were characterized by a Ta-Ta coordination number of approximately 2, consistent with the presence of tritantalum clusters, on average. When these were reduced in H{sub 2} and reoxidized in O{sub 2}, the cluster nuclearity remained essentially unchanged, although reduction and oxidation occurred, respectively, as shown by XANES and UV-vis spectra; in the reoxidation, the tantalum oxidation state change was approximately two electronic charges per tritantalum cluster. The data demonstrate an analogy between the chemistry of group 5 metals on the SiO{sub 2} support and their chemistry in solution, as determined by the group of Cotton.

  17. Dependency of magnetic microwave absorption on surface architecture of Co20Ni80 hierarchical structures studied by electron holography

    NASA Astrophysics Data System (ADS)

    Liu, Qinhe; Xu, Xianhui; Xia, Weixing; Che, Renchao; Chen, Chen; Cao, Qi; He, Jingang

    2015-01-01

    To design and fabricate rational surface architecture of individual particles is one of the key factors that affect their magnetic properties and microwave absorption capability, which is still a great challenge. Herein, a series of Co20Ni80 hierarchical structures with different surface morphologies, including flower-, urchin-, ball-, and chain-like morphologies, were obtained using structure-directing templates via a facile one-step solvothermal treatment. The microwave reflection loss (RL) of urchin-like Co20Ni80 hierarchical structures reaches as high as -33.5 dB at 3 GHz, with almost twice the RL intensity of the ball- and chain-like structures, and the absorption bandwidth (<-10 dB) is about 5.5 GHz for the flower-like morphology, indicating that the surface nanospikes and nanoflakes on the Co20Ni80 microsphere surfaces have great influences on their magnetic microwave absorption properties. Electron holography analysis reveals that the surface nanospikes and nanoflakes could generate a high density of stray magnetic flux lines and contribute a large saturation magnetization (105.62 emu g-1 for urchin-like and 96.41 emu g-1 for flower-like morphology), leading the urchin-like and flower-like Co20Ni80 to possess stronger microwave RL compared with the ball-like and chain-like Co20Ni80 alloys. The eddy-current absorption mechanism μ''(μ')-2(f)-1 is dominant in the frequency region above 8 GHz, implying that eddy-current loss is a vital factor for microwave RL in the high frequency range. It can be supposed from our findings that different surface morphologies of magnetic hierarchical structures might become an effective path to achieve high-performance microwave absorption for electromagnetic shielding and stealth camouflage applications.To design and fabricate rational surface architecture of individual particles is one of the key factors that affect their magnetic properties and microwave absorption capability, which is still a great challenge. Herein, a

  18. 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.

  19. High temperature emissivity, reflectivity, and x-ray absorption of BiFeO3

    NASA Astrophysics Data System (ADS)

    Massa, Néstor E.; del Campo, Leire; de Souza Meneses, Domingos; Echegut, Patrick; Fabbris, Gilberto F. L.; Azevedo, G. de M.; Martínez-Lope, María Jesús; Alonso, José Antonio

    2010-10-01

    We report on the lattice evolution of BiFeO3 as function of temperature using far infrared emissivity, reflectivity, and x-ray absorption local structure. A power law fit to the lowest frequency soft phonon in the magnetic ordered phase yields an exponent β =0.25 as for a tricritical point. At about 200 K below TN˜640 K it ceases softening as consequence of BiFeO3 metastability. We identified this temperature as corresponding to a crossover transition to an order-disorder regime. Above ˜700 K strong band overlapping, merging, and smearing of modes are consequence of thermal fluctuations and chemical disorder. Vibrational modes show band splits in the ferroelectric phase as emerging from triple degenerated species as from a paraelectric cubic phase above TC˜1090 K. Temperature dependent x-ray absorption near edge structure (XANES) at the Fe K edge shows that lower temperature Fe3+ turns into Fe2+. While this matches the FeO wüstite XANES profile, the Bi LIII-edge downshift suggests a high temperature very complex bond configuration at the distorted A perovskite site. Overall, our local structural measurements reveal high temperature defect-induced irreversible lattice changes, below, and above the ferroelectric transition, in an environment lacking of long-range coherence. We did not find an insulator to metal transition prior to melting.

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

    PubMed

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

    2013-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

    The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO2 aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn2+ ions are at the tetrahedral sites and trivalent Fe3+ ions occupy octahedral sites (normal spinel). When particle size decreases, Zn2+ ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix.

  2. Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

    PubMed Central

    Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

    2015-01-01

    The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

  3. THE STRUCTURE OF THE ULTRAVIOLET ABSORPTION SPECTRA OF CERTAIN PROTEINS AND AMINO ACIDS

    PubMed Central

    Coulter, Calvin B.; Stone, Florence M.; Kabat, Elvin A.

    1936-01-01

    1. The absorption spectra of a number of proteins in the region 2500 to 3000 A. have been found to comprise from six to nine narrow bands. In consequence of variation in the relative intensity of these bands from protein to protein, the absorption curve has a characteristic configuration for each protein. 2. These bands correspond closely in position with the narrow bands which appear in the absorption spectra of tryptophan, tyrosin, and phenylalanine. Tryptophan and tyrosin each present three bands, phenylalanine shows nine. 3. The bands in the proteins are accordingly attributed to these amino acids. In the proteins the bands are displaced from the positions which they occupy in the uncombined amino acids, in most instances, by 10 to 35 A. toward longer wavelengths. 4. The absorption spectrum of Pneumococcus Type I antibody resembles that of normal pseudoglobulin but shows characteristic differences. PMID:19872958

  4. X-ray absorption and photoemission spectroscopy of zinc protoporphyrin adsorbed on rutile TiO{sub 2}(110) prepared by in situ electrospray deposition

    SciTech Connect

    Rienzo, Anna; Mayor, Louise C.; Magnano, Graziano; Satterley, Christopher J.; O'Shea, James N.; Ataman, Evren; Schnadt, Joachim; Schulte, Karina

    2010-02-28

    Zinc-protoporphyrin, adsorbed on the rutile TiO{sub 2}(110) surface, has been studied using photoemission spectroscopy and near-edge absorption fine structure spectroscopy to deduce the nature of the molecule-surface bonding and the chemical environment of the central metal atom. To overcome the difficulties associated with sublimation of the porphyrin molecules, samples were prepared in situ using ultrahigh vacuum electrospray deposition, a technique which facilitates the deposition of nonvolatile and fragile molecules. Monolayers of Zn protoporphyrin are found to bond to the surface via the oxygen atoms of the deprotonated carboxyl groups. The molecules initially lie largely parallel to the surface, reorienting to an upright geometry as the coverage is increased up to a monolayer. For those molecules directly chemisorbed to the surface, the interaction is sufficiently strong to pull the central metal atom out of the molecule.

  5. Solvent Dependence of the Molecular Order in Ion-Exchanged Self-Assembled dialkylammonium Monolayers on Mica Studied with Soft X-ray Absorption

    SciTech Connect

    Hahner,G.; Zwahlen, M.; Caseri, W.

    2005-01-01

    Dialkyldimethylammonium films on mica prepared via ion exchange from solution have been reported to be of high quality in terms of their density and molecular orientation. Different preparation procedures are described in the literature. The molecular order and the inclination of the alkyl chains, however, are often deduced from indirect experimental evidence such as the wettability and the film thickness. In the present study we employed near edge X-ray absorption fine structure spectroscopy (NEXAFS) to determine directly the order of the molecules adsorbed from different solvents (water, methanol, water/methanol 1:1, cyclohexanol, and chloroform). It was found that films prepared from different solvents are displaying large differences in the established surface coverage and orientation. In particular, NEXAFS disclosed that the orientation of the alkyl chains can differ significantly even when similar water contact angle values are observed.

  6. Simulating Cl K-edge X-ray absorption spectroscopy in MCl62- (M= U, Np, Pu) complexes and UOCl5- using time-dependent density functional theory

    SciTech Connect

    Govind, Niranjan; De Jong, Wibe A.

    2014-02-21

    We report simulations of the X-ray absorption near edge structure (XANES) at the Cl K-edge of actinide hexahalides MCl62- (M = U, Np, Pu) and the UOCl5- complex using linear-response time-dependent density functional theory (LR-TDDFT) extended for core excitations. To the best of our knowledge, these are the first calculations of the Cl K-edge spectra of NpCl62- and PuCl62-. In addition, the spectra are simulated with and without the environmental effects of the host crystal as well as ab initio molecular dynamics (AIMD) to capture the dynamical effects due to atomic motion. The calculated spectra are compared with experimental results, where available and the observed trends are discussed.

  7. Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study

    NASA Astrophysics Data System (ADS)

    Helmbrecht, C.; Lützenkirchen-Hecht, D.; Frank, W.

    2015-03-01

    Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES

  8. Structural studies of amorphous titanium diboride thin films by extended x-ray-absorption fine-structure and extended electron-energy-loss fine-structure techniques

    NASA Astrophysics Data System (ADS)

    Kaloyeros, Alain E.; Hoffman, Mark P.; Williams, Wendell S.; Greene, Alex E.; McMillan, Joyce A.

    1988-10-01

    The local atomic structure of amorphous titanium diboride thin films, prepared by electron-beam vaporization (EBV) of the crystalline compound onto liquid-nitrogen-cooled substrates, was studied using extended x-ray-absorption fine-structure (EXAFS) and extended energy-loss fine-structure (EXELFS) techniques. From a comparison of the extended fine-structure spectra of the amorphous films with corresponding spectra of crystalline titanium diboride, accurate information was derived on the nature of the local structure, or short-range order, and on the coordination numbers, interatomic distances, and nanostructural atomic disorder in amorphous TiB2. A relaxation of the interatomic spacing and a reduction of coordination number for the nearest-neighbor atoms was inferred for the amorphous state. Local prismatic coordination with random 90° rotations about prismatic planes is proposed as a likely atomic structure consistent with the data for the amorphous form. Finally, EXAFS and EXELFS were employed to examine in detail the structural changes induced in amorphous TiB2 by variations in the EBV deposition parameters, and to determine a set of optimized parameters for the EBV deposition of a TiB2 stable amorphous phase.

  9. Development of an in-situ structure/photo-absorption coincident measurement system for precise structure-optical property relationship research at SPring-8

    NASA Astrophysics Data System (ADS)

    Kim, Jungeun; Kato, Kenichi; Moritomo, Yutaka; Takata, Masaki

    2010-06-01

    We have developed the structure and optical property coincident measurement system equipped with the photo-absorption system to the Large Debye-Scherrer Camera at BL44B2 of the SPring-8. Both photo-absorption detecting systems, the Si pin-photo diode for a 532 nm CW laser and the absorption spectrum covered the range of UV-IR (200˜1400 nm) for a white beam, are adopted. In order to verify the coincident measurement system, the X-ray powder diffraction and photo-absorption with the cyanide complex were performed individually and simultaneously under the temperature changes. As a result, the coincident measurement system performed successfully the one-to-one corresponding measurement between X-ray diffraction and photo-absorption. In addition, the monitoring of the photo-absorption informed us the property change of the material for the measurement condition and the sample transformation by temperature, laser etc. as well as damage by high-brilliance synchrotron radiation X-ray beam.

  10. Structural studies of the phase separation of amorphous FexGe100-x alloys

    NASA Astrophysics Data System (ADS)

    Lorentz, Robert D.; Bienenstock, Arthur; Morrison, Timothy I.

    1994-02-01

    Small-angle x-ray scattering and x-ray-absorption near-edge spectroscopy (XANES) experiments have been performed on amorphous FexGe100-x alloys over the composition range 0<=x<=72. The observed small-angle x-ray-scattering patterns were compared both with those calculated for a model assuming segregation of the alloys into particular phases and with scattering patterns calculated for voids in a homogeneous matrix. The x-ray-absorption near-edge-structure data were used to test for phase separation. No large-scale phase separation is observed in the semiconductor-metal transition region (15-25 at. % Fe), but fine-scale, kinetically limited phase separation or other types of composition fluctuations cannot be ruled out. The results also indicate that phase separation occurs for alloys with 37<=x<=72, with data consistent with separation into amorphous FeGe2 and Fe3Ge. Thus, ferromagnetic moment formation occurs in the phase-separated region, with the transition composition (40-43 at. % Fe) probably linked to a-Fe3Ge percolation, as hypothesized by Janot for the related FexSn100-x system. This phase separation explains the Mossbauer observation of ``magnetic'' and ``nonmagnetic'' Fe atoms in these alloys.

  11. Complex Resonance Absorption Structure in the X-Ray Spectrum of IRAS 13349+2438

    NASA Technical Reports Server (NTRS)

    Sako, M.; Kahn, S. M.; Behar, E.; Kaastra, J. S.; Brinkman, A. C.; Boller, Th.; Puchnarewicz, E. M.; Starling, R.; Liedahl, D. A.; Clavel, J.

    2000-01-01

    The luminous infrared-loud quasar IRAS 13349+2438 was observed with the XMM - Newton Observatory as part of the Performance Verification program. The spectrum obtained by the Reflection Grating Spectrometer (RGS) exhibits broad (FWHM - 1400 km/s) absorption lines from highly ionized elements including hydrogen- and helium-like carbon, nitrogen, oxygen, and neon, and several iron L - shell ions (Fe XVII - XX). Also shown in the spectrum is the first astrophysical detection of a broad absorption feature around lambda = 16 - 17 A identified as an unresolved transition array (UTA) of 2p - 3d inner-shell absorption by iron M-shell ions in a much cooler medium; a feature that might be misidentified as an O VII edge when observed with moderate resolution spectrometers. No absorption edges are clearly detected in the spectrum. We demonstrate that the RGS spectrum of IRAS 13349+2438 exhibits absorption lines from two distinct regions, one of which is tentatively associated with the medium that produces the optical/UV reddening.

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

    PubMed

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

    2014-11-12

    We report on Raman and Ni K-edge x-ray absorption investigations of a NiS(2-x)Se(x) (with x = 0.00, 0.50/0.55, 0.60, and 1.20) pyrite family. The Ni K-edge absorption edge shows a systematic shift going from an insulating phase (x = 0.00 and 0.50) to a metallic phase (x = 0.60 and 1.20). The near-edge absorption features show a clear evolution with Se doping. The extended x-ray absorption fine structure data reveal the evolution of the local structure with Se doping which mainly governs the local disorder. We also describe the decomposition of the NiS(2-x)Se(x) Raman spectra and investigate the weights of various phonon modes using Gaussian and Lorentzian profiles. The effectiveness of the fitting models in describing the data is evaluated by means of Bayes factor estimation. The Raman analysis clearly demonstrates the disorder effects due to Se alloying in describing the phonon spectra of NiS(2-x)Se(x) pyrites. PMID:25320052

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

    PubMed

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

    2014-11-12

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

  14. Vibronic Structures in Absorption and Fluorescence Spectra of Firefly Oxyluciferin in Aqueous Solutions.

    PubMed

    Hiyama, Miyabi; Noguchi, Yoshifumi; Akiyama, Hidefumi; Yamada, Kenta; Koga, Nobuaki

    2015-01-01

    To elucidate the factors determining the spectral shapes and widths of the absorption and fluorescence spectra for keto and enol oxyluciferin and their conjugate bases in aqueous solutions, the intensities of vibronic transitions between their ground and first electronic excited states were calculated for the first time via estimation of the vibrational Franck-Condon factors. The major normal modes, overtones and combination tones in absorption and fluorescence spectra are similar for all species. The theoretical full widths at half maximum of absorption spectra are 0.4-0.7 eV and those for the fluorescence spectra are 0.4-0.5 eV, except for phenolate-keto that exhibits exceptionally sharp peak widths due to the dominance of the 0-0' or 0'-0 band. These spectral shapes and widths explain many relevant features of the experimentally observed spectra. PMID:25946599

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

    SciTech Connect

    Piskorska-Hommel, E.; Winiarski, M. J.; Kunert, G.; Falta, J.; Demchenko, I. N.; Roshchupkina, O. D.; Grenzer, J.; Hommel, D.; Holý, V.

    2015-02-14

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

  16. Excited-state molecular structures captured by X-ray transient absorption spectroscopy: a decade and beyond.

    PubMed

    Chen, Lin X; Zhang, Xiaoyi; Lockard, Jenny V; Stickrath, Andrew B; Attenkofer, Klaus; Jennings, Guy; Liu, Di-Jia

    2010-03-01

    Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes have been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled. PMID:20164647

  17. Excited-state molecular structures captured by x-ray transient absorption spectroscopy : a decade and beyond.

    SciTech Connect

    Chen, L. X.; Zhang, X.; Lockard, J. V.; Stickrath, A. B.; Attenkofer, K.; Jennings, G.; Liu, D.-J.; Northwestern Univ.

    2010-03-02

    Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes have been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled.

  18. Absorption spectroscopy of the rubidium dimer in an overheated vapor: An accurate check of molecular structure and dynamics

    SciTech Connect

    Beuc, R.; Movre, M.; Horvatic, V.; Vadla, C.; Dulieu, O.; Aymar, M.

    2007-03-15

    Experimental studies of the absorption spectrum of the Rb{sub 2} dimer are performed in the 600-1100 nm wavelength range for temperatures between 615 and 745 K. The reduced absorption coefficient is measured by spatially resolved white light absorption in overheated rubidium vapor with a radial temperature gradient, which enables simultaneous measurements at different temperatures. Semiclassical and quantum spectral simulations are obtained by taking into account all possible transitions involving the potential curves stemming from the 5 {sup 2}S+5 {sup 2}S and 5 {sup 2}S+5 {sup 2}P asymptotes. The most accurate experimental potential curves are used where available, and newly calculated potential curves and transition dipole moments otherwise. The overall consistency of the theoretical model with the experimental interpretation is obtained only if the radial dependence of both the calculated transition dipole moments and the spin-orbit coupling is taken into account. This highlights the low-resolution absorption spectroscopy as a valuable tool for checking the accuracy of molecular electronic structure calculations.

  19. High temperature extended x-ray absorption fine structure study of multiferroic BiFeO3

    NASA Astrophysics Data System (ADS)

    Raghavendra Reddy, V.; Meneghini, Carlo; Kothari, Deepti; Gupta, Ajay; Aquilanti, Giuliana

    2012-08-01

    Local atomic structure modifications around Fe atoms in polycrystalline multiferroic BiFeO3 are studied by Fe K edge x-ray absorption spectroscopy as a function of temperature across the Néel temperature (TN = 643 K) in order to reveal local structure modifications related to the magnetic transition. This work demonstrates that on crossing TN the local structure around Fe shows peculiar changes: the Fe-O bond lengths get shorter, the ligand symmetry increases and the Fe-O bond length disorder (σ2) deviates from Debye behaviour. These results suggest that the structural transition at the ferroelectric Curie temperature (TC = 1103 K) is anticipated by early local rearrangement of the structure starting already at TN.

  20. Electronic structure of ReO3Me by variable photon energy photoelectron spectroscopy, absorption spectroscopy and density functional calculations.

    PubMed

    de Simone, Monica; Coreno, Marcello; Green, Jennifer C; McGrady, Sean; Pritchard, Helen

    2003-03-24

    Valence photoelectron (PE) spectra have been measured for ReO(3)Me using a synchrotron source for photon energies ranging between 20 and 110 eV. Derived branching ratios (BR) and relative partial photoionization cross sections (RPPICS) are interpreted in the context of a bonding model calculated using density functional theory (DFT). Agreement between calculated and observed ionization energies (IE) is excellent. The 5d character of the orbitals correlates with the 5p --> 5d resonances of the associated RPPICS; these resonances commence around 47 eV. Bands with 5d character also show a RPPICS maximum at 35 eV. The RPPICS associated with the totally symmetric 4a(1) orbital, which has s-like character, shows an additional shape resonance with an onset of 43 eV. The PE spectrum of the inner valence and core region measured with photon energies of 108 and 210 eV shows ionization associated with C 2s, O 2s, and Re 4f and 5p electrons. Absorption spectra measured in the region of the O1s edge showed structure assignable to excitation to the low lying empty "d" orbitals of this d(0) molecule. The separation of the absorption bands corresponded with the calculated orbital splitting and their intensity with the calculated O 2p character. Broad bands associated with Re 4d absorption were assigned to (2)D(5/2) and (2)D(3/2) hole states. Structure was observed associated with the C1s edge but instrumental factors prevented firm assignment. At the Re 5p edge, structure was observed on the (2)P(3/2) absorption band resulting from excitation to the empty "d" levels. The intensity ratios differed from that of the O 1s edge structure but were in good agreement with the calculated 5d character of these orbitals. An absorption was observed at 45 eV, which, in the light of the resonance in the 4a(1) RPPICS, is assigned to a 4a(1) --> ne, na(2) transition. The electronic structure established for ReO(3)Me differs substantially from that of TiCl(3)Me and accounts for the difference in

  1. 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.

  2. Does complex absorption behavior leading to conditioning and damage in KDP/DKDP reflect the electronic structure of initiators?

    SciTech Connect

    Feit, M D; DeMange, P P; Negres, R A; Rubenchik, A M; Demos, S G

    2007-10-24

    Currently, most of our thinking about the defects responsible for initiating laser damage considers them as featureless absorbers. However, an increasing body of evidence, particularly involving multi-wavelength irradiation, suggests electronic structure of damage initiators is important in determining both initiation and conditioning behaviors in KDP. The effective absorption coefficient of energy under multi-wavelength irradiation cannot be accounted for by a structureless absorber, but is consistent with an initiator with a multi-level structure. We outline the evidence and assess the ability of such a simple multi-level model to explain these and other experimentally observed behaviors.

  3. Studying the local structures of novel materials using the Extended X-ray Absorption Fine Structure technique

    NASA Astrophysics Data System (ADS)

    Jiang, Yu

    2009-12-01

    In this dissertation, investigations on the local lattice structures for a variety of novel materials using Extended X-ray Absorption Fine Structure (EXAFS) technique are presented. Different experiment schemes were applied to obtain EXAFS data with high quality, and some interesting results were obtained by careful analysis. The power of the EXAFS technique was once again proved. In Chapter 1, I first briefly introduce the EXAFS theory and experiments, then give readers who are not familiar with this technique a short introduction on data reduction and analysis, and finally discuss some problems that are easily ignored in the interpretation of the experiment results. In Chapter 2, a temperature-dependent EXAFS investigation of La 1-xCaxMnO 3 is presented for the concentration range that spans the ferromagnetic-insulator (FMI) to ferromagnetic-metal (FMM) transition region, x = 0.16, 0.18, 0.20, and 0.22; the titrated hole concentrations are slightly higher y = 0.2, 0.22, 0.24, and 0.25 respectively. In Chapter 3, I report EXAFS studies of n- and p-type Ba8Ga 16Ge30 samples (type I clathrate) at the Ga, Ge, and Ba K-edges, to probe the local structure, particularly around the Ba atoms located inside 20- and 24-atom cages (Ba1 and Ba2 sites respectively) formed of Ga/Ge atoms. In agreement with diffraction analysis we find Ba2 is off-center, with a component in the bc plane (0.15 A) comparable to that found in diffraction; however, under the assumption of a stiff cage we also require a significant a component. This suggests a coupling or attraction between the Ba2 atoms and the hexagonal rings at the top or bottom of the cage that encloses the Ba2 site. In Chapter 4, I report detailed degradation and rejuvenation studies for AC electro-luminescence (EL) devices made using the phosphor ZnS:Cu,CI. We find that the AC EL emission spectra vary considerably with AC driving frequency but all spectra can be fit to a sum of four Gaussians. The combined experiments place

  4. 21 centimeter HI absorption at z = 0. 437 against the extended radio structure of 3c 196

    SciTech Connect

    Brown, R.L.; Mitchell, K.J.

    1983-01-01

    We report the detection of an absorption line at 988.7. MHz toward the quasar 3C 196. We identify this line as the lambda21 cm line of neutral atomic hydrogen seen at a redshift of z/sub abs/ = 0.4366. No optical absorption lines have been noted in the z/sub em/ = 0.871 quasar 3C 196 heretofore. All the radio emission of 3C 196 is contained in two thetaroughly-equal3'' extended lobes symmetrically placed (position angle approx.26/sup 0/) about the optical object. The optical QSO itself is an extremely weak, <1 mJy, radio source. Thus to account for the approx.0.5 Jy seen in the absorption line we infer that the diameter of the absorbing region must be at least as large as 750 pc and perhaps as large as, or larger than, 30 kpc. We note further than an optical wisp is seen extending approx.3'' x 1'' from the QSO at position angle approx.120/sup 0/, that is in a direction perpendicular to the separation of the radio lobes. If this wisp is the disk of an intervening galaxy, then the H i absorption is direct evidence for absorption in a galactic halo. Puzzles abound; (1) If the optical wisp seen superposed on the QSO is an intervening galaxy then what aspects, if any, of the emission from 3C 196 are gravitational lens effects. (2) If the wisp is associated with the QSO, why is it radio quiet and why is it orthogonal to the extended radio structure of 3C 196. (3) Is it significant that z/sub abs/ is one-half z/sub em/ within the errors.

  5. Fabrication of controllable form submicrometer structures on positive photoresist by one-photon absorption direct laser writing technique

    NASA Astrophysics Data System (ADS)

    Tong, Quang Cong; Do, Minh Thanh; Journet, Bernard; Ledoux-Rak, Isabelle; Lai, Ngoc Diep

    2016-04-01

    We demonstrate a very simple and low-cost method based on one-photon absorption direct laser writing technique to fabricate arbitrary two-dimensional (2D) polymeric submicrometer structures with controllable form. In this technique, a continuous-wave green laser beam (532 nm) with very weak power is tightly focused into a positive photoresist (S1805) by a high numerical aperture (NA) objective lens (OL), depolymerizing the polymer in a local submicrometer region. The focusing spot is then moved in a controllable trajectory by a 3D piezo translation stage, resulting in desired structures. The low absorption effect of the photoresist at the excitation wavelength allows obtaining structures with submicrometer size and great depth. In particular, by controlling the exposure dose, e.g. the scanning speed, and the scanning configuration, the structures have been created in positive (cylindrical material in air) or negative (air holes) form. The 2D square structures with periods in between 0.6 μm and 1 μm and with a feature size of about 150 nm have been demonstrated with an OL of NA = 0.9 (air-immersion). The fabricated results are well consistent with those obtained numerically by using a vectorial diffraction theory for high NA OLs. This investigation should be very useful for fabrication of photonic and plasmonic templates.

  6. Structure vs. excitonic transitions in self-assembled porphyrin nanotubes and their effect on light absorption and scattering.

    PubMed

    Arteaga, Oriol; Canillas, Adolf; El-Hachemi, Zoubir; Crusats, Joaquim; Ribó, Josep M

    2015-12-28

    The optical properties of diprotonated meso-tetrakis(4-sulphonatophenyl)porphyrin (TPPS(4)) J-aggregates of elongated thin particles (nanotubes in solution and ribbons when deposited on solid interfaces) are studied by different polarimetric techniques. The selective light extinction in these structures, which depends on the alignment of the nanoparticle with respect to the polarization of light, is contributed by excitonic absorption bands and by resonance light scattering. The optical response as a function of the polarization of light is complex because, although the quasi-one-dimensional structure confines the local fields along the nanotube axis, there are two orthogonal excitonic bands, of H- and J-character, that can work in favor of or against the field confinement. Results suggest that resonance light scattering is the dominant effect in solid state preparations, i.e. in collective groups (bundles) of ribbons but in diluted solutions, i.e. with isolated nanotubes, the absorption at the excitonic transitions remains dominant and linear dichroism spectra can be a direct probe of the exciton orientations. Therefore, by analyzing scattering and absorption data we can determine the alignment of the excitonic bands within the nanoparticle, i.e. of the orientation of the basic 2D porphyrin architecture in the nanoparticle. This is a necessary first step for understanding the directions of energy transport, charge polarization and non-linear optical properties in these materials.

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  8. Superparamagnetic nanoplatforms for theragnostic applications: a structural investigation

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  9. Further constraints on variation of the fine-structure constant from alkali-doublet QSO absorption lines

    NASA Astrophysics Data System (ADS)

    Murphy, M. T.; Webb, J. K.; Flambaum, V. V.; Prochaska, J. X.; Wolfe, A. M.

    2001-11-01

    Comparison of quasar (QSO) absorption-line spectra with laboratory spectra provides a precise probe for variability of the fine-structure constant, α, over cosmological time-scales. We constrain variation in α in 21 Keck/HIRES Siiv absorption systems using the alkali-doublet (AD) method in which changes in α are related to changes in the doublet spacing. The precision obtained with the AD method has been increased by a factor of 3: Δα/α=(-0.5+/-1.3)×10-5. We also analyse potential systematic errors in this result. Finally, we compare the AD method with the many-multiplet method, which has achieved an order of magnitude greater precision, and we discuss the future of the AD method.

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

    SciTech Connect

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

    2012-08-15

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

  11. The spatial and kinematic structure of QSO metal-line absorption systems

    NASA Technical Reports Server (NTRS)

    Lanzetta, Kenneth M.

    1992-01-01

    Recent attempts to infer the spatial and kinematic distributions of the material responsible for absorption lines observed in the spectra of background QSOs are presented. Current models of the absorbing regions are compared, and initial observational results are described. This research is expected to lead eventually to a detailed picture of the extended gaseous halo regions of galaxies at early evolutionary stages and to an understanding of the physical processes at work in these halos.

  12. Endocrine tumour in kidney affecting small bowel structure, motility, and absorptive function 1

    PubMed Central

    Gleeson, M. H.; Bloom, S. R.; Polak, J. M.; Henry, K.; Dowling, R. H.

    1971-01-01

    A 44-year-old woman is described with an endocrine tumour arising in the kidney. There were associated abnormalities of small intestinal morphology, motility, and absorptive function. These abnormalities reversed on removal of the tumour. Detailed studies showed that the tumour contained, and was secreting, glucagon. It is postulated that the intestinal abnormalities may have resulted from glucagon itself or another, as yet unidentified, hormone. ImagesFig. 1Fig. 2Fig. 3Fig. 4Fig. 5Fig. 6 PMID:4941684

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

    NASA Astrophysics Data System (ADS)

    Liu, Xiangxin

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

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

    NASA Astrophysics Data System (ADS)

    Qamoshi, Khadijeh; Rasuli, Reza

    2016-09-01

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

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

    SciTech Connect

    Fukui, Akihiro; Hatai, Keigo; Cho, Shinatora; Arakawa, Yoshihiro; Komurasaki, Kimiya

    2008-04-28

    In Repetitively Pulsed (RP) Laser Propulsion, laser energy irradiated to a vehicle is converted to blast wave enthalpy during the Laser Supported Detonation (LSD) regime. Based on the measured post-LSD electron number density profiles by two-wavelength Mach Zehnder interferometer in a line-focusing optics, electron temperature and absorption coefficient were estimated assuming Local Thermal Equilibrium. A 10J/pulse CO{sub 2} laser was used. As a result, laser absorption was found completed in the layer between the shock wave and the electron density peak. Although the LSD-termination timing was not clear from the shock-front/ionization-front separation in the shadowgraph images, there observed drastic changes in the absorption layer thickness from 0.2 mm to 0.5 mm and in the peak heating rate from 12-17x10{sup 13} kW/m{sup 3} to 5x10{sup 13} kW/m{sup 3} at the termination.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  17. The role of solvent structure in the absorption spectrum of solvated electrons: Mixed quantum/classical simulations in tetrahydrofuran

    NASA Astrophysics Data System (ADS)

    Bedard-Hearn, Michael J.; Larsen, Ross E.; Schwartz, Benjamin J.

    2005-04-01

    In polar fluids such as water and methanol, the peak of the solvated electron's absorption spectrum in the red has been assigned as a sum of transitions between an s-like ground state and three nearly degenerate p-like excited states bound in a quasispherical cavity. In contrast, in weakly polar solvents such as tetrahydrofuran (THF), the solvated electron has an absorption spectrum that peaks in the mid-infrared, but no definitive assignment has been offered about the origins of the spectrum or the underlying structure. In this paper, we present the results of adiabatic mixed quantum/classical molecular dynamic simulations of the solvated electron in THF, and provide a detailed explanation of the THF-solvated electron's absorption spectrum and electronic structure. Using a classical solvent model and a fully quantum mechanical excess electron, our simulations show that although the ground and first excited states are bound in a quasispherical cavity, a multitude of other, nearby solvent cavities support numerous, nearly degenerate, bound excited states that have little Franck-Condon overlap with the ground state. We show that these solvent cavities, which are partially polarized so that they act as electron trapping sites, are an inherent property of the way THF molecules pack in the liquid. The absorption spectrum is thus assigned to a sum of bound-to-bound transitions between a localized ground state and multiple disjoint excited states scattered throughout the fluid. Furthermore, we find that the usual spherical harmonic labels (e.g., s-like, p-like) are not good descriptors of the excited-state wave functions of the solvated electron in THF. Our observation of multiple disjoint excited states is consistent with femtosecond pump-probe experiments in the literature that suggest that photoexcitation of solvated electrons in THF causes them to relocalize into solvent cavities far from where they originated.

  18. X-ray excited optical luminescence from hexagonal boron nitride nanotubes: electronic structures and the role of oxygen impurities.

    PubMed

    Liu, Lijia; Sham, Tsun-Kong; Han, Weiqiang; Zhi, Chunyi; Bando, Yoshio

    2011-01-25

    We report a study on the optical luminescence properties and the electronic structures of boron nitride nanotubes (BNNTs). BNNTs with natural B (80% (11)B and 20% (10)B) and pure (10)B are investigated in comparison with hexagonal BN crystals using X-ray absorption near-edge structures (XANES) and X-ray excited optical luminescence (XEOL). We find that the BNNT specimen synthesized with natural B contains more oxide impurities than that with pure (10)B, resulting in significantly different behavior in optical luminescence. All BN samples with hexagonal structures are found to emit strong luminescence, but the emission spectra are strongly morphology- and structure-dependent. XEOL and XANES measurements were carried out at the B K-edge, N K-edge, and O K-edge in order to reveal the origin of different luminescence channels and the corresponding electronic structures in these BN materials.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  1. Metal-line absorption around z ≈ 2.4 star-forming galaxies in the Keck Baryonic Structure Survey

    NASA Astrophysics Data System (ADS)

    Turner, Monica L.; Schaye, Joop; Steidel, Charles C.; Rudie, Gwen C.; Strom, Allison L.

    2014-11-01

    We study metal absorption around 854 z ≈ 2.4 star-forming galaxies taken from the Keck Baryonic Structure Survey. The galaxies examined in this work lie in the fields of 15 hyperluminous background quasi-stellar objects, with galaxy impact parameters ranging from 35 proper kpc (pkpc) to 2 proper Mpc (pMpc). Using the pixel optical depth technique, we present the first galaxy-centred 2D maps of the median absorption by O VI, N V, C IV, C III, and Si IV, as well as updated results for H I. At small galactocentric radii we detect a strong enhancement of the absorption relative to randomly located regions that extend out to at least 180 pkpc in the transverse direction, and ±240 km s-1 along the line of sight (LOS, ˜1 pMpc in the case of pure Hubble flow) for all ions except N V. For C IV (and H I) we detect a significant enhancement of the absorption signal out to 2 pMpc in the transverse direction, corresponding to the maximum impact parameter in our sample. After normalizing the median absorption profiles to account for variations in line strengths and detection limits, in the transverse direction we find no evidence for a sharp drop-off in metals distinct from that of H I. We argue instead that non-detection of some metal-line species in the extended circumgalactic medium is consistent with differences in the detection sensitivity. Along the LOS, the normalized profiles reveal that the enhancement in the absorption is more extended for O VI, C IV, and Si IV than for H I. We also present measurements of the scatter in the pixel optical depths, covering fractions, and equivalent widths as a function of projected galaxy distance. Limiting the sample to the 340 galaxies with redshifts measured from nebular emission lines does not decrease the extent of the enhancement along the LOS compared to that in the transverse direction. This rules out redshift errors as the source of the observed redshift-space anisotropy and thus implies that we have detected the signature

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

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

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

  3. High-Pressure Evolution of Fe2O3 Electronic Structure Revealed by X-ray Absorption

    SciTech Connect

    Kao, Chi-Chang

    2011-08-12

    We report the first high pressure measurement of the Fe K-edge in hematite (Fe{sub 2}O{sub 3}) by X-ray absorption spectroscopy in partial fluorescence yield geometry. The pressure-induced evolution of the electronic structure as Fe{sub 2}O{sub 3} transforms from a high-spin insulator to a low-spin metal is reflected in the x-ray absorption pre-edge. The crystal field splitting energy was found to increase monotonically with pressure up to 48 GPa, above which a series of phase transitions occur. Atomic multiplet, cluster diagonalization, and density-functional calculations were performed to simulate the pre-edge absorption spectra, showing good qualitative agreement with the measurements. The mechanism for the pressure-induced phase transitions of Fe{sub 2}O{sub 3} is discussed and it is shown that ligand hybridization significantly reduces the critical high-spin/low-spin gap pressure.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  5. Exploration of Heterogeneous Chemistry in Model Atmospheric Particles Using Extended X-ray Absorption Fine Structure Analysis

    SciTech Connect

    Bramante,J.; Hinrichs, R.; Brown, E.; Calvin, S.

    2007-01-01

    As models of the composition and heterogeneous chemical reactions of the troposphere undergo refinement, novel application of state-of-the-art analytical techniques will be necessary to propound realistic characterizations of mineral dust chemistry. In this study, strontium carbonate particles treated with gaseous nitric acid and nitrogen dioxide were examined with X-ray absorption fine structure analysis (EXAFS). The X-ray spectra of carbonate and nitrate standards were fitted to ab initio calculations, which were used to determine the structure and consistency of strontium nitrate formed on strontium carbonate. By examining differences in mean square radial displacement and lattice spacing values obtained for bulk Sr(NO3)2 as compared to Sr(NO3)2 formed on SrCO3, EXAFS proves effective as a tool for investigating the local structure and composition of heterogeneous aerosol particles. The implications of findings on reacted strontium carbonate for atmospheric models of calcium carbonate aerosol are discussed.

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

    PubMed

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

    2016-05-23

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

  7. Possible evidence for a variable fine-structure constant from QSO absorption lines: motivations, analysis and results

    NASA Astrophysics Data System (ADS)

    Murphy, M. T.; Webb, J. K.; Flambaum, V. V.; Dzuba, V. A.; Churchill, C. W.; Prochaska, J. X.; Barrow, J. D.; Wolfe, A. M.

    2001-11-01

    An experimental search for variation in the fundamental coupling constants is strongly motivated by modern high-energy physics theories. Comparison of quasar (QSO) absorption-line spectra with laboratory spectra provides a sensitive probe for variability of the fine-structure constant, α, over cosmological time-scales. We have previously developed and applied a new method providing an order-of-magnitude gain in precision over previous optical astrophysical constraints. Here we extend that work by including new quasar spectra of damped Lyman-α absorption systems. We also reanalyse our previous lower-redshift data and confirm our initial results. The constraints on α come from simultaneous fitting of absorption lines of subsets of the following species: Mgi, Mgii, Alii, Aliii, Siii, Crii, Feii, Niii and Znii. We present a detailed description of our methods and results based on an analysis of 49 quasar absorption systems (towards 28 QSOs) covering the redshift range [formmu2]0.5

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  9. Non-equilibrium-state x-ray absorption spectroscopy: a local structure study of photo-induced phase transition

    NASA Astrophysics Data System (ADS)

    Oyanagi, H.; Tayagaki, T.; Tanaka, K.

    2003-01-01

    We describe non-equilibrium-state x-ray absorption spectroscopy focusing on local structure of photo-excited states trapped at low temperature. For this purpose, a novel Ge 100 pixel array detector with a packing density of 88% was developed. The local structure of photo-induced phase of Fe(II) spin crossover complex, [Fe(2-pic)3]Cl2EtOH (2-pic=2-aminomethyl pyridine), was investigated at low temperature (T <150 K). The use of pixel array detector and high-flux synchrotron x-ray source (multipole wiggler) successfully provided x-ray absorption spectra with high quality, in-situ, during the photo-excitation. It was found that the photo-induced phase under optical pumping at low temperature (T < 50 K) has an octahedral geometry with the elongated Fe-N distance (2.16 ± 0.01 Å), stabilizing the high spin state (S=2) configuration. No indication of symmetry breaking of FeN6 clusters upon LS↔HS spin-state switching was observed. It was demonstrated that the technique is a promising means to probe the local structure of non-equilibrium state such as trapped excited states or metastable states.

  10. Encapsulation of lead sulfide molecular clusters into solid matrices. Structural analysis with x-ray absorption spectroscopy

    SciTech Connect

    Moller, K.; Bein, T. ); Herron, N.; Mahler, W.; Wang, Ying )

    1989-07-26

    Molecular-size PbS species have been stabilized in the open-pore structure of zeolite Y and mordenite via ion exchange with Pb(II) and subsequent treatment with H{sub 2}S at 295 K. Detailed analysis of synchrotron x-ray absorption data of the Pb L{sub III}-edge shows that intrazeolite PbO{sub 2}(O{sub z} = zeolite oxygen) species in zeolite Y react with H{sub 2}S to form monomolecular S{sub 2}Pb(I{sub z}){sub 3} species that are still anchored to the zeolite framework. The intrazeolite PbS phase appears to be more ordered at high loading levels of lead in zeolite Y than at low loading levels. The coordination of Pb(II) and the structure of PbS in the mordenite host is less ordered but basically very similar to that of the monomolecular species in Y. Optical absorption data for these samples agree very well with the structural EXAFS results. Larger PbS clusters have been stabilized in 85% ethylene-15% methacrylic acid copolymer films by a similar preparation procedure. EXAFS data indicate that the reaction forms PbS clusters with several Pb coordination shells and that the conversion of PbS is a function of Pb(II) loading levels. 23 refs., 9 figs., 3 tabs.

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

    SciTech Connect

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

    2015-01-14

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

  12. Time-variability of the fine-structure constant expected from the Oklo constraint and the QSO absorption lines

    NASA Astrophysics Data System (ADS)

    Fujii, Yasunori

    2003-10-01

    The data from the QSO absorption lines indicating a nonzero time-variability of the fine-structure constant has been re-analyzed on the basis of a ``damped-oscillator'' fit, as motivated by the same type of behavior of a scalar field, dilaton, which mimics a cosmological constant to understand the accelerating universe. We find nearly as good fit to the latest data as the simple weighted mean. In this way, we offer a way to fit the more stringent result from the Oklo phenomenon, as well.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  14. Investigation of protein conformation and interactions with salts via X-ray absorption spectroscopy

    PubMed Central

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

    2010-01-01

    Nitrogen K-edge spectra of aqueous triglycine were measured using liquid microjets, and the effects of Hofmeister-active salts on the spectra were observed. Spectra simulated using density functional theory, sampled from room temperature classical molecular dynamics trajectories, capture all major features in the measured spectra. The spectrum of triglycine in water is quite similar to that in the presence of chaotropic sodium bromide (and other halides), which raises the solubility of proteins. However, a new feature is found when kosmotropic Na2SO3, which lowers solubility, is present; this feature results from excitations of the nitrogen atom in the terminal amino group of triglycine. Both direct interactions between this salt and the protonated amino terminus, as well as corresponding changes in the conformational dynamics of the system, contribute to this new feature. These molecular measurements support a different mechanism for the Hofmeister effect than has previously been suggested based on thermodynamic measurements. It is also shown that near edge X-ray absorption fine structure (NEXAFS) is sensitive to strong direct interaction between certain salts and charged peptides. However, by investigating the sensitivity of NEXAFS to the extreme structural differences between model β-sheets and α-helices, we conclude that this technique is relatively insensitive to secondary structure of peptides and proteins. PMID:20660784

  15. Optical absorption, photoluminescence and structural analysis of CdS quantum dots in weak confinement

    NASA Astrophysics Data System (ADS)

    Mishra, Rakesh K.; Vedeshwar, A. G.; Tandon, R. P.

    2014-02-01

    The diffusion-controlled growth of CdS quantum dots (QDs) dispersed in a silicate glass matrix was investigated. It was found that the size of CdS QDs can be controlled by either heat treatment at various temperatures for a fixed duration or varying times at a constant temperature. Pastel yellow colored glass samples were obtained due to the presence of CdS petite crystals. X-ray diffraction (XRD) was used for determining the average dot size which varied from 3.8 to 30 nm. The typical quantum confinement effect was clearly observed from the blue shift measured in the optical absorption edge with decreasing dot size in the absorption spectroscopy. The band gap of CdS QDs ranges from 2.41 to 2.82 eV. Measured photoluminescence (PL) at an excitation wavelength of 350 nm showed the red shift of emission wavelength with increasing thermal treatment time and temperature in agreement with the increasing dot sizes. The half-width of PL spectra seems to indicate qualitatively the size distribution of dots and is consistent with the treatment parameters.

  16. Structure, Optical Absorption, and Performance of Organic Solar Cells Improved by Gold Nanoparticles in Buffer Layers.

    PubMed

    Yang, Yingguo; Feng, Shanglei; Li, Meng; Wu, Zhongwei; Fang, Xiao; Wang, Fei; Geng, Dongping; Yang, Tieying; Li, Xiaolong; Sun, Baoquan; Gao, Xingyu

    2015-11-11

    11-Mercaptoundecanoic acid (MUA)-stabilized gold nanoparticles (AuNPs) embedded in copper phthalocyanine (CuPc) were used as a buffer layer between a poly(3-hexyl-thiophene) (P3HT)/[6,6]-phenyl C61-butyric acid methyl ester (PCBM) bulk heterojunction and anodic indium-tin oxide (ITO) substrate. As systematic synchrotron-based grazing incidence X-ray diffraction (GIXRD) experiments demonstrated that the AuNPs present in the buffer layer can improve the microstructure of the active layer with a better lamella packing of P3HT from the surface to the interior, UV-visible absorption spectrum measurements revealed enhanced optical absorption due to the localized surface plasma resonance (LSPR) generated by the AuNPs. The device of ITO/poly(3,4-ethylenedioxythiophene):polystyrenesulfonate/CuPc:MUA-stabilized AuNPs/P3HT:PCBM/LiF/Al was found with over 24% enhancement of power conversion efficiency (PCE) in comparison with reference devices without AuNPs. This remarkable improvement in PCE should be partially attributed to LSPR generated by the AuNPs and partially to improved crystallization as well as preferred orientation order of P3HT due to the presence of the AuNPs, which would promote more applications of metal NPs in the organic photovoltaic devices and other organic multilayer devices. PMID:26477556

  17. Structural properties of fluorozirconate-based glass ceramics doped with multivalent europium

    SciTech Connect

    PaBlick, C.; Müller, O.; Lützenkirchen-Hecht, D.; Frahm, R.; Johnson, J.A.; Schweizer, S.

    2012-10-10

    The structure/property relationships of fluorochlorozirconate glass ceramics as a function of divalent and trivalent europium (Eu) co-doping and thermal processing have been investigated; the influence of doping ratio on the formation of barium chloride (BaCl2) nanocrystals therein was elucidated. X-ray absorption near-edge structure spectroscopy shows that the post-thermal annealing changes the Eu valence of the as-poured glass slightly, but during the melting process Eu3+ is more strongly reduced to Eu2+, in particular, when doped as a chloride instead of fluoride compound. The Eu2+-to-Eu3+ doping ratio also plays a significant role in chemical equilibrium in the melt. X-ray diffraction measurements indicate that a higher Eu2+ fraction leads to a BaCl2 phase transition from hexagonal to orthorhombic structure at a lower temperature.

  18. Electronic structure and room temperature ferromagnetism of C doped TiO2

    NASA Astrophysics Data System (ADS)

    Ablat, Abduleziz; Wu, Rong; Mamat, Mamatrishat; Ghupur, Yasin; Aimidula, Aimierding; Bake, Muhammad Ali; Gholam, Turghunjan; Wang, Jiaou; Qian, Haijie; Wu, Rui; Ibrahim, Kurash

    2016-10-01

    C-doped TiO2 nanoparticles were successfully synthesized using a simple hydrothermal synthesis method. After this preparation, a portion of the samples were annealed separately in air on the one hand, and in argon on the other, and another portion remained untreated. The results of X-ray diffraction show that the untreated samples primarily display anatase and rutile structures. However, after annealing, the samples displayed the rutile structure only. The Ti K-edge and L-edge Near Edge X-ray Absorption Fine Structure analyses clearly show that C atoms were successfully incorporated into the TiO2 host lattice. All doped samples exhibit ferromagnetism at room temperature. The saturation magnetization (Ms) and coercive fields (Hc) tend to decrease after the samples are annealed in argon and in air. The maximum Ms of the untreated samples was approximately 0.038 emu/g.

  19. X-ray studies on optical and structural properties of ZnO nanostructured thin films

    NASA Astrophysics Data System (ADS)

    Larcheri, S.; Armellini, C.; Rocca, F.; Kuzmin, A.; Kalendarev, R.; Dalba, G.; Graziola, R.; Purans, J.; Pailharey, D.; Jandard, F.

    2006-01-01

    X-ray absorption near-edge fine structure (XANES) studies have been carried out on nanostructured ZnO thin films prepared by atmospheric pressure chemical vapour deposition (APCVD). Films have been characterized by X-ray diffraction (XRD) and optical luminescence spectroscopy exciting with laser light (PL) or X-ray (XEOL). According to XRD measurements, all the APCVD samples reveal a highly (002) oriented crystalline structure. The samples have different thickness (less than 1 μm) and show significant shifts of the PL and XEOL bands in the visible region. Zn K-edge XANES spectra were recorded using synchrotron radiation at BM08 of ESRF (France), by detecting photoluminescence yield (PLY) and X-ray fluorescence yield (FLY). The differences between the PLY- and FLY-XANES confirm the possibility of studying the local environment in the luminescence centres and to correlate the structural and optical properties of ZnO nanostructured samples.

  20. Structural properties of fluorozirconate-based glass ceramics doped with multivalent europium

    SciTech Connect

    Passlick, C.; Mueller, O.; Luetzenkirchen-Hecht, D.; Frahm, R.; Johnson, J. A.; Schweizer, S.

    2011-12-01

    The structure/property relationships of fluorochlorozirconate glass ceramics as a function of divalent and trivalent europium (Eu) co-doping and thermal processing have been investigated; the influence of doping ratio on the formation of barium chloride (BaCl{sub 2}) nanocrystals therein was elucidated. X-ray absorption near-edge structure spectroscopy shows that the post-thermal annealing changes the Eu valence of the as-poured glass slightly, but during the melting process Eu{sup 3+} is more strongly reduced to Eu{sup 2+}, in particular, when doped as a chloride instead of fluoride compound. The Eu{sup 2+}-to-Eu{sup 3+} doping ratio also plays a significant role in chemical equilibrium in the melt. X-ray diffraction measurements indicate that a higher Eu{sup 2+} fraction leads to a BaCl{sub 2} phase transition from hexagonal to orthorhombic structure at a lower temperature.

  1. 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

  2. Genesis of a Cerium Oxide-Supported Gold Catalyst for CO Oxidation: Transformation of Mononuclear Gold Complexes into Clusters as Characterized by X-Ray Absorption Spectroscopy

    SciTech Connect

    Aguilar-Guerrero, V.; Lobo-Lapidus, R; Gates, B

    2009-01-01

    CeO{sub 2}-supported mononuclear gold species synthesized from Au(CH{sub 3}){sub 2}(acac) catalyzed CO oxidation at 353 K, with a turnover frequency of 6.5 x 10{sup -3} molecules of CO (Au atom s){sup -1} at CO and O{sub 2} partial pressures of 1.0 and 0.5 kPa, respectively. As the catalyst functioned in a flow reactor, the activity increased markedly so that within about 10 h the conversion of CO had increased from about 1% to almost 100%. Activated catalyst samples were characterized by X-ray absorption spectroscopy and found to incorporate clusters of gold, which increased in size, undergoing reduction, with increasing time of operation. The X-ray absorption near-edge structure spectrum of the catalyst used for the longest period was indistinguishable from that characterizing gold foil. Extended X-ray absorption fine structure data characterizing the catalyst after the longest period of operation indicated the presence of clusters of approximately 30 Au atoms each, on average. The evidence that the catalytic activity increased as the clusters grew is contrasted with earlier reports pointing to increasing activity of supported gold clusters as they were made smallerin a cluster size range largely exceeding ours.

  3. SiO2/bi-layer GZO/Ag structures for near-infrared broadband wide-angle perfect absorption

    NASA Astrophysics Data System (ADS)

    Zhu, Chaoting; Li, Jia; Yang, Ye; Huang, Jinhua; Lu, Yuehui; Zhao, Xunna; Tan, Ruiqin; Dai, Ning; Song, Weijie

    2016-10-01

    In this work, near-infrared (NIR) perfect absorbers with a silicon dioxide (SiO2)/gallium-doped zinc oxide (GZO)/silver (Ag) multi-layer structure were designed and experimentally demonstrated. The results show that a broadband perfect absorption (PA) from 1.24 µm to 1.49 µm was achieved by adopting bi-layer GZO thin films with different carrier concentrations. This absorption remained higher than 97% for incident angles up to 60°. The perfect NIR absorber reported here has a simple structure as well as broadband and wide-angle absorption features, which is promising for practical applications.

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

    PubMed

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

    2016-05-01

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

  5. Tailoring the crystal structure of TiO{sub 2} thin films from the anatase to rutile phase

    SciTech Connect

    Kotake, Haruka; Jia, Junjun; Nakamura, Shin-ichi; Shigesato, Yuzo; Okajima, Toshihiro

    2015-07-15

    TiO{sub 2} films with various Sn concentrations were deposited on quartz substrates using rf reactive magnetron sputtering. The crystal structure was investigated by using x-ray diffraction, Raman spectroscopy, and transmission electron microscopy, and the chemical states of Ti and Sn were analyzed by x-ray absorption near edge structure (XANES) spectroscopy. Without Sn doping, TiO{sub 2} films change the crystal structure from rutile to anatase as the total gas pressure increases in the sputtering deposition. On the other hand, Sn doping induces the transformation of TiO{sub 2} crystalline structure from anatase to rutile phase, where the XANES spectra implied that Sn substitutes into Ti site of rutile TiO{sub 2}. Atomic force microscope analyses revealed that the Sn-doped TiO{sub 2} films exhibited a flat surface with the roughness of approximately 2 nm.

  6. Local structure studies of Fe2TeO6 using x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Singh, Harishchandra; Yadav, A. K.

    2016-05-01

    In the present study, we have performed EXAFS measurements on powder samples of Fe2TeO6 (FTO) to probe the local structure surrounding at the Fe site. The structural parameters (atomic coordination and lattice parameters) of FTO used for simulation of theoretical EXAFS spectra of the samples have been obtained from Rietveld refined structure on synchrotron X-ray Diffraction (SXRD) data. Quite similar and satisfactory structural parameters have been obtained from both the study, indicating goodness of synchrotron structural analysis over EXAFS analysis. SXRD and EXAFS results shows absence of any secondary phase proves current synthesis superior over reported techniques.

  7. Optical absorption edge in α-Fe2O3: The exciton-magnon structure

    NASA Astrophysics Data System (ADS)

    Galuza, A. I.; Beznosov, A. B.; Eremenko, V. V.

    1998-10-01

    Transmission spectra of synthetic and natural hematite (α-Fe2O3) crystals are measured at temperatures 10, 25, and 300 K in the wavelength range 500-1100 nm, and the absorption spectra are computed. Pure exciton and exciton-magnon d-d transition bands are revealed, the corresponding wavelengths at 10 K being λ0=1020 nm and λ1=965 nm respectively. The half-widths and oscillator forces are g0=84 cm-1, f0=4×10-9, g1=60 cm-1, f1=1.4×10-7 for 10 K, g0=85 cm-1, f0=5×10-9, g1=110 cm-1, f1=2.1×10-7 for 25 K. The mechanisms of band formation for weakly allowed d-d transitions in hematite are analyzed.

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

    NASA Astrophysics Data System (ADS)

    Corrales, Lia; Garcia, Javier; Wilms, Joern; Baganoff, Frederick K.

    2016-04-01

    In high resolution X-ray spectroscopy, dust scattering significantly enhances the total extinction optical depth and alters the shape of photoelectric absorption edges. This effect is modulated by the dust grain size distribution, spatial location along the line of sight, and the imaging resolution of the X-ray telescope. We focus in particular on the Fe L-edge at 0.7 keV, fitting a template for the total extinction to the high resolution spectrum of three X-ray binaries from the Chandra archive: GX 9+9, XTE J1817-330, and Cyg X-1. In cases where dust is intrinsic to the source, a covering factor based on the angular extent of the dusty material must be applied to the extinction curve, regardless of imaging resolution. We discuss the various astrophysical cases in which scattering effects need to be taken into account.

  9. X-ray absorption fine structure study of aging behavior of oxidized copper in CdTe films

    SciTech Connect

    Liu, Xiangxin; Compaan, A.D.; Terry, J.

    2005-10-19

    We have used the MR-CAT beamline of the Advanced Photon Source at Argonne National Laboratory to study the fine structure in the Cu K-edge X-ray absorption in 2 {micro}m thick polycrystalline films of CdTe on fused silica. 4 nm of evaporated Cu is diffused either with or without prior vapor CdCl{sub 2} treatments in dry air. The phase-uncorrected radial distribution function inferred from the absorption fine structure indicates predominantly Cu{sub 2}Te when Cu is diffused into the as-deposited CdTe film but indicates a Cu{sub 2}O environment when Cu is diffused after the vapor CdCl{sub 2} treatment. We believe most of the diffused Cu decorates grain boundaries as oxides, consistent with the low doping densities typically observed in CdTe solar cells. This Cu{sub 2}O likely plays a role in grain-boundary passivation. We also found that the chemical environment around Cu atoms in both CdTe and real cells can change with light soaking. This instability of Cu{sub 2}O in sputtered CdTe could contribute to cell degradation.

  10. Carrier effects on the excitonic absorption in GaAs quantum-well structures: Phase-space filling

    SciTech Connect

    Huang, D.; Chyi, J.; Morkoc, H. )

    1990-09-15

    The carrier effects on the excitonic absorption in GaAs quantum-well structures have been investigated both theoretically and experimentally. A two-dimensional model was used to calculate the oscillator strength and binding energy of excitons associated with filled subbands, with phase-space filling being taken into account. The calculation gives explicitly the oscillator strength of excitons as a function of two-dimensional carrier density. The results are compared with measured absorption data from a series of {ital p}-type modulation-doped GaAs/Al{sub {ital x}}Ga{sub 1{minus}{ital x}}As multiple-quantum-well structures, and quantitative agreement is obtained. The calculation shows that the effect of phase-space filling on the binding energy of a bound state can be described by an effective dielectric constant as a function of carrier density. It predicts the decrease of exciton binding energy with carrier density due to phase-space filling, which has been experimentally observed.

  11. 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}.

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

    SciTech Connect

    Klymenko, M. V.; Shulika, O. V.; Sukhoivanov, I. A.

    2014-05-15

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

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

    SciTech Connect

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

    2010-05-02

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

  14. Atomic Resolution Mapping of the Excited-State Electronic Structure of Cu2O with Time-Resolved X-Ray Absorption Spectroscopy

    SciTech Connect

    Hillyard, Patrick B.; Kuchibhatla, Satyanarayana V N T; Glover, T. E.; Hertlein, M. P.; Huse, N.; Nachimuthu, Ponnusamy; Saraf, Laxmikant V.; Thevuthasan, Suntharampillai; Gaffney, Kelly J.

    2009-09-29

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

  15. Long- and Short-Range Structure of Ferrimagnetic Iron-Chromium Maghemites.

    PubMed

    García-Guaderrama, Marco; Montero-Cabrera, María E; Morán, Emilio; Alario-Franco, Miguel A; Fuentes-Cobas, Luis E; Macías-Ríos, Edgar; Esparza-Ponce, Hilda E; Fuentes-Montero, María E

    2015-12-01

    Maghemite-like materials containing Fe(3+) and Cr(3+) in comparable amounts have been prepared by solution-combustion synthesis. The conditions of synthesis and the magnetic properties are described. These materials are ferrimagnetic and are much more stable than pure iron maghemite since their maghemite-hematite transformation takes place at about ∼ 700 °C instead of ∼ 300 °C, as usually reported. These materials were studied by synchrotron radiation X-ray diffraction (XRD) and by X-ray absorption fine structure (XAFS) of the K-absorption edge of two elements. High-resolution XRD patterns were processed by means of the Rietveld method. Thus, maghemites were studied by XAFS in both Fe and Cr K-edges to clarify the short-range structure of the investigated systems. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure transitions were performed. The extended X-ray absorption fine structure (EXAFS) spectra were fitted considering the facts that the central atom of Fe is able to occupy octahedral and tetrahedral sites, each with a weight adjustment, while Cr occupies only octahedral sites. Interatomic distances were determined for x = 1, by fitting simultaneously both Fe and Cr K-edges average EXAFS spectra. The results showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO3).

  16. Infrared absorption band and vibronic structure of the nitrogen-vacancy center in diamond

    NASA Astrophysics Data System (ADS)

    Kehayias, P.; Doherty, M. W.; English, D.; Fischer, R.; Jarmola, A.; Jensen, K.; Leefer, N.; Hemmer, P.; Manson, N. B.; Budker, D.

    2013-10-01

    Negatively charged nitrogen-vacancy (NV-) color centers in diamond have generated much interest for use in quantum technology. Despite the progress made in developing their applications, many questions about the basic properties of NV- centers remain unresolved. Understanding these properties can validate theoretical models of NV-, improve their use in applications, and support their development into competitive quantum devices. In particular, knowledge of the phonon modes of the 1A1 electronic state is key for understanding the optical pumping process. Using pump-probe spectroscopy, we measured the phonon sideband of the 1E→1A1 electronic transition in the NV- center. From this we calculated the 1E→1A1 one-phonon absorption spectrum and found it to differ from that of the 3E→3A2 transition, a result which is not anticipated by previous group-theoretical models of the NV- electronic states. We identified a high-energy 169-meV localized phonon mode of the 1A1 level.

  17. Electronic Structure of Manganites Determined by Spin-Polarized X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Qian, Qing; Tyson, Trevor; Savrassov, S.; Kao, C.-C.; Croft, M.

    2003-03-01

    A systematic study of spin dependent Mn K-edge x-ray absorption spectra was performed on La_1-xCa_xMnO3 and other Mn oxide systems. A model was developed to predict the temperature dependent changes in the local magnetic ordering based on changes in spin-polarized Mn K-Edge measurements. With this model, one can ascertain the change of local ordering that occurs on transiting the magnetic ordering temperature. Parallel LDA and LDA+U computations are used to label the symmetries of the unoccupied bands, determine the degree of electron correlation and to provide a direct comparison with the band ordering predicted by the temperature dependent spin-polarized measurements. The spin magnetic moment and ordering of the t_2g and eg states are also determined. We find that the occupied t_2g orbitals are always ordered with lobes near 45° to the local Mn-O directions. The Mn K-Edge main line splitting is discussed in terms of the effective spin-polarized charge density. Comparison with bandstructure computations are made. The oxygen hole contribution to the net magnetic moment is seen to be important. We survey the spin-polarized XANES spectra of a large group of manganese oxides showing the general trends in the main line spin splitting as a function of valence. This work is supported by NSF Career Grant DMR-9733862 and DMR-0216858.

  18. Vibration absorption in a building like structure by means of piezoelectric patches and positive acceleration feedback

    NASA Astrophysics Data System (ADS)

    Rios-Gutierrez, Max A.; Silva-Navarro, Gerardo

    2010-04-01

    This paper is about mechanical vibration suppression in a three story building like structure. The experimental platform is a laboratory prototype made of aluminum alloy with bolted joints and an elctromagnetic shaker used as a disturbance source. This prototype can be used as a representation of a civil structure as well as an industrial machinery element. This structure is modeled and validated by the application of finite element methods and experimental modal analysis. The system response is controlled by a piezoelectric actuator, properly located on the structure, and with the synthesis of a feedback control law based on the well-known positive acceleration feedback control scheme. Some numerical simulations and experiments results are performed to illustrate the overall system performance in presence of several types of excitation.

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

    SciTech Connect

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

    2008-06-15

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

  20. Extended X-Ray Absorption Fine Structure Measurements of Quasi-Isentropically Compressed Vanadium Targets on the OMEGA Laser

    SciTech Connect

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

    2008-07-21

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

  1. Atomic form factors and photoelectric absorption cross-sections near absorption edges in the soft X-ray region

    NASA Astrophysics Data System (ADS)

    Chantler, C. T.

    2003-01-01

    Reliable knowledge of the complex X-ray form factor [Re(f) and Im(f)] and the photoelectric attenuation coefficient (σPE) is required for crystallography, medical diagnosis, radiation safety and XAFS studies. Key discrepancies in earlier theoretical work are due to the smoothing of edge structure, the use of non-relativistic wave functions, and the lack of appropriate convergence of wave functions. These discrepancies lead to significant corrections for most comprehensive (i.e. all-Z) tabulations. This work has led to a major comprehensive database tabulation [Chantler, C. T. (2000). J. Phys. Chem. Ref. Data, 29, 597-1048] which serves as a sequel and companion to earlier relativistic Dirac-Fock computations [Chantler, C. T. (1995). J. Phys. Chem. Ref. Data, 24, 71-643]. The paper finds that earlier work needs improvement in the near-edge region for soft X-ray energies, and derives new theoretical results of substantially higher accuracy in near-edge soft X-ray regions. Fine grids near edges are tabulated demonstrating the current comparison with alternate theory and with available experimental data. The best experimental data and the observed experimental structure as a function of energy are strong indicators of the validity of the current approach. New developments in experimental measurement hold great promise in making critical comparisons with theory in the near future. This work forms the latest component of the FFAST NIST database [http://physics.nist.gov/PhysRefData/FFast02/Text/cover.html].

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  3. Electronic structure of nitinol surfaces oxidized by low-energy ion bombardment

    SciTech Connect

    Petravic, M. Varasanec, M.; Peter, R.; Kavre, I.; Metikos-Hukovic, M.; Yang, Y.-W.

    2014-06-28

    We have studied the electronic structure of nitinol exposed to low-energy oxygen-ion bombardment, using x-ray photoemission spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. XPS spectra reveal a gradual transformation of nitinol surfaces into TiO{sub 2} with increased dose of implanted oxygen. No oxidation of Ni atoms has been detected. NEXAFS spectra around O K-edge and Ti L{sub 2,3}-edge, reflecting the element-specific partial density of empty electronic states, exhibit features, which can be attributed to the creation of molecular orbitals, crystal field splitting, and the absence of long-range order, characteristic of the amorphous TiO{sub 2}. Based on these results, we discuss the oxidation kinetics of nitinol under low-energy oxygen-ion bombardment.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  5. Effects of Organic Molecules with Different Structures and Absorption Bandwidth on Modulating Photoresponse of MoS2 Photodetector.

    PubMed

    Huang, Yanmin; Zheng, Wei; Qiu, Yunfeng; Hu, PingAn

    2016-09-01

    Organic dye molecules possessing modulated optical absorption bandwidth and molecular structures can be utilized as sensitizing species for the enhancement of photodetector performance of semiconductor via photoinduced charge transfer mechanism. MoS2 photodetector were modified by drop-casting of methyl orange (MO), rhodamine 6G (R6G), and methylene blue (MB) with different molecular structures and extinction coefficients, and enhanced photodetector performance in terms of photocurrent, photoresponsity, photodetectivity, and external quantum efficiency were obtained after modification of MO, R6G, and MB, respectively. Furthermore, dyes showed different modulating abilities for photodetector performance after combination with MoS2, mainly due to the variation of molecular structures and optical absorption bandwidth. Among tested dyes, deposition of MB onto monolayer MoS2 grown by CVD resulted in photocurrent ∼20 times as high as pristine MoS2 due to favorable photoinduced charge transfer of photoexcited electrons from flat MB molecules to the MoS2 layer. Meanwhile, the corresponding photoresponsivity, photodetectivity, and an external quantum efficiency are 9.09 A W(1-), 2.2 × 10(11) Jones, 1729% at 610 nm, respectively. Photoinduced electron-transfer measurements of the pristine MoS2 and dye-modified MoS2 indicated the n-doping effect of dye molecules on the MoS2. Additionally, surface-enhanced Raman measurements also confirmed the direct correlation with charge transfer between organic dyes and MoS2 taking into account the chemically enhanced Raman scattering mechanism. Present work provides a new clue for the manipulation of high-performance of two-dimensional layered semiconductor-based photodetector via the combination of organic dyes. PMID:27530058

  6. Effects of Organic Molecules with Different Structures and Absorption Bandwidth on Modulating Photoresponse of MoS2 Photodetector.

    PubMed

    Huang, Yanmin; Zheng, Wei; Qiu, Yunfeng; Hu, PingAn

    2016-09-01

    Organic dye molecules possessing modulated optical absorption bandwidth and molecular structures can be utilized as sensitizing species for the enhancement of photodetector performance of semiconductor via photoinduced charge transfer mechanism. MoS2 photodetector were modified by drop-casting of methyl orange (MO), rhodamine 6G (R6G), and methylene blue (MB) with different molecular structures and extinction coefficients, and enhanced photodetector performance in terms of photocurrent, photoresponsity, photodetectivity, and external quantum efficiency were obtained after modification of MO, R6G, and MB, respectively. Furthermore, dyes showed different modulating abilities for photodetector performance after combination with MoS2, mainly due to the variation of molecular structures and optical absorption bandwidth. Among tested dyes, deposition of MB onto monolayer MoS2 grown by CVD resulted in photocurrent ∼20 times as high as pristine MoS2 due to favorable photoinduced charge transfer of photoexcited electrons from flat MB molecules to the MoS2 layer. Meanwhile, the corresponding photoresponsivity, photodetectivity, and an external quantum efficiency are 9.09 A W(1-), 2.2 × 10(11) Jones, 1729% at 610 nm, respectively. Photoinduced electron-transfer measurements of the pristine MoS2 and dye-modified MoS2 indicated the n-doping effect of dye molecules on the MoS2. Additionally, surface-enhanced Raman measurements also confirmed the direct correlation with charge transfer between organic dyes and MoS2 taking into account the chemically enhanced Raman scattering mechanism. Present work provides a new clue for the manipulation of high-performance of two-dimensional layered semiconductor-based photodetector via the combination of organic dyes.

  7. Solar cells based on particulate structure of active layer: Investigation of light absorption by an ordered system of spherical submicron silicon particles

    NASA Astrophysics Data System (ADS)

    Miskevich, Alexander A.; Loiko, Valery A.

    2015-12-01

    Enhancement of the performance of photovoltaic cells through increasing light absorption due to optimization of an active layer is considered. The optimization consists in creation of particulate structure of active layer. The ordered monolayers and multilayers of submicron crystalline silicon (c-Si) spherical particles are examined. The quasicrystalline approximation (QCA) and the transfer matrix method (TMM) are used to calculate light absorption in the wavelength range from 0.28 μm to 1.12 μm. The integrated over the terrestial solar spectral irradiance "Global tilt" ASTM G173-03 absorption coefficient is calculated. In the wavelength range of small absorption index of c-Si (0.8-1.12 μm) the integral absorption coefficient of monolayer can be more than 20 times higher than the one of the plane-parallel plate of the equivalent volume of material. In the overall considered range (0.28-1.12 μm) the enhancement factor up to ~1.45 for individual monolayer is observed. Maximum value of the spectral absorption coefficient approaches unity for multilayers consisting of large amount of sparse monolayers of small particles. Multilayers with variable concentration and size of particles in the monolayer sequences are considered. Absorption increasing by such gradient multilayers as compared to the non-gradient ones is illustrated. The considered structures are promising for creation of high efficiency thin-film solar cells.

  8. Local Fine Structural Insight into Mechanism of Electrochemical Passivation of Titanium.

    PubMed

    Wang, Lu; Yu, Hongying; Wang, Ke; Xu, Haisong; Wang, Shaoyang; Sun, Dongbai

    2016-07-20

    Electrochemically formed passive film on titanium in 1.0 M H2SO4 solution and its thickness, composition, chemical state, and local fine structure are examined by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure. AES analysis reveals that the thickness and composition of oxide film are proportional to the reciprocal of current density in potentiodynamic polarization. XPS depth profiles of the chemical states of titanium exhibit the coexistence of various valences cations in the surface. Quantitative X-ray absorption near edge structure analysis of the local electronic structure of the topmost surface (∼5.0 nm) shows that the ratio of [TiO2]/[Ti2O3] is consistent with that of passivation/dissolution of electrochemical activity. Theoretical calculation and analysis of extended X-ray absorption fine structure spectra at Ti K-edge indicate that both the structures of passivation and dissolution are distorted caused by the appearance of two different sites of Ti-O and Ti-Ti. And the bound water in the topmost surface plays a vital role in structural disorder confirmed by XPS. Overall, the increase of average Ti-O coordination causes the electrochemical passivation, and the dissolution is due to the decrease of average Ti-Ti coordination. The structural variations of passivation in coordination number and interatomic distance are in good agreement with the prediction of point defect model. PMID:27355902

  9. Nuclear Magnetic Resonance and X-Ray Absorption Spectroscopic Studies of Lithium Insertion in Silver Vanadium Oxide Cathodes

    SciTech Connect

    Leifer,N.; Colon, A.; Martocci, k.; Greenbaum, S.; Alamgir, F.; Reddy, T.; Gleason, N.; Leising, R.; Takeuchi, E.

    2007-01-01

    Structural studies have been carried out on Ag{sub 2}V{sub 4}O{sub 11} (silver vanadium oxide, SVO) and Li{sub x}Ag{sub 2}V{sub 4}O{sub 11}, lithiated SVO with x=0.72, 2.13, and 5.59 using nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy (XAS). Lithium-7 NMR indicates the formation of a solid electrolyte interphase layer on the x=0.72 sample and lithium intercalation into both octahedral and tetrahedral sites in the SVO lattice, and that most but not all of the Ag (I) is reduced prior to initiation of V(V) reduction. Vanadium-51 NMR studies of SVO and lithiated SVO show decreased crystallinity with increased lithiation, as previously reported. Silver XAS studies indicate the formation of metallic silver crystallites in all the lithiated samples. A comparison of X-ray absorption near edge spectroscopy spectra for vanadium in these samples with those of reference compounds shows that some reduction of vanadium (V) occurs in the lithiated SVO with x=0.72 and increases with further lithiation leading to the formation of V(IV) and V(III) species. The results of this study indicate that vanadium(V) reduction occurs in parallel with silver (I) reduction during the initial stages of SVO lithiation, leading ultimately to the formation of vanadium (IV) and (III) species with further lithiation.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

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

    PubMed

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

    2016-02-24

    Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

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

    PubMed Central

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

    2016-01-01

    Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge. PMID:26908198

  13. Structures of Liquid GaSb and InSb Studied with the Extended X-Ray-Absorption Fine-Structure Method

    NASA Astrophysics Data System (ADS)

    Wang, Yuren; Lu, Kunquan; Li, Chenxi

    1997-11-01

    The extended x-ray-absorption fine-structure technique is applied to study the local atomic structures of liquid GaSb and InSb using an improved sample holding method. The partial pair distribution functions and coordination distributions of the two liquids are given by using reverse Monte Carlo simulation. The coordination numbers in liquid GaSb are mostly 5 and 6, in addition to which there are about 15% of 4 coordination and about 10% of 7 coordination. On average, the coordination number is 5.4. The results are similar in liquid InSb. This structural study provides some hints of the metallic behavior and density increase in the liquid.

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

    PubMed Central

    Remko, Milan; Remková, Anna; Broer, Ria

    2016-01-01

    Theoretical chemistry methods have been used to study the molecular properties of antiplatelet agents (ticlopidine, clopidogrel, prasugrel, elinogrel, ticagrelor and cangrelor) and several thiol-containing active metabolites. The geometries and energies of most stable conformers of these drugs have been computed at the Becke3LYP/6-311++G(d,p) level of density functional theory. Computed dissociation constants show that the active metabolites of prodrugs (ticlopidine, clopidogrel and prasugrel) and drugs elinogrel and cangrelor are completely ionized at pH 7.4. Both ticagrelor and its active metabolite are present at pH = 7.4 in neutral undissociated form. The thienopyridine prodrugs ticlopidine, clopidogrel and prasugrel are lipophilic and insoluble in water. Their lipophilicity is very high (about 2.5–3.5 logP values). The polar surface area, with regard to the structurally-heterogeneous character of these antiplatelet drugs, is from very large interval of values of 3–255 Å2. Thienopyridine prodrugs, like ticlopidine, clopidogrel and prasugrel, with the lowest polar surface area (PSA) values, exhibit the largest absorption. A high value of polar surface area (PSA) of cangrelor (255 Å2) results in substantial worsening of the absorption in comparison with thienopyridine drugs. PMID:27007371

  15. Occupied and unoccupied electronic structures of an L-cysteine film studied by core-absorption and resonant photoelectron spectroscopies

    NASA Astrophysics Data System (ADS)

    Kamada, M.; Hideshima, T.; Azuma, J.; Yamamoto, I.; Imamura, M.; Takahashi, K.

    2016-04-01

    Unoccupied and occupied electronic structures of an L-cysteine film have been studied by absorption and resonant photoelectron spectroscopies. Core absorptions at S-L, C-K, N-K, and O-K levels indicate that the lower unoccupied states are predominantly composed of oxygen-2p, carbon-2p, and sulfur-4s+3d orbitals, while higher unoccupied states may be attributed dominantly to nitrogen-np (n ≥ 3), oxygen-np (n ≥ 3), and sulfur-ns+md (n ≥ 4, m ≥ 3) orbitals. Resonant photoelectron spectra at S-L23 and O-K levels indicate that the highest occupied state is originated from sulfur-3sp orbitals, while oxygen-2sp orbitals contribute to the deeper valence states. The delocalization lifetimes of the oxygen-1s and sulfur-2p excited states are estimated from a core-hole clock method to be about 9 ± 1 and 125 ± 25 fs, respectively.

  16. Synthesis and water absorption transport mechanism of a pH-sensitive polymer network structured on vinyl-functionalized pectin.

    PubMed

    Guilherme, Marcos R; Moia, Thais A; Reis, Adriano V; Paulino, Alexandre T; Rubira, Adley F; Mattoso, Luiz H C; Muniz, Edvani C; Tambourgi, Elias B

    2009-01-12

    Polysaccharide-structured copolymer hydrogel having excellent pH-sensitivity was developed from N,N-dimethylacrylamide (DMAc) and vinyl-functionalized Pectin (Pec). The Pec was vinyl-functionalized by way of chemical reaction with glycidyl metacrylate (GMA) in water under acidic and thermal stimuli. 13C NMR, 1H NMR, and FT-IR spectra revealed that the vinyl groups coming from the GMA were attached onto backbone of the polysaccharide. The hydrogels were obtained by polymerization of the Pec-vinyl with the DMAc. 13C-CP/MAS NMR and FTIR spectra confirmed that the gelling process occurred by way of the vinyl groups attached on Pec-vinyl backbone. The values of apparent swelling rate constant (k) decreased appreciably for pH greater than 6, demonstrating the swelling process of the hydrogel becomes slower at more alkaline conditions. There was an increase of diffusional exponent (n) with increasing pH of the surrounding liquid. This means the water absorption profile becomes more dependent on the polymer relaxation in basified swelling media. In this condition, a longer water absorption half-time (t1/2) was verified, suggesting the polymer relaxation mechanism of the hydrogel would have a considerable effect on the t1/2.

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

    PubMed Central

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

    2016-01-01

    Understanding Warm Dense Matter (WDM), the state of planetary interiors, is a new frontier in scientific research. There exists very little experimental data probing WDM states at the atomic level to test current models and those performed up to now are limited in quality. Here, we report a proof-of-principle experiment that makes microscopic investigations of materials under dynamic compression easily accessible to users and with data quality close to that achievable at ambient. Using a single 100 ps synchrotron x-ray pulse, we have measured, by K-edge absorption spectroscopy, ns-lived equilibrium states of WDM Fe. Structural and electronic changes in Fe are clearly observed for the first time at such extreme conditions. The amplitude of the EXAFS oscillations persists up to 500 GPa and 17000 K, suggesting an enduring local order. Moreover, a discrepancy exists with respect to theoretical calculations in the value of the energy shift of the absorption onset and so this comparison should help to refine the approximations used in models. PMID:27246145

  18. Electronic structure of d{sup 0} vanadates obtained by x-ray absorption and emission spectroscopies

    SciTech Connect

    Herrera, G.; Jimenez-Mier, J.; Chavira, E.; Moewes, A.; Wilks, R.

    2009-01-29

    We present experimental results for x-ray absorption at the L{sub 2,3}-edge of vanadium in V{sub 2}O{sub 5}, YVO{sub 4} and LaVO{sub 4} compounds and at the M{sub 4,5}-edge of lanthanum in LaVO{sub 4} compound. The data are interpreted in terms of the multiplet structure of the transition metal ion V{sup 5+} (d{sup 0}) and rare earth ion La{sup 3+} (d{sup 10}). The data are compared with calculations in the free-ion approximation for La and including the effects of the D{sub 4h} ligand field and charge transfer for V. These calculations allow a direct interpretation of the absorption spectra. Good overall agreement between experiment and theory is found. We also show resonant x-ray emission (XES) data for these compounds obtained at the top of the L{sub 2} excitation.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  20. Optimized absorption of solar radiations in nano-structured thin films of crystalline silicon via a genetic algorithm

    NASA Astrophysics Data System (ADS)

    Mayer, Alexandre; Muller, Jérôme; Herman, Aline; Deparis, Olivier

    2015-08-01

    We developed a genetic algorithm to achieve optimal absorption of solar radiation in nano-structured thin films of crystalline silicon (c-Si) for applications in photovoltaics. The device includes on the front side a periodic array of inverted pyramids, with conformal passivation layer (a-Si:H or AlOx) and anti-reflection coating (SiNx). The device also includes on the back side a passivation layer (a-Si:H) and a flat reflector (ITO and Ag). The geometrical parameters of the inverted pyramids as well as the thickness of the different layers must be adjusted in order to maximize the absorption of solar radiations in the c-Si. The genetic algorithm enables the determination of optimal solutions that lead to high performances by evaluating only a reduced number of parameter combinations. The results achieved by the genetic algorithm for a 40μm thick c-Si lead to short-circuit currents of 37 mA/cm2 when a-Si:H is used for the front-side passivation and 39.1 mA/cm2 when transparent AlOx is used instead.