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Sample records for x-ray absorption spectroscopy

  1. SMB, X-ray Absorption Spectroscopy

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Absorption Spectroscopy X-ray Absorption Spectroscopy X-ray absorption spectroscopy (XAS) is a well-established technique for simultaneous local geometric and electronic structure...

  2. X-ray transient absorption and picosecond IR spectroscopy of...

    Office of Scientific and Technical Information (OSTI)

    X-ray transient absorption and picosecond IR spectroscopy of fulvalene(tetracarbonyl)diruthenium on photoexcitation Citation Details In-Document Search Title: X-ray transient ...

  3. Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free...

    Office of Scientific and Technical Information (OSTI)

    Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser: Application to Spin Crossover Dynamics Citation Details In-Document Search Title: Femtosecond X-ray...

  4. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; Cromer, C. L.; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-03-02

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also presentmore » data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.« less

  5. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    SciTech Connect (OSTI)

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; Cromer, C. L.; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-03-02

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

  6. X-ray absorption spectroscopy study of Gd[superscript 3+]-loaded...

    Office of Scientific and Technical Information (OSTI)

    Journal Article: X-ray absorption spectroscopy study of Gdsuperscript 3+-loaded ultra-short carbon nanotubes Citation Details In-Document Search Title: X-ray absorption ...

  7. X-ray absorption fine-structure spectroscopy (Book) | SciTech...

    Office of Scientific and Technical Information (OSTI)

    X-ray absorption fine-structure spectroscopy Citation Details In-Document Search Title: X-ray absorption fine-structure spectroscopy Authors: Newville, M. 1 + Show Author ...

  8. Femtosecond x-ray absorption spectroscopy with hard x-ray free electron laser

    SciTech Connect (OSTI)

    Katayama, Tetsuo; Togashi, Tadashi; Tono, Kensuke; Kameshima, Takashi; Inubushi, Yuichi; Sato, Takahiro; Hatsui, Takaki; Yabashi, Makina; Obara, Yuki; Misawa, Kazuhiko; Bhattacharya, Atanu; Kurahashi, Naoya; Ogi, Yoshihiro; Suzuki, Toshinori; Molecular Reaction Dynamics Research Team, RIKEN Center for Advanced Photonics, 2-1 Hirosawa, Wako 351-0198

    2013-09-23

    We have developed a method of dispersive x-ray absorption spectroscopy with a hard x-ray free electron laser (XFEL), generated by a self-amplified spontaneous emission (SASE) mechanism. A transmission grating was utilized for splitting SASE-XFEL light, which has a relatively large bandwidth (ΔE/E ∼ 5 × 10{sup −3}), into several branches. Two primary split beams were introduced into a dispersive spectrometer for measuring signal and reference spectra simultaneously. After normalization, we obtained a Zn K-edge absorption spectrum with a photon-energy range of 210 eV, which is in excellent agreement with that measured by a conventional wavelength-scanning method. From the analysis of the difference spectra, the noise ratio was evaluated to be ∼3 × 10{sup −3}, which is sufficiently small to trace minute changes in transient spectra induced by an ultrafast optical laser. This scheme enables us to perform single-shot, high-accuracy x-ray absorption spectroscopy with femtosecond time resolution.

  9. Gas cell for in situ soft X-ray transmission-absorption spectroscopy...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    cell for in situ soft X-ray transmission-absorption spectroscopy of materials Previous ... Abstract: A simple gas cell design, constructed primarily from commercially available ...

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

    SciTech Connect (OSTI)

    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.

  11. Low-dimensional systems investigated by x-ray absorption spectroscopy...

    Office of Scientific and Technical Information (OSTI)

    Title: Low-dimensional systems investigated by x-ray absorption spectroscopy: a selection of 2D, 1D and 0D cases Authors: Mino, Lorenzo ; Agostini, Giovanni ; Borfecchia, Elisa ; ...

  12. In Situ Diffuse Reflectance IR Spectroscopy and X-ray Absorption Spectroscopy for Fast Catalytic Processes

    SciTech Connect (OSTI)

    N Marinkovic; Q Wang; A Frenkel

    2011-12-31

    A new instrument for synchronous in situ investigations of catalytic materials by IR and X-ray absorption spectroscopies was designed and built at the X18A beamline of the National Synchrotron Light Source of Brookhaven National Laboratory. It provides analytical tools for solving structural, electronic and kinetic problems in catalysis science by two complementary methods. Among the features attractive for catalysis research are the broad range of catalytically active elements that can be investigated (starting with Ni and beyond), the wide range of reaction conditions (temperatures up to 873 K, various reactive gases) and time scales (starting from tens of seconds). The results of several representative experiments that illustrate the attractive capabilities of the new set-up are discussed.

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

    SciTech Connect (OSTI)

    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.

  14. Note: Sample chamber for in situ x-ray absorption spectroscopy studies of battery materials

    SciTech Connect (OSTI)

    Pelliccione, CJ; Timofeeva, EV; Katsoudas, JP; Segre, CU

    2014-12-01

    In situ x-ray absorption spectroscopy (XAS) provides element-specific characterization of both crystalline and amorphous phases and enables direct correlations between electrochemical performance and structural characteristics of cathode and anode materials. In situ XAS measurements are very demanding to the design of the experimental setup. We have developed a sample chamber that provides electrical connectivity and inert atmosphere for operating electrochemical cells and also accounts for x-ray interactions with the chamber and cell materials. The design of the sample chamber for in situ measurements is presented along with example XAS spectra from anode materials in operating pouch cells at the Zn and Sn K-edges measured in fluorescence and transmission modes, respectively. (C) 2014 AIP Publishing LLC.

  15. X-ray absorption spectroscopy studies of electrochemically deposited thin oxide films.

    SciTech Connect (OSTI)

    Balasubramanian, M.

    1998-06-02

    We have utilized ''in situ'' X-ray Absorption Fine Structure Spectroscopy to investigate the structure and composition of thin oxide films of nickel and iron that have been prepared by electrodeposition on a graphite substrate from aqueous solutions. The films are generally disordered. Structural information has been obtained from the analysis of the data. We also present initial findings on the local structure of heavy metal ions, e.g. Sr and Ce, incorporated into the electrodeposited nickel oxide films. Our results are of importance in a number of technological applications, among them, batteries, fuel cells, electrochromic and ferroelectric materials, corrosion protection, as well as environmental speciation and remediation.

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

    SciTech Connect (OSTI)

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

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O? lattice in an irradiated (60 MW d kg?) MOX sample was performed employing micro-X-ray fluorescence (-XRF) and micro-X-ray absorption fine structure (-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (~0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am? species within an [AmO?]? coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix. - Graphical abstract: Americium LIII XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 ?m300 ?m beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO? matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. The americium redox state as determined from XAS data of irradiated fuel material was Am(III). In the sample, the Am? face an AmO??coordination environment in the (Pu,U)O? matrix. The americium dioxide is reduced by the uranium dioxide matrix.

  17. New Homogeneous Standards by Atomic Layer Deposition for Synchrotron X-ray Fluorescence and Absorption Spectroscopies.

    SciTech Connect (OSTI)

    Butterworth, A.L.; Becker, N.; Gainsforth, Z.; Lanzirotti, A.; Newville, M.; Proslier, T.; Stodolna, J.; Sutton, S.; Tyliszczak, T.; Westphal, A.J.; Zasadzinski, J.

    2012-03-13

    Quantification of synchrotron XRF analyses is typically done through comparisons with measurements on the NIST SRM 1832/1833 thin film standards. Unfortunately, these standards are inhomogeneous on small scales at the tens of percent level. We are synthesizing new homogeneous multilayer standards using the Atomic Layer Deposition technique and characterizing them using multiple analytical methods, including ellipsometry, Rutherford Back Scattering at Evans Analytical, Synchrotron X-ray Fluorescence (SXRF) at Advanced Photon Source (APS) Beamline 13-ID, Synchrotron X-ray Absorption Spectroscopy (XAS) at Advanced Light Source (ALS) Beamlines 11.0.2 and 5.3.2.1 and by electron microscopy techniques. Our motivation for developing much-needed cross-calibration of synchrotron techniques is borne from coordinated analyses of particles captured in the aerogel of the NASA Stardust Interstellar Dust Collector (SIDC). The Stardust Interstellar Dust Preliminary Examination (ISPE) team have characterized three sub-nanogram, {approx}1{micro}m-sized fragments considered as candidates to be the first contemporary interstellar dust ever collected, based on their chemistries and trajectories. The candidates were analyzed in small wedges of aerogel in which they were extracted from the larger collector, using high sensitivity, high spatial resolution >3 keV synchrotron x-ray fluorescence spectroscopy (SXRF) and <2 keV synchrotron x-ray transmission microscopy (STXM) during Stardust ISPE. The ISPE synchrotron techniques have complementary capabilities. Hard X-ray SXRF is sensitive to sub-fg mass of elements Z {ge} 20 (calcium) and has a spatial resolution as low as 90nm. X-ray Diffraction data were collected simultaneously with SXRF data. Soft X-ray STXM at ALS beamline 11.0.2 can detect fg-mass of most elements, including cosmochemically important oxygen, magnesium, aluminum and silicon, which are invisible to SXRF in this application. ALS beamline 11.0.2 has spatial resolution

  18. Millisecond Kinetics of Nanocrystal Cation Exchange UsingMicrofluidic X-ray Absorption Spectroscopy

    SciTech Connect (OSTI)

    Chan, Emory M.; Marcus, Matthew A.; Fakra, Sirine; Elnaggar,Mariam S.; Mathies, Richard A.; Alivisatos, A. Paul

    2007-05-07

    We describe the use of a flow-focusing microfluidic reactorto measure the kinetics of theCdSe-to-Ag2Se nanocrystal cation exchangereaction using micro-X-ray absorption spectroscopy (mu XAS). The smallmicroreactor dimensions facilitate the millisecond mixing of CdSenanocrystal and Ag+ reactant solutions, and the transposition of thereaction time onto spatial coordinates enables the in situ observation ofthe millisecond reaction with mu XAS. XAS spectra show the progression ofCdSe nanocrystals to Ag2Se over the course of 100 ms without the presenceof long-lived intermediates. These results, along with supporting stoppedflow absorption experiments, suggest that this nanocrystal cationexchange reaction is highly efficient and provide insight into how thereaction progresses in individual particles. This experiment illustratesthe value and potential of in situ microfluidic X-ray synchrotrontechniques for detailed studies of the millisecond structuraltransformations of nanoparticles and other solution-phase reactions inwhich diffusive mixing initiates changes in local bond structures oroxidation states.

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

    SciTech Connect (OSTI)

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

    2009-05-26

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

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

    SciTech Connect (OSTI)

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

    2007-11-27

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

  1. Correlated Single-Crystal Electronic Absorption Spectroscopy and X-ray Crystallography at NSLS Beamline X26-C

    SciTech Connect (OSTI)

    A Orville; R Buono; M Cowan; A Heroux; G Shea-McCarthy; D Schneider; J Skinner; M Skinner; D Stoner-Ma; R Sweet

    2011-12-31

    The research philosophy and new capabilities installed at NSLS beamline X26-C to support electronic absorption and Raman spectroscopies coupled with X-ray diffraction are reviewed. This beamline is dedicated full time to multidisciplinary studies with goals that include revealing the relationship between the electronic and atomic structures in macromolecules. The beamline instrumentation has been fully integrated such that optical absorption spectra and X-ray diffraction images are interlaced. Therefore, optical changes induced by X-ray exposure can be correlated with X-ray diffraction data collection. The installation of Raman spectroscopy into the beamline is also briefly reviewed. Data are now routinely generated almost simultaneously from three complementary types of experiments from the same sample. The beamline is available now to the NSLS general user population.

  2. X-ray Absorption Spectroscopy Beamline at the Siam Photon Laboratory

    SciTech Connect (OSTI)

    Klysubun, Wantana; Tarawarakarn, Pongjakr; Sombunchoo, Panidtha; Klinkhieo, Supat; Chaiprapa, Jitrin; Songsiriritthigul, Prayoon

    2007-01-19

    A bending magnet beamline has been constructed and commissioned for x-ray absorption spectroscopy (XAS) at the Siam Photon Laboratory. The photon energy is tunable from 1830 eV to 8000 eV using a Lemmonier-type, fixed-exit double crystal monochromator equipped with InSb(111), Si(111), Ge(220) crystals. Elemental K-edges are then accessible from silicon to iron. A series of low conductance vacuum tubes has been designed and installed between the pumping chambers in the front end to obtain the proper pressure difference between the upstream and the downstream of the front end. Thus lower-energy photons, around K-edges of silicon, phosphorous, and sulfur, can be delivered to the experimental XAS station without being absorbed by a window. In this report, the design of the beamline is described. The commissioning results including the measured photon flux at sample and experimental XAS spectra are presented.

  3. A multi-channel monolithic Ge detector system for fluorescence x-ray absorption spectroscopy

    SciTech Connect (OSTI)

    Bucher, J.J.; Allen, P.G.; Edelstein, N.M.; Shuh, D.K.; Madden, N.W.; Cork, C.; Luke, P.; Pehl, D.; Malone, D.

    1995-03-01

    Construction and performance of a monolithic quad-pixel Ge detector for fluorescence x-ray absorption spectroscopy (XAS) at synchrotron radiation sources are described. The detector semiconductor element has an active surface area of 4.0 cm{sup 2} which is electrically separated into four 1.0 cm{sup 2} pixels, with little interfacial dead volume. Spatial response of the array shows that cross-talk between adjacent pixels is < 10% for 5.9 keV photons that fall within 0.5 mm of the pixel boundaries. The detector electronics system uses pre-amplifiers built at LBNL with commercial Tennelec Model TC 244 amplifiers. Using an {sup 55}Fe test source (MnK{sub {alpha}}, 5.9 keV), energy resolution of better than 200 eV is achieved with a 4 {mu}sec peaking time. At 0.5 {mu}sec peaking time, pulse pileup results in a 75% throughput efficiency for an incoming count rate of 100 kHz. Initial XAS fluoresncece measurements at the beamline 4 wiggler end stations at SSRL show that the detector system has several advantages over commercial x-ray spectrometers for low-concentration counting.

  4. Observing heme doming in myoglobin with femtosecond X-ray absorption spectroscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Levantino, M.; Lemke, H. T.; Schirò, G.; Glownia, M.; Cupane, A.; Cammarata, M.

    2015-07-01

    We report time-resolved X-ray absorption measurements after photolysis of carbonmonoxy myoglobin performed at the LCLS X-ray free electron laser with nearly 100 fs (FWHM) time resolution. Data at the Fe K-edge reveal that the photoinduced structural changes at the heme occur in two steps, with a faster (~70 fs) relaxation preceding a slower (~400 fs) one. We tentatively attribute the first relaxation to a structural rearrangement induced by photolysis involving essentially only the heme chromophore and the second relaxation to a residual Fe motion out of the heme plane that is coupled to the displacement of myoglobin F-helix.

  5. X-ray Absorption Spectroscopy Characterization of a Li/S Cell

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; Feng, Bingmei; Liu, Yi-Sheng; Marcus, Matthew A.; Feng, Jun; Cairns, Elton J.; Guo, Jinghua; Zhu, Junfa

    2016-01-11

    The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br₋) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface duringmore » the charge/discharge processes make the capacity decay. Lastly, a modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.« less

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

    SciTech Connect (OSTI)

    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.

  7. SMB, X-ray Emission Spectroscopy

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    include X-ray Emission Spectroscopy (XES), Resonant Inelastic X-ray Scattering (RIXS), High Energy Resolution Fluorescence Detection (HERFD) and X-ray Raman Spectroscopy (XRS). ...

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

    SciTech Connect (OSTI)

    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.

  9. Voltage-controlled magnetic anisotropy in Fe|MgO tunnel junctions studied by x-ray absorption spectroscopy

    SciTech Connect (OSTI)

    Miwa, Shinji Matsuda, Kensho; Tanaka, Kazuhito; Goto, Minori; Suzuki, Yoshishige; Kotani, Yoshinori; Nakamura, Tetsuya

    2015-10-19

    In this study, voltage-controlled magnetic anisotropy (VCMA) in Fe|MgO tunnel junctions was investigated via the magneto-optical Kerr effect, soft x-ray absorption spectroscopy, and magnetic circular dichroism spectroscopy. The Fe|MgO tunnel junctions showed enhanced perpendicular magnetic anisotropy under external negative voltage, which induced charge depletion at the Fe|MgO interface. Despite the application of voltages of opposite polarity, no trace of chemical reaction such as a redox reaction attributed to O{sup 2−} migration was detected in the x-ray absorption spectra of the Fe. The VCMA reported in the Fe|MgO-based magnetic tunnel junctions must therefore originate from phenomena associated with the purely electric effect, that is, surface electron doping and/or redistribution induced by an external electric field.

  10. Local electronic states of Fe{sub 4}N films revealed by x-ray absorption spectroscopy and x-ray magnetic circular dichroism

    SciTech Connect (OSTI)

    Ito, Keita; Toko, Kaoru; Suemasu, Takashi; Takeda, Yukiharu; Saitoh, Yuji; Oguchi, Tamio; Kimura, Akio

    2015-05-21

    We performed x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) measurements at Fe L{sub 2,3} and N K-edges for Fe{sub 4}N epitaxial films grown by molecular beam epitaxy. In order to clarify the element specific local electronic structure of Fe{sub 4}N, we compared experimentally obtained XAS and XMCD spectra with those simulated by a combination of a first-principles calculation and Fermi's golden rule. We revealed that the shoulders observed at Fe L{sub 2,3}-edges in the XAS and XMCD spectra were due to the electric dipole transition from the Fe 2p core-level to the hybridization state generated by ?* anti-bonding between the orbitals of N 2p at the body-centered site and Fe 3d on the face-centered (II) sites. Thus, the observed shoulders were attributed to the local electronic structure of Fe atoms at II sites. As to the N K-edge, the line shape of the obtained spectra was explained by the dipole transition from the N 1s core-level to the hybridization state formed by ?* and ?* anti-bondings between the Fe 3d and N 2p orbitals. This hybridization plays an important role in featuring the electronic structures and physical properties of Fe{sub 4}N.

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

    SciTech Connect (OSTI)

    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.; Strmer, 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.

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

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    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

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

    SciTech Connect (OSTI)

    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.

  14. Theoretical study of Raman chirped adiabatic passage by X-ray absorption spectroscopy: Highly excited electronic states and rotational effects

    SciTech Connect (OSTI)

    Engin, Selma; Sisourat, Nicolas Selles, Patricia; Taïeb, Richard; Carniato, Stéphane

    2014-06-21

    Raman Chirped Adiabatic Passage (RCAP) is an efficient method to climb the vibrational ladder of molecules. It was shown on the example of fixed-in-space HCl molecule that selective vibrational excitation can thus be achieved by RCAP and that population transfer can be followed by X-ray Photoelectron spectroscopy [S. Engin, N. Sisourat, P. Selles, R. Taïeb, and S. Carniato, Chem. Phys. Lett. 535, 192–195 (2012)]. Here, in a more detailed analysis of the process, we investigate the effects of highly excited electronic states and of molecular rotation on the efficiency of RCAP. Furthermore, we propose an alternative spectroscopic way to monitor the transfer by means of X-ray absorption spectra.

  15. Ligand-field symmetry effects in Fe(II) polypyridyl compounds probed by transient X-ray absorption spectroscopy

    SciTech Connect (OSTI)

    Cho, Hana; Strader, Matthew L.; Hong, Kiryong; Jamula, Lindsey; Kim, Tae Kyu; Groot, Frank M. F. de; McCusker, James K.; Schoenlein, Robert W.; Huse, Nils

    2012-02-28

    Ultrafast excited-state evolution in polypyridyl FeII complexes are of fundamental interest for understanding the origins of the sub-ps spin-state changes that occur upon photoexcitation of this class of compounds as well as for the potential impact such ultrafast dynamics have on incorporation of these compounds in solar energy conversion schemes or switchable optical storage technologies. We have demonstrated that ground-state and, more importantly, ultrafast time-resolved x-ray absorption methods can offer unique insights into the interplay between electronic and geometric structure that underpin the photo-induced dynamics of this class of compounds. The present contribution examines in greater detail how the symmetry of the ligand field surrounding the metal ion can be probed using these x-ray techniques. In particular, we show that steady-state K-edge spectroscopy of the nearest-neighbour nitrogen atoms reveals the characteristic chemical environment of the respective ligands and suggests an interesting target for future charge-transfer femtosecond and attosecond spectroscopy in the x-ray water window.

  16. Simulating Cl K-edge X-ray absorption spectroscopy in MCl62-...

    Office of Scientific and Technical Information (OSTI)

    using time-dependent density functional theory Citation Details In-Document Search ... using time-dependent density functional theory We report simulations of the X-ray ...

  17. In operando observation system for electrochemical reaction by soft X-ray absorption spectroscopy with potential modulation method

    SciTech Connect (OSTI)

    Nagasaka, Masanari Kosugi, Nobuhiro; Yuzawa, Hayato; Horigome, Toshio

    2014-10-15

    In order to investigate local structures of electrolytes in electrochemical reactions under the same scan rate as a typical value 100 mV/s in cyclic voltammetry (CV), we have developed an in operando observation system for electrochemical reactions by soft X-ray absorption spectroscopy (XAS) with a potential modulation method. XAS spectra of electrolytes are measured by using a transmission-type liquid flow cell with built-in electrodes. The electrode potential is swept with a scan rate of 100 mV/s at a fixed photon energy, and soft X-ray absorption coefficients at different potentials are measured at the same time. By repeating the potential modulation at each fixed photon energy, it is possible to measure XAS of electrochemical reaction at the same scan rate as in CV. We have demonstrated successful measurement of the Fe L-edge XAS spectra of aqueous iron sulfate solutions and of the change in valence of Fe ions at different potentials in the Fe redox reaction. The mechanism of these Fe redox processes is discussed by correlating the XAS results with those at different scan rates.

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

    SciTech Connect (OSTI)

    Cinco, Roehl M.

    1999-12-16

    Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH{sub 2}OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees {+-} 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese cluster in PS II and a family of synthetic manganese complexes containing the distorted cubane [Mn{sub 4}O{sub 3}X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn{sub 4}O{sub 3}Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The EXAFS method detects the small changes in the core structures as X is varied in this series, and serves to exclude these distorted cubanes of C3v symmetry as a topological model for the Mn catalytic cluster. The sulfur K-edge x-ray absorption near-edge structure (XANES) spectra for the amino acids cysteine, methionine, their corresponding oxidized forms cystine and methionine sulfoxide, and glutathione show distinct

  19. High energy resolution five-crystal spectrometer for high quality fluorescence and absorption measurements on an x-ray absorption spectroscopy beamline

    SciTech Connect (OSTI)

    Llorens, Isabelle; Lahera, Eric; Delnet, William; Proux, Olivier; Dermigny, Quentin; Gelebart, Frederic; Morand, Marc; Shukla, Abhay; Bardou, Nathalie; Ulrich, Olivier; and others

    2012-06-15

    Fluorescence detection is classically achieved with a solid state detector (SSD) on x-ray absorption spectroscopy (XAS) beamlines. This kind of detection however presents some limitations related to the limited energy resolution and saturation. Crystal analyzer spectrometers (CAS) based on a Johann-type geometry have been developed to overcome these limitations. We have tested and installed such a system on the BM30B/CRG-FAME XAS beamline at the ESRF dedicated to the structural investigation of very dilute systems in environmental, material and biological sciences. The spectrometer has been designed to be a mobile device for easy integration in multi-purpose hard x-ray synchrotron beamlines or even with a laboratory x-ray source. The CAS allows to collect x-ray photons from a large solid angle with five spherically bent crystals. It will cover a large energy range allowing to probe fluorescence lines characteristic of all the elements from Ca (Z = 20) to U (Z = 92). It provides an energy resolution of 1-2 eV. XAS spectroscopy is the main application of this device even if other spectroscopic techniques (RIXS, XES, XRS, etc.) can be also achieved with it. The performances of the CAS are illustrated by two experiments that are difficult or impossible to perform with SSD and the complementarity of the CAS vs SSD detectors is discussed.

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

    SciTech Connect (OSTI)

    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+?} 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+?} 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+?}. 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+?} using XAS analysis. EXAFS and XANES analysis showed that Fe was likely to be situated in the RS layer structure. Changes in TE property with Fe content was due to charge transfer between the CoO{sub 2} and

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

    SciTech Connect (OSTI)

    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.

  2. New developments in micro-X-ray diffraction and X-ray absorption spectroscopy for high-pressure research at 16-BM-D at the Advanced Photon Source

    SciTech Connect (OSTI)

    Park, Changyong Popov, Dmitry; Ikuta, Daijo; Lin, Chuanlong; Kenney-Benson, Curtis; Rod, Eric; Bommannavar, Arunkumar; Shen, Guoyin

    2015-07-15

    The monochromator and focusing mirrors of the 16-BM-D beamline, which is dedicated to high-pressure research with micro-X-ray diffraction (micro-XRD) and X-ray absorption near edge structure (XANES) (6-45 keV) spectroscopy, have been recently upgraded. Monochromatic X-rays are selected by a Si (111) double-crystal monochromator operated in an artificial channel-cut mode and focused to 5 μm × 5 μm (FWHM) by table-top Kirkpatrick-Baez type mirrors located near the sample stage. The typical X-ray flux is ∼5 × 10{sup 8} photons/s at 30 keV. The instrumental resolution, Δq/q{sub max}, reaches to 2 × 10{sup −3} and is tunable through adjustments of the detector distance and X-ray energy. The setup is stable and reproducible, which allows versatile application to various types of experiments including resistive heating and cryogenic cooling as well as ambient temperature compression. Transmission XANES is readily combined with micro-XRD utilizing the fixed-exit feature of the monochromator, which allows combined XRD-XANES measurements at a given sample condition.

  3. X-ray absorption spectroscopy of aluminum z-pinch plasma with tungsten backlighter planar wire array source

    SciTech Connect (OSTI)

    Osborne, G. C.; Kantsyrev, V. L.; Safronova, A. S.; Esaulov, A. A.; Weller, M. E.; Shrestha, I.; Shlyaptseva, V. V.; Ouart, N. D.

    2012-10-15

    Absorption features from K-shell aluminum z-pinch plasmas have recently been studied on Zebra, the 1.7 MA pulse power generator at the Nevada Terawatt Facility. In particular, tungsten plasma has been used as a semi-backlighter source in the generation of aluminum K-shell absorption spectra by placing a single Al wire at or near the end of a single planar W array. All spectroscopic experimental results were recorded using a time-integrated, spatially resolved convex potassium hydrogen phthalate (KAP) crystal spectrometer. Other diagnostics used to study these plasmas included x-ray detectors, optical imaging, laser shadowgraphy, and time-gated and time-integrated x-ray pinhole imagers. Through comparisons with previous publications, Al K-shell absorption lines are shown to be from much lower electron temperature ({approx}10-40 eV) plasmas than emission spectra ({approx}350-500 eV).

  4. Probing the Electronic Structure of a Photoexcited Solar Cell Dye with Transient X-ray Absorption Spectroscopy

    SciTech Connect (OSTI)

    Kuiken, Benjamin E. Van; Huse, Nils; Cho, Hana; Strader, Matthew L.; Lynch, Michael S.; Schoenlein, Robert W.; Khalil, Munira

    2012-05-01

    This study uses transient X-ray absorption (XA) spectroscopy and timedependent density functional theory (TD-DFT) to directly visualize the charge density around the metal atom and the surrounding ligands following an ultrafast metal-to-ligand charge-transfer (MLCT) process in the widely used RuII solar cell dye, Ru(dcbpy)2(NCS)2 (termed N3). We measure the Ru L-edge XA spectra of the singlet ground (1A1) and the transient triplet (3MLCT) excited state of N34 and perform TD-DFT calculations of 2p core-level excitations, which identify a unique spectral signature of the electron density on the NCS ligands. We find that the Ru 2p, Ru eg, and NCS orbitals are stabilized by 2.0, 1.0, and 0.6 eV, respectively, in the transient 3MLCT state of the dye. These results highlight the role of the NCS ligands in governing the oxidation state of the Ru center.

  5. Determining copper and lead binding in Larrea tridentata through chemical modification and X-ray absorption spectroscopy

    SciTech Connect (OSTI)

    Polette, L.; Gardea-Torresdey, J.L.; Chianelli, R.; Pickering, I.J.; George, G.N.

    1997-12-31

    Metal contamination in soils has become a widespread problem. Emerging technologies, such as phytoremediation, may offer low cost cleanup methods. The authors have identified a desert plant, Larrea tridentata (creosote bush), which naturally grows and uptakes copper and lead from a contaminated area near a smelting operation. They determined, through chemical modification of carboxyl groups with methanol, that these functional groups may be responsible for a portion of copper(II) binding. In contrast, lead binding was minimally affected by modification of carboxyl groups. X-ray absorption spectroscopy studies conducted at Stanford Synchrotron Radiation Laboratory (SSRL) further support copper binding to oxygen-coordinated ligands and also imply that the binding is not solely due to phytochelatins. The EXAFS data indicate the presence of both Cu-O and Cu-S back scatters, no short Cu-Cu interactions, but with significant Cu-Cu back scattering at 3.7 {angstrom} (unlike phytochelatins with predominantly Cu-S coordination and short Cu-Cu interactions at 2.7 {angstrom}). Cu EXAFS of roots and leaves also vary depending on the level of heavy metal contamination in the environment from which the various creosote samples were obtained. In contrast, Pb XANES data of roots and leaves of creosote collected from different contaminated sites indicate no difference in valence states or ligand coordination.

  6. X-ray absorption spectroscopy of LiBF 4 in propylene carbonate. A model lithium ion battery electrolyte

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Smith, Jacob W.; Lam, Royce K.; Sheardy, Alex T.; Shih, Orion; Rizzuto, Anthony M.; Borodin, Oleg; Harris, Stephen J.; Prendergast, David; Saykally, Richard J.

    2014-08-20

    Since their introduction into the commercial marketplace in 1991, lithium ion batteries have become increasingly ubiquitous in portable technology. Nevertheless, improvements to existing battery technology are necessary to expand their utility for larger-scale applications, such as electric vehicles. Advances may be realized from improvements to the liquid electrolyte; however, current understanding of the liquid structure and properties remains incomplete. X-ray absorption spectroscopy of solutions of LiBF4 in propylene carbonate (PC), interpreted using first-principles electronic structure calculations within the eXcited electron and Core Hole (XCH) approximation, yields new insight into the solvation structure of the Li+ ion in this model electrolyte.more » By generating linear combinations of the computed spectra of Li+-associating and free PC molecules and comparing to the experimental spectrum, we find a Li+–solvent interaction number of 4.5. This result suggests that computational models of lithium ion battery electrolytes should move beyond tetrahedral coordination structures.« less

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

    SciTech Connect (OSTI)

    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.

  8. SMB, X-Ray Spectroscopy & Imaging

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Home » X-Ray Spectroscopy & Imaging X-Ray Spectroscopy & Imaging SSRL has five hard X-ray Spectroscopy beamlines and three Microfocus Imaging beamlines dedicated to Biological and Biomedical research funded by the NIH and DOE-BER. The SMB group supports and develops technical instrumentation and theoretical methods for state-of-the-art tender and hard X-ray spectroscopy and EXAFS studies on metalloproteins, cofactors and metals in medicine. The SMB group has also contributed to the

  9. Particle size effect of hydride formation and surface hydrogen absorption of nanosized palladium catalysts : L{sub 3} edge vs K edge x-ray absorption spectroscopy.

    SciTech Connect (OSTI)

    Tew, M. W.; Miller, J. T.; van Bokhoven, J. A.

    2009-08-01

    The particle size effect on the formation of palladium hydride and on surface hydrogen adsorption was studied at room temperature using in situ X-ray absorption spectroscopy at the Pd K and L{sub 3} edges. Hydride formation was indirectly observed by lattice expansion in Pd K edge XANES spectra and by EXAFS analysis. Hydride formation was directly detected in the L{sub 3} edge spectra. A characteristic spectral feature caused by the formation of a Pd-H antibonding state showed strong particle size dependence. The L{sub 3} edge spectra were reproduced using full multiple scattering analysis and density of state calculations, and the contributions of bulk absorbed and surface hydrogen to the XANES spectra could be distinguished. The ratio of hydrogen on the surface versus that in the bulk increased with decreasing particle size, and smaller particles dissolved less hydrogen.

  10. Direct speciation analysis of arsenic in sub-cellular compartments using micro-X-ray absorption spectroscopy

    SciTech Connect (OSTI)

    Bacquart, Thomas; Deves, Guillaume; Ortega, Richard

    2010-07-15

    Identification of arsenic chemical species at a sub-cellular level is a key to understanding the mechanisms involved in arsenic toxicology and antitumor pharmacology. When performed with a microbeam, X-ray absorption near-edge structure ({mu}-XANES) enables the direct speciation analysis of arsenic in sub-cellular compartments avoiding cell fractionation and other preparation steps that might modify the chemical species. This methodology couples tracking of cellular organelles in a single cell by confocal or epifluorescence microscopy with local analysis of chemical species by {mu}-XANES. Here we report the results obtained with a {mu}-XANES experimental setup based on Kirkpatrick-Baez X-ray focusing optics that maintains high flux of incoming radiation (>10{sup 11} ph/s) at micrometric spatial resolution (1.5x4.0 {mu}m{sup 2}). This original experimental setup enabled the direct speciation analysis of arsenic in sub-cellular organelles with a 10{sup -15} g detection limit. {mu}-XANES shows that inorganic arsenite, As(OH){sub 3}, is the main form of arsenic in the cytosol, nucleus, and mitochondrial network of cultured cancer cells exposed to As{sub 2}O{sub 3}. On the other hand, a predominance of As(III) species is observed in HepG2 cells exposed to As(OH){sub 3} with, in some cases, oxidation to a pentavalent form in nuclear structures of HepG2 cells. The observation of intra-nuclear mixed redox states suggests an inter-individual variability in a cell population that can only be evidenced with direct sub-cellular speciation analysis.

  11. High resolution absorption spectroscopy of exploding wire plasmas using an x-pinch x-ray source and spherically bent crystal

    SciTech Connect (OSTI)

    Knapp, P. F.; Pikuz, S. A.; Shelkovenko, T. A.; Hammer, D. A.; Hansen, S. B.

    2011-06-15

    We present here the use of absorption spectroscopy of the continuum radiation from x-pinch-produced point x-ray sources as a diagnostic to investigate the properties of aluminum plasmas created by pulsed power machines. This technique is being developed to determine the charge state, temperature, and density as a function of time and space under conditions that are inaccessible to x-ray emission spectroscopic diagnostics. The apparatus and its characterization are described, and the spectrometer dispersion, magnification, and resolution are calculated and compared with experimental results. Spectral resolution of about 5000 and spatial resolution of about 20 {mu}m are demonstrated. This spectral resolution is the highest available to date in an absorption experiment. The beneficial properties of the x-pinch x-ray source as the backlighter for this diagnostic are the small source size (<5 {mu}m), smooth continuum radiation, and short pulse duration (<0.1 ns). Results from a closely spaced (1 mm) exploding wire pair are shown and the general features are discussed.

  12. Hard x-ray delay line for x-ray photon correlation spectroscopy...

    Office of Scientific and Technical Information (OSTI)

    Hard x-ray delay line for x-ray photon correlation spectroscopy and jitter-free pump-probe experiments at LCLS Citation Details In-Document Search Title: Hard x-ray delay line for...

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

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    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

  14. Soft-x-ray spectroscopy study of nanoscale materials

    SciTech Connect (OSTI)

    Guo, J.-H.

    2005-07-30

    The ability to control the particle size and morphology of nanoparticles is of crucial importance nowadays both from a fundamental and industrial point of view considering the tremendous amount of high-tech applications. Controlling the crystallographic structure and the arrangement of atoms along the surface of nanostructured material will determine most of its physical properties. In general, electronic structure ultimately determines the properties of matter. Soft X-ray spectroscopy has some basic features that are important to consider. X-ray is originating from an electronic transition between a localized core state and a valence state. As a core state is involved, elemental selectivity is obtained because the core levels of different elements are well separated in energy, meaning that the involvement of the inner level makes this probe localized to one specific atomic site around which the electronic structure is reflected as a partial density-of-states contribution. The participation of valence electrons gives the method chemical state sensitivity and further, the dipole nature of the transitions gives particular symmetry information. The new generation synchrotron radiation sources producing intensive tunable monochromatized soft X-ray beams have opened up new possibilities for soft X-ray spectroscopy. The introduction of selectively excited soft X-ray emission has opened a new field of study by disclosing many new possibilities of soft X-ray resonant inelastic scattering. In this paper, some recent findings regarding soft X-ray absorption and emission studies of various nanostructured systems are presented.

  15. Setup for in situ investigation of gases and gas/solid interfaces by soft x-ray emission and absorption spectroscopy

    SciTech Connect (OSTI)

    Benkert, A. E-mail: l.weinhardt@kit.edu; Blum, M.; Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720 ; Meyer, F.; Wilks, R. G.; Yang, W.; Bär, M.; Solar Energy Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin; Insitut für Physik und Chemie, Brandenburgische Technische Universität Cottbus-Senftenberg, Konrad-Wachsmann-Allee 1, 03046 Cottbus ; and others

    2014-01-15

    We present a novel gas cell designed to study the electronic structure of gases and gas/solid interfaces using soft x-ray emission and absorption spectroscopies. In this cell, the sample gas is separated from the vacuum of the analysis chamber by a thin window membrane, allowing in situ measurements under atmospheric pressure. The temperature of the gas can be regulated from room temperature up to approximately 600 °C. To avoid beam damage, a constant mass flow can be maintained to continuously refresh the gaseous sample. Furthermore, the gas cell provides space for solid-state samples, allowing to study the gas/solid interface for surface catalytic reactions at elevated temperatures. To demonstrate the capabilities of the cell, we have investigated a TiO{sub 2} sample behind a mixture of N{sub 2} and He gas at atmospheric pressure.

  16. The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Tobin, J. G.

    2013-05-03

    X-ray absorption spectroscopy (XAS) and related derivative measurements have been used to demonstrate that the Pu 5f states are strongly relativistic and have a 5f occupation number near 5. Owing to the success in this regime, it has been argued that the XAS measurements should be a powerful tool to probe 5f occupation variation, both as a function of elemental nature (actinide atomic number) and as a function of physical and chemical perturbation, e.g., oxidation state. We show that XAS and its related measurements fail in this latter aspect for a wide variety of uranium compounds and materials. Possible causesmore » will be discussed.« less

  17. Correlation between Active Center Structure and Enhanced Dioxygen Binding in Co(salen) Nanoparticles: Characterization by In Situ Infrared, Raman, and X-ray Absorption Spectroscopies

    SciTech Connect (OSTI)

    Johnson,C.; Long, B.; Nguyen, J.; Day, V.; Borovik, A.; Subramaniam, B.; Guzman, J.

    2008-01-01

    The structure and ligand environment of Co(salen) nanoparticles and unprocessed Co(salen) have been determined by the combined application of infrared, Raman, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies, and X-ray diffraction (XRD) experiments before and during interaction with O2. The Co(salen) nanoparticles were prepared by the precipitation with compressed antisolvent (PCA) technique using commercially obtained Co(salen) [denoted as unprocessed Co(salen)] as the parent compound. The unprocessed Co(salen) particles exist as dimer species with a square-pyramidal coordination geometry that display no measurable O2 binding at room temperature. In sharp contrast, the Co(salen) nanoparticles show near-stoichiometric O2 adsorption, as demonstrated by microbalance gas binding experiments. The spectroscopy results indicate the presence of CoII centers with distorted tetrahedral geometry in the Co(salen) nanoparticles with no evidence of metallic Co clusters, confirmed by the lack of Co-Co contributions at bonding distances in the EXAFS spectra and the presence of characteristic features of CoII in the XANES spectra. The EXAFS data also indicate that there are on average two Co-N and two Co-O bonds with a distance of 1.81 {+-} 0.02 and 1.90 {+-} 0.02 Angstroms, respectively, consistent with typical metal salen structures. Upon O2 binding on the Co(salen) nanoparticles, the XANES results indicate oxidation of the CoII to CoIII, consistent with the vibrational data showing new bands associated with oxygen species bonded to Co centers and the increase in the oxygen coordination number from 1.8 to 2.9 in the EXAFS data. The results indicate that the enhanced O2 binding properties of Co(salen) nanoparticles are related to the unique distorted tetrahedral geometry, which is not observed in the unprocessed samples that contain mainly dimers with square planar geometry. The results presented here provide a

  18. X-ray spectroscopy of manganese clusters

    SciTech Connect (OSTI)

    Grush, M.M.

    1996-06-01

    Much of this thesis represents the groundwork necessary in order to probe Mn clusters more productively than with conventional Mn K-edge XAS and is presented in Part 1. Part 2 contains the application of x-ray techniques to Mn metalloproteins and includes a prognosis at the end of each chapter. Individual Mn oxidation states are more readily distinguishable in Mn L-edge spectra. An empirical mixed valence simulation routine for determining the average Mn oxidation state has been developed. The first Mn L-edge spectra of a metalloprotein were measured and interpreted. The energy of Mn K{beta} emission is strongly correlated with average Mn oxidation state. K{beta} results support oxidation states of Mn(III){sub 2}(IV){sub 2} for the S{sub 1} state of Photosystem II chemical chemically reduced preparations contain predominantly Mn(II). A strength and limitation of XAS is that it probes all of the species of a particular element in a sample. It would often be advantageous to selectively probe different forms of the same element. The first demonstration that chemical shifts in x-ray fluorescence energies can be used to obtain oxidation state-selective x-ray absorption spectra is presented. Spin-dependent spectra can also be used to obtain a more simplified picture of local structure. The first spin-polarized extended x-ray absorption fine structure using Mn K{beta} fluorescence detection is shown.

  19. Electronic structure of Al-doped ZnO transparent conductive thin films studied by x-ray absorption and emission spectroscopies

    SciTech Connect (OSTI)

    Huang, W. H.; Sun, S. J.; Chiou, J. W.; Chou, H.; Chan, T. S.; Lin, H.-J.; Kumar, Krishna; Guo, J.-H.

    2011-11-15

    This study used O K-, Zn L{sub 3}-, Zn K-, and Al K-edges x-ray absorption near-edge structure (XANES) and O K-edge x-ray emission spectroscopy (XES) measurements to investigate the electronic structure of transparent Al-doped ZnO (AZO) thin film conductors. The samples were prepared on glass substrates at a low temperature near 77 K by using a standard RF sputtering method. High-purity Ne (5N) was used as the sputtering gas. The crystallography of AZO thin films gradually transformed from the ZnO wurtize structure to an amorphous structure during sample deposition, which suggests the suitability to grow on flexible substrates, eliminating the severe degradation due to fragmentation by repeated bending. The O K- and Zn L{sub 3}-edges XANES spectra of AZO thin films revealed a decrease in the number of both O 2p and Zn 3d unoccupied states when the pressure of Ne was increased from 5 to 100 mTorr. In contrast, Al K-edges XANES spectra showed that the number of unoccupied states of Al 3p increased in conjunction with the pressure of Ne, indicating an electron transfer from Al to O atoms, and suggesting that Al doping increases the negative effective charge of oxygen ions. XES and XANES spectra of O 2p states at the O K-edge also revealed that Al doping not only raised the conduction-band-minimum, but also increased the valence-band-maximum and the band-gap. The results indicate that the reduction in conductivity of AZO thin films is due to the generation of ionic characters, the increase in band-gap, and the decrease in density of unoccupied states of oxygen.

  20. X-ray Attenuation and Absorption Calculations.

    Energy Science and Technology Software Center (OSTI)

    1988-02-25

    This point-source, polychromatic, discrete energy X-ray transport and energy deposition code system calculates first-order spectral estimates of X-ray energy transmission through slab materials and the associated spectrum of energy absorbed by the material.

  1. Simulating Ru L3-Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    SciTech Connect (OSTI)

    Kuiken, Benjamin E. Van; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira

    2013-04-26

    Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.

  2. Dissolution of thin iron oxide films used as models for iron passive films studied by in situ X-ray absorption near-edge spectroscopy

    SciTech Connect (OSTI)

    Virtanen, S; Schmuki, P.; Davenport, A.J.; Vitus, C.M.

    1997-01-01

    This paper reports results from X-ray absorption near-edge spectroscopy (XANES) studies during polarization of thin sputter-deposited iron oxide films in acidic solutions. The dissolution rate of iron oxides in acidic solutions was found to be strongly increased by the presence of Fe{sup 2+} in the oxide. During anodic polarization in acidic solutions, it is found that dissolution is accelerated by chloride anions in comparison with sulfates. In HCl solutions of increasing concentration, not only does the pH decrease, but also the increasing chloride concentration accelerates dissolution. On the other hand, the dissolution rate in sulfuric acid does not depend on the sulfate (bisulfate) concentration. During anodic polarization, the dissolution rate is fairly independent of the potential, except at very high anodic potentials, and the XANES spectra reveal no changes in the average oxide valence during anodic polarization. Thus the dissolution that takes place is mostly chemical rather than electrochemical. During cathodic polarization, the dissolution rate is independent of the anion in the electrolyte. The findings are interpreted in terms of the negative surface charge of n-type oxides at potentials lower than the flatband potential, retarding anion adsorption on the surface. Hence it is suggested that the detrimental role of chloride anions on the stability of iron oxide films is due to a surface complexation effect. The findings and their relevance to the stability of natural passive films on iron surfaces are discussed.

  3. X-ray absorption spectroscopy of LiBF 4 in propylene carbonate. A model lithium ion battery electrolyte

    SciTech Connect (OSTI)

    Smith, Jacob W.; Lam, Royce K.; Sheardy, Alex T.; Shih, Orion; Rizzuto, Anthony M.; Borodin, Oleg; Harris, Stephen J.; Prendergast, David; Saykally, Richard J.

    2014-08-20

    Since their introduction into the commercial marketplace in 1991, lithium ion batteries have become increasingly ubiquitous in portable technology. Nevertheless, improvements to existing battery technology are necessary to expand their utility for larger-scale applications, such as electric vehicles. Advances may be realized from improvements to the liquid electrolyte; however, current understanding of the liquid structure and properties remains incomplete. X-ray absorption spectroscopy of solutions of LiBF4 in propylene carbonate (PC), interpreted using first-principles electronic structure calculations within the eXcited electron and Core Hole (XCH) approximation, yields new insight into the solvation structure of the Li+ ion in this model electrolyte. By generating linear combinations of the computed spectra of Li+-associating and free PC molecules and comparing to the experimental spectrum, we find a Li+–solvent interaction number of 4.5. This result suggests that computational models of lithium ion battery electrolytes should move beyond tetrahedral coordination structures.

  4. Probing the f-state configuration of URu2Si2 with U LIII-edge resonant x-ray absorption spectroscopy

    SciTech Connect (OSTI)

    Medling, S. A.; Booth, C. H.; Tobin, J. G.; Baumbach, R. E.; Bauer, E. D.; Sokaras, D.; Nordlund, D.; Weng, T. C.

    2015-09-05

    It has often been said that the most interesting ph- syics occurs when competing interactions are of nearly the same magnitude. Such a situation is surely oc- curing at URu2Si2’s so-called “hidden-order transition”, which garners its name from the missing entropy at a 17.5 K phase transition relative to that expected for a conventional antiferromagnetic phase transition, de- spite the presence of only a very small ordered mag- netic moment.? Despite this discrepancy being identi- fied in 1985, the identification of the order parameter remains elusive, although progress toward understand- ing this transition has been steady since that time, and URu2Si2 remains an important research subject today.? The work described below provides measures of the 5f orbital occupancy and itinerancy using resonant x-ray emission spectroscopy (RXES) at the U LIII absorption edge and measuring U L 1 emission that potentially acts as a dividing line between different classes of “hidden- order” theories.

  5. Ambient Pressure Photoelectron Spectroscopy Using Soft X-ray...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Ambient Pressure Photoelectron Spectroscopy Using Soft X-ray and Hard X-ray, and its applications in electrochemistry Friday, December 14, 2012 - 3:30pm SSRL, Bldg. 137, room 322...

  6. XRMS: X-Ray Spectroscopy of Magnetic Solids

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    XRMS: X-Ray Spectroscopy of Magnetic Solids October 22-23, 2011 SLAC National Accelerator Laboratory, Menlo Park, CA More information...

  7. In situ soft X-ray absorption spectroscopy investigation of electrochemical corrosion of copper in aqueous NaHCO3 solution

    SciTech Connect (OSTI)

    Jiang, Peng; Chen, Jeng-Lung; Borondics, Ferenc; Glans, Per-Anders; West, Mark W.; Chang, Ching-Lin; Salmeron, Miquel; Guo, Jinghua

    2010-03-31

    A novel electrochemical setup has been developed for soft x-ray absorption studies of the electronic structure of electrode materials during electrochemical cycling. In this communication we illustrate the operation of the cell with a study of the corrosion behavior of copper in aqueous NaHCO3 solution via the electrochemically induced changes of its electronic structure. This development opens the way for in situ investigations of electrochemical processes, photovoltaics, batteries, fuel cells, water splitting, corrosion, electrodeposition, and a variety of important biological processes.

  8. TU-A-9A-07: X-Ray Acoustic Computed Tomography (XACT): 100% Sensitivity to X-Ray Absorption

    SciTech Connect (OSTI)

    Xiang, L; Ahmad, M; Nikoozadeh, A; Pratx, G; Khuri-Yakub, B; Xing, L

    2014-06-15

    Purpose: To assess whether X-ray acoustic computed tomography (XACT) is more sensitive to X-ray absorption than that of the conventional X-ray imaging. Methods: First, a theoretical model was built to analyze the X-ray absorption sensitivity of XACT imaging and conventional X-ray imaging. Second, an XACT imaging system was developed to evaluate the X-ray induced acoustic signal generation as well as the sensitivity improvement over transmission x-ray imaging. Ultra-short x-ray pulses (60-nanosecond) were generated from an X-ray source operated at the energy of 150 kVp with a 10-Hz repetition rate. The X-ray pulse was synchronized with the acoustic detection via a x-ray scintillation triggering to acquire the X-ray induced acoustic signal. Results: Theoretical analysis shows that X-ray induced acoustic signal is sensitive only to the X-ray absorption, while completely insensitive to out the X-ray scattering and fluorescence. XACT has reduced background and increased contrast-to-noise ratio, and therefore has increased sensitivity compared to transmission x-ray imaging. For a 50-μm size, gadolinium insertion in tissue exposed to 40 keV X-rays; the sensitivity of XACT imaging is about 28.9 times higher than that of conventional X-ray imaging. Conclusion: X-ray acoustic computer tomography (XACT) as a new imaging modality combines X-ray absorption contrast and high ultrasonic resolution in a single modality. It is feasible to improve the imaging sensitivity with XACT imaging compared with conventional X-ray imaging. Taking advantage of the high ultrasonic resolution, it is possible to perform 3-D imaging with a single x-ray pulse with arrays of transducers without any mechanical motion of the imaging system. This single-shot capability offers the potential of reducing radiation dose by a factor of 1000, and imaging 100 times faster when compared to the conventional X-ray CT, and thus revolutionizing x-ray imaging applications in medicine and biology. The authors

  9. 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 (OSTI)

    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.

  10. Soft X-ray absorption spectroscopy of La{sub 0.7}Ca{sub 0.3}Mn{sub 1−X}Al{sub X}O{sub 3} thin films

    SciTech Connect (OSTI)

    Kumar, Manish Choudhary, R. J. Phase, D. M.

    2014-04-24

    Epitaxial thin films of rare earth manganites have generated much attention recently due to their rich phase diagram. The electronic structure of these films is playing a very crucial role and demands a fundamental understanding prior to device fabrication. We have investigated the electronic structure of La{sub 0.7}Ca{sub 0.3}Mn{sub 1−X}Al{sub X}O{sub 3} (X=0, 0.15) epitaxial thin films by soft X-ray absorption spectroscopy technique using the surface sensitive total electron yield (TEY) mode.

  11. Characterization of Gas Shales by X-ray Raman Spectroscopy |...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Characterization of Gas Shales by X-ray Raman Spectroscopy Thursday, February 23, 2012 - 10:30am SSRL Third Floor Conference Room 137-322 Drew Pomerantz, Schlumberger ...

  12. Characterization of Gas Shales by X-ray Raman Spectroscopy |...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Characterization of Gas Shales by X-ray Raman Spectroscopy Monday, May 14, 2012 - 3:30pm SSRL Conference Room 137-322 Drew Pomerantz, Schlumberger Unconventional hydrocarbon ...

  13. Effect of Biogeochemical Redox Processes on the Fate and Transport of As and U at an Abandoned Uranium Mine Site: an X-ray Absorption Spectroscopy Study

    SciTech Connect (OSTI)

    Troyer, Lyndsay D.; Stone, James J.; Borch, Thomas

    2014-01-28

    Although As can occur in U ore at concentrations up to 10 wt-%, the fate and transport of both U and As at U mine tailings have not been previously investigated at a watershed scale. The major objective of this study was to determine primary chemical and physical processes contributing to transport of both U and As to a down gradient watershed at an abandoned U mine site in South Dakota. Uranium is primarily transported by erosion at the site, based on decreasing concentrations in sediment with distance from the tailings. equential extractions and U X-ray absorption near-edge fine structure (XANES) fitting indicate that U is immobilised in a near-source sedimentation pond both by prevention of sediment transport and by reduction of UVI to UIV. In contrast to U, subsequent release of As to the watershed takes place from the pond partially due to reductive dissolution of Fe oxy(hydr)oxides. However, As is immobilised by adsorption to clays and Fe oxy(hydr)oxides in oxic zones and by formation of Assulfide mineral phases in anoxic zones down gradient, indicated by sequential extractions and As XANES fitting. This study indicates that As should be considered during restoration of uranium mine sites in order to prevent transport.

  14. Multilayer graphene stacks grown by different methods-thickness measurements by X-ray diffraction, Raman spectroscopy and optical transmission

    SciTech Connect (OSTI)

    Tokarczyk, M. Kowalski, G.; Kępa, H.; Grodecki, K.; Drabińska, A.; Strupiński, W.

    2013-12-15

    X-ray diffraction, Raman spectroscopy and Optical absorption estimates of the thickness of graphene multi layer stacks (number of graphene layers) are presented for three different growth techniques. The objective of this work was focused on comparison and reconciliation of the two already widely used methods for thickness estimates (Raman and Absorption) with the calibration of the X-ray method as far as Scherer constant K is concerned and X-ray based Wagner-Aqua extrapolation method.

  15. New focusing multilayer structures for X-ray plasma spectroscopy

    SciTech Connect (OSTI)

    Bibishkin, M S; Luchin, V I; Salashchenko, N N; Chernov, V V; Chkhalo, N I; Kazakov, E D; Shevelko, A P

    2008-02-28

    New focusing short-period multilayer structures are developed which opens up wide possibilities for X-ray and VUV spectroscopy. Multilayer structures are deposited on a flat surface of a mica crystal which is then bent to a small-radius cylinder. The use of this structure in a von Hamos spectrometer for X-ray laser plasma diagnostics is demonstrated. (interaction of laser radiation with matter. laser plasma)

  16. A table-top femtosecond time-resolved soft x-ray transient absorption spectrometer

    SciTech Connect (OSTI)

    Leone, Stephen; Loh, Zhi-Heng; Khalil, Munira; Correa, Raoul E.; Leone, Stephen R.

    2008-05-21

    A laser-based, table-top instrument is constructed to perform femtosecond soft x-ray transient absorption spectroscopy. Ultrashort soft x-ray pulses produced via high-order harmonic generation of the amplified output of a femtosecond Ti:sapphire laser system are used to probe atomic core-level transient absorptions in atoms and molecules. The results provide chemically specific, time-resolved dynamics with sub-50-fs time resolution. In this setup, high-order harmonics generated in a Ne-filled capillary waveguide are refocused by a gold-coated toroidal mirror into the sample gas cell, where the soft x-ray light intersects with an optical pump pulse. The transmitted high-order harmonics are spectrally dispersed with a home-built soft x-ray spectrometer, which consists of a gold-coated toroidal mirror, a uniform-line spaced plane grating, and a soft x-ray CCD camera. The optical layout of the instrument, design of the soft x-ray spectrometer, and spatial and temporal characterization of the high-order harmonics are described. Examples of static and time-resolved photoabsorption spectra collected on this apparatus are presented.

  17. Ultrafast conversions between hydrogen bonded structures in liquid water observed by femtosecond x-ray spectroscopy

    SciTech Connect (OSTI)

    Wen, Haidan; Huse, Nils; Schoenlein, Robert W.; Lindenberg, Aaron M.

    2010-05-01

    We present the first femtosecond soft x-ray spectroscopy in liquids, enabling the observation of changes in hydrogen bond structures in water via core-hole excitation. The oxygen K-edge of vibrationally excited water is probed with femtosecond soft x-ray pulses, exploiting the relation between different water structures and distinct x-ray spectral features. After excitation of the intramolecular OH stretching vibration, characteristic x-ray absorption changes monitor the conversion of strongly hydrogen-bonded water structures to more disordered structures with weaker hydrogen-bonding described by a single subpicosecond time constant. The latter describes the thermalization time of vibrational excitations and defines the characteristic maximum rate with which nonequilibrium populations of more strongly hydrogen-bonded water structures convert to less-bonded ones. On short time scales, the relaxation of vibrational excitations leads to a transient high-pressure state and a transient absorption spectrum different from that of statically heated water.

  18. High resolution absorption spectroscopy of exploding wire plasmas...

    Office of Scientific and Technical Information (OSTI)

    Published Article: High resolution absorption spectroscopy of exploding wire plasmas using an x-pinch x-ray source and spherically bent crystal Title: High resolution absorption ...

  19. High pressure effects on U L[subscript 3] x-ray absorption in...

    Office of Scientific and Technical Information (OSTI)

    High pressure effects on U Lsubscript 3 x-ray absorption in partial fluorescence yield ... Citation Details In-Document Search Title: High pressure effects on U Lsubscript 3 x-ray ...

  20. High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

    SciTech Connect (OSTI)

    Wang, Xin

    1996-12-01

    X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). The spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of K{alpha} and K{beta} emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS.

  1. High-order multilayer coated blazed gratings for high resolution soft x-ray spectroscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Voronov, Dmitriy L.; Goray, Leonid I.; Warwick, Tony; Yashchuk, Valeriy V.; Padmore, Howard A.

    2015-02-17

    A grand challenge in soft x-ray spectroscopy is to drive the resolving power of monochromators and spectrometers from the 104 achieved routinely today to well above 105. This need is driven mainly by the requirements of a new technique that is set to have enormous impact in condensed matter physics, Resonant Inelastic X-ray Scattering (RIXS). Unlike x-ray absorption spectroscopy, RIXS is not limited by an energy resolution dictated by the core-hole lifetime in the excitation process. Using much higher resolving power than used for normal x-ray absorption spectroscopy enables access to the energy scale of soft excitations in matter. Thesemoreexcitations such as magnons and phonons drive the collective phenomena seen in correlated electronic materials such as high temperature superconductors. RIXS opens a new path to study these excitations at a level of detail not formerly possible. However, as the process involves resonant excitation at an energy of around 1 keV, and the energy scale of the excitations one would like to see are at the meV level, to fully utilize the technique requires the development of monochromators and spectrometers with one to two orders of magnitude higher energy resolution than has been conventionally possible. Here we investigate the detailed diffraction characteristics of multilayer blazed gratings. These elements offer potentially revolutionary performance as the dispersive element in ultra-high resolution x-ray spectroscopy. In doing so, we have established a roadmap for the complete optimization of the grating design. Traditionally 1st order gratings are used in the soft x-ray region, but we show that as in the optical domain, one can work in very high spectral orders and thus dramatically improve resolution without significant loss in efficiency.less

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

    SciTech Connect (OSTI)

    Westre, T.E.

    1996-01-01

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

  3. Performance and analysis of absorption experiments on x-ray heated low-Z constrained samples

    SciTech Connect (OSTI)

    Lee, R.W.; Cauble, R.; Perry, T.S.; Springer, P.T.; Fields, D.F.; Bach, D.R.; Serduke, F.J.D.; Iglesias, C.A.; Rogers, F.J.; Nash, J.K.; Chen, M.H.; Wilson, B.G.; Goldstein, W.H.; Ward, R.A.; Kilkenny, J.D.; Doyas, R.; Da Silva, L.B.; Back, C.A.; Davidson, S.J.; Foster, J.M.; Smith, C.C.

    1996-05-01

    Results of experiments on the absorption of niobium in a hot, dense plasma are presented. These results represent a major step in the development of absorption techniques necessary for the quantitative characterization of hot, dense matter. A general discussion is presented of the requirements for performing quantitative analysis of absorption spectra. Hydrodynamic simulations are used to illustrate the behavior of tamped X-ray-heated matter and to indicate effects that can arise from the two dimensional aspects of the experiment. The absorption spectrum of a low-Z material, in this case aluminum, provides a temperature diagnostic and indicates the advance of the absorption measurement technique to the level of application. The experimental technique is placed in context with a review of other measurements using absorption spectroscopy to probe hot, dense matter.

  4. X-ray imaging crystal spectroscopy for use in plasma transport...

    Office of Scientific and Technical Information (OSTI)

    X-ray imaging crystal spectroscopy for use in plasma transport research Citation Details In-Document Search Title: X-ray imaging crystal spectroscopy for use in plasma transport ...

  5. In Operando Soft X-ray Spectroscopy of 3D Graphene Supercapacitor...

    Office of Scientific and Technical Information (OSTI)

    In Operando Soft X-ray Spectroscopy of 3D Graphene Supercapacitor Electrodes Citation Details In-Document Search Title: In Operando Soft X-ray Spectroscopy of 3D Graphene ...

  6. X-ray line polarization spectroscopy of Li-like satellite line...

    Office of Scientific and Technical Information (OSTI)

    X-ray line polarization spectroscopy of Li-like satellite line spectra Citation Details In-Document Search Title: X-ray line polarization spectroscopy of Li-like satellite line ...

  7. Soft X-Ray and Vacuum Ultraviolet Based Spectroscopy of the Actinides...

    Office of Scientific and Technical Information (OSTI)

    Conference: Soft X-Ray and Vacuum Ultraviolet Based Spectroscopy of the Actinides Citation Details In-Document Search Title: Soft X-Ray and Vacuum Ultraviolet Based Spectroscopy of ...

  8. Soft X-Ray and Vacuum Ultraviolet Based Spectroscopy of the Actinides...

    Office of Scientific and Technical Information (OSTI)

    Conference: Soft X-Ray and Vacuum Ultraviolet Based Spectroscopy of the Actinides Citation Details In-Document Search Title: Soft X-Ray and Vacuum Ultraviolet Based Spectroscopy of...

  9. Hubbard model corrections in real-space x-ray spectroscopy theory...

    Office of Scientific and Technical Information (OSTI)

    Hubbard model corrections in real-space x-ray spectroscopy theory Citation Details In-Document Search Title: Hubbard model corrections in real-space x-ray spectroscopy theory ...

  10. Calibration of Spherically Bent Crystals used in X-Ray Spectroscopy...

    Office of Scientific and Technical Information (OSTI)

    Calibration of Spherically Bent Crystals used in X-Ray Spectroscopy. Citation Details In-Document Search Title: Calibration of Spherically Bent Crystals used in X-Ray Spectroscopy. ...

  11. High-Resolution Structure of the Photosynthetic Mn4Ca Catalyst from X-ray Spectroscopy

    SciTech Connect (OSTI)

    Yachandra, Vittal; Yano, Junko; Kern, Jan; Pushkar, Yulia; Sauer, Kenneth; Glatzel, Pieter; Bergmann, Uwe; Messinger, Johannes; Zouni, Athina; Yachandra, Vittal K.

    2007-08-01

    The application of high-resolution X-ray spectroscopy methods to study the photosynthetic water oxidizing complex, which contains a unique hetero-nuclear catalytic Mn4Ca cluster, are described. Issues of X-ray damage especially at the metal sites in the Mn4Ca cluster are discussed. The structure of the Mn4Ca catalyst at high-resolution which has so far eluded attempts of determination by X-ray diffraction, EXAFS and other spectroscopic techniques has been addressed using polarized EXAFS techniques applied to oriented PS II membrane preparations and PS II single crystals. A review of how the resolution of traditional EXAFS techniques can be improved, using methods such as range-extended EXAFS is presented, and the changes that occur in the structure of the cluster as it advances through the catalytic cycle are described. X-ray absorption and emission techniques (XANES and K? emission) have been used earlier to determine the oxidation states of the Mn4Ca cluster, and in this report we review the use of X-ray resonant Raman spectroscopy to understand the electronic structure of the Mn4Ca cluster as it cycles through the intermediate S-states.

  12. X-Ray Absorption Spectroscopic Study of Sodium Iodide and Iodine...

    Office of Scientific and Technical Information (OSTI)

    Supercapacitor Citation Details In-Document Search Title: X-Ray Absorption Spectroscopic Study of Sodium Iodide and Iodine Mediators in a Solid-State Supercapacitor ...

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

    SciTech Connect (OSTI)

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

    2009-05-28

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

  14. A new spectrometer design for the x-ray spectroscopy of laser...

    Office of Scientific and Technical Information (OSTI)

    the x-ray spectroscopy of laser-produced plasmas with high (sub-ns) time resolution Citation Details In-Document Search Title: A new spectrometer design for the x-ray ...

  15. Ambient Pressure Photoelectron Spectroscopy Using Soft X-ray and Hard

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    X-ray, and its applications in electrochemistry | Stanford Synchrotron Radiation Lightsource Ambient Pressure Photoelectron Spectroscopy Using Soft X-ray and Hard X-ray, and its applications in electrochemistry Friday, December 14, 2012 - 3:30pm SSRL, Bldg. 137, room 322 Zhi Liu The synchrotron based ambient pressure x-ray photoelectron spectroscopy (AP-XPS) endstation[1] pioneered at ALS based on differentially pumped electron energy analyzer has been recognized by scientific communities as

  16. A doubly curved elliptical crystal spectrometer for the study of localized x-ray absorption in hot plasmas

    SciTech Connect (OSTI)

    Cahill, Adam D. Hoyt, Cad L.; Pikuz, Sergei A.; Shelkovenko, Tania; Hammer, David A.

    2014-10-15

    X-ray absorption spectroscopy is a powerful tool for the diagnosis of plasmas over a wide range of both temperature and density. However, such a measurement is often limited to probing plasmas with temperatures well below that of the x-ray source in order to avoid object plasma emission lines from obscuring important features of the absorption spectrum. This has excluded many plasmas from being investigated by this technique. We have developed an x-ray spectrometer that provides the ability to record absorption spectra from higher temperature plasmas than the usual approach allows without the risk of data contamination by line radiation emitted by the plasma under study. This is accomplished using a doubly curved mica crystal which is bent both elliptically and cylindrically. We present here the foundational work in the design and development of this spectrometer along with initial results obtained with an aluminum x-pinch as the object plasma.

  17. Core and Valence Excitations in Resonant X-ray Spectroscopy using Restricted Excitation Window Time-dependent Density Functional Theory

    SciTech Connect (OSTI)

    Zhang, Yu; Biggs, Jason D.; Healion, Daniel; Govind, Niranjan; Mukamel, Shaul

    2012-11-21

    We report simulations of X-ray absorption near edge structure (XANES), resonant inelastic X-ray scattering (RIXS) and 1D stimulated X-ray Raman spectroscopy (SXRS) signals of cysteine at the oxygen, nitrogen and sulfur K and L2,3 edges. The simulated XANES signals from the restricted window time-dependent density functional theory (REW-TDDFT) and the static exchange (STEX) method are compared with experiments, showing that REW-TDDFT is more accurate and computationally less expensive than STEX. Simulated RIXS and 1D SXRS signals from REW-TDDFT give some insights on the correlation of different excitations in the molecule.

  18. Removal of Ca2+ from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn4O5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Lohmiller, Thomas; Shelby, Megan L.; Long, Xi; Yachandra, Vittal K.; Yano, Junko

    2015-05-19

    We studied Ca2+ -depleted and Ca2+ -reconstituted spinach photosystem II using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca2+ ion in the Mn4O5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca2+ -depleted S1 (S1') and S2 (S2') states, the S2'YZ• state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca2+ -reconstituted S1 state. Polarized Mn K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all statesmore » of Ca2+ -depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca2+ -containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca2+ ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca2+ ion in the OEC is not critical for structural maintenance of the cluster, at least in the S1 and S2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca2+ removal are discussed, attributing to the Ca2+ ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to YZ• (D1-Tyr161).« less

  19. ON RELATIVISTIC DISK SPECTROSCOPY IN COMPACT OBJECTS WITH X-RAY CCD CAMERAS

    SciTech Connect (OSTI)

    Miller, J. M.; Cackett, E. M. [Department of Astronomy, University of Michigan, 500 Church Street, Ann Arbor, MI 48109 (United States); D'Ai, A. [Dipartimento di Scienze Fisiche ed Astronomiche, Universita di Palermo, Palermo (Italy); Bautz, M. W.; Nowak, M. A. [Kavli Institute for Astrophysics and Space Research, MIT, 77 Massachusetts Avenue, Cambridge, MA 02139 (United States); Bhattacharyya, S. [Department of Astronomy and Astrophysics, Tata Institute of Fundamental Research, Mumbai 400005 (India); Burrows, D. N.; Kennea, J. [Department of Astronomy and Astrophysics, Pennsylvania State University, 525 Davey Lab, College Park, PA 16802 (United States); Fabian, A. C.; Reis, R. C. [Institute of Astronomy, University of Cambridge, Madingley Road, Cambridge, CB3 OHA (United Kingdom); Freyberg, M. J.; Haberl, F. [Max-Planck-Institut fuer extraterrestrische Physik, Giessenbachstrasse, 85748 Garching (Germany); Strohmayer, T. E. [Astrophysics Science Division, NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Tsujimoto, M., E-mail: jonmm@umich.ed [Japan Aerospace Exploration Agency, Institute of Space and Astronomical Sciences, 3-1-1 Yoshino-dai, Sagamihara, Kanagawa 229-8510 (Japan)

    2010-12-01

    X-ray charge-coupled devices (CCDs) are the workhorse detectors of modern X-ray astronomy. Typically covering the 0.3-10.0 keV energy range, CCDs are able to detect photoelectric absorption edges and K shell lines from most abundant metals. New CCDs also offer resolutions of 30-50 (E/{Delta}E), which is sufficient to detect lines in hot plasmas and to resolve many lines shaped by dynamical processes in accretion flows. The spectral capabilities of X-ray CCDs have been particularly important in detecting relativistic emission lines from the inner disks around accreting neutron stars and black holes. One drawback of X-ray CCDs is that spectra can be distorted by photon 'pile-up', wherein two or more photons may be registered as a single event during one frame time. We have conducted a large number of simulations using a statistical model of photon pile-up to assess its impacts on relativistic disk line and continuum spectra from stellar-mass black holes and neutron stars. The simulations cover the range of current X-ray CCD spectrometers and operational modes typically used to observe neutron stars and black holes in X-ray binaries. Our results suggest that severe photon pile-up acts to falsely narrow emission lines, leading to falsely large disk radii and falsely low spin values. In contrast, our simulations suggest that disk continua affected by severe pile-up are measured to have falsely low flux values, leading to falsely small radii and falsely high spin values. The results of these simulations and existing data appear to suggest that relativistic disk spectroscopy is generally robust against pile-up when this effect is modest.

  20. Core and Valence Excitations in Resonant X-ray Spectroscopy using...

    Office of Scientific and Technical Information (OSTI)

    Window Time-dependent Density Functional Theory Citation Details In-Document Search ... Window Time-dependent Density Functional Theory We report simulations of X-ray absorption ...

  1. 3D Imaging of Nickel Oxidation States using Full Field X-ray Absorption Near Edge Structure Nanotomography

    SciTech Connect (OSTI)

    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.

  2. New developments in high pressure x-ray spectroscopy beamline at High Pressure Collaborative Access Team

    SciTech Connect (OSTI)

    Xiao, Y. M. Chow, P.; Boman, G.; Bai, L. G.; Rod, E.; Bommannavar, A.; Kenney-Benson, C.; Sinogeikin, S.; Shen, G. Y.

    2015-07-15

    The 16 ID-D (Insertion Device - D station) beamline of the High Pressure Collaborative Access Team at the Advanced Photon Source is dedicated to high pressure research using X-ray spectroscopy techniques typically integrated with diamond anvil cells. The beamline provides X-rays of 4.5-37 keV, and current available techniques include X-ray emission spectroscopy, inelastic X-ray scattering, and nuclear resonant scattering. The recent developments include a canted undulator upgrade, 17-element analyzer array for inelastic X-ray scattering, and an emission spectrometer using a polycapillary half-lens. Recent development projects and future prospects are also discussed.

  3. Development of Time Resolved X-ray Spectroscopy in High Intensity...

    Office of Scientific and Technical Information (OSTI)

    Title: Development of Time Resolved X-ray Spectroscopy in High Intensity Laser-Plasma Interactions Authors: Notley, M ; Weber, R ; Fell, B ; Jefferies, J ; Freeman, R ; Mackinnon, ...

  4. SSRL School on Synchrotron X-ray Spectroscopy Techniques in Environmen...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Transportation Tourism & Dining SSRL School on Synchrotron X-ray Spectroscopy Techniques in Environmental and Materials Sciences: Theory and Application June 2-5, 2009 Group...

  5. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectropscopy using IFEFFIT

    SciTech Connect (OSTI)

    Ravel, B.; Newville, M.

    2010-07-20

    A software package for the analysis of X-ray absorption spectroscopy (XAS) data is presented. This package is based on the IFEFFIT library of numerical and XAS algorithms and is written in the Perl programming language using the Perl/Tk graphics toolkit. The programs described here are: (i) ATHENA, a program for XAS data processing, (ii) ARTEMIS, a program for EXAFS data analysis using theoretical standards from FEFF and (iii) HEPHAESTUS, a collection of beamline utilities based on tables of atomic absorption data. These programs enable high-quality data analysis that is accessible to novices while still powerful enough to meet the demands of an expert practitioner. The programs run on all major computer platforms and are freely available under the terms of a free software license.

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

    SciTech Connect (OSTI)

    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.

  7. Phase Effects on Mesoscale Object X-ray Absorption Images

    SciTech Connect (OSTI)

    Martz, Jr., H E; Aufderheide, M B; Barty, A; Lehman, S K; Kozioziemski, B J; Schneberk, D J

    2004-09-24

    At Lawrence Livermore National Laboratory particular emphasis is being placed on the nondestructive characterization (NDC) of 'mesoscale' objects.[Martz and Albrecht 2003] We define mesoscale objects as objects that have mm extent with {micro}m features. Here we confine our discussions to x-ray imaging methods applicable to mesoscale object characterization. The goal is object recovery algorithms including phase to enable emerging high-spatial resolution x-ray imaging methods to ''see'' inside or image mesoscale-size materials and objects. To be successful our imaging characterization effort must be able to recover the object function to one micrometer or better spatial resolution over a few millimeters field-of-view with very high contrast.

  8. Stimulated X-Ray Emission for Spectroscopy | Stanford Synchrotron...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Room 108A Speaker: Clemens Weninger, Max Planck Institute for the Physics of Complex Systems Program Description The recent advance of x-ray free electron lasers (XFELs)...

  9. Staff Research Physicist (X-Ray Spectroscopy) | Princeton Plasma...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    of X-ray spectrometers for high energy density plasma at the National Ignition Facility (NIF) at the Lawrence Livermore National Laboratory (LLNL, Livermore, California). In...

  10. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies...

    Office of Scientific and Technical Information (OSTI)

    Journal Article: In Situ Ambient Pressure X-ray ... Citation Details In-Document Search Title: In Situ Ambient ... Resource Relation: Journal Name: Scientific Reports; Journal ...

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

    SciTech Connect (OSTI)

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

    2010-11-24

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

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

    SciTech Connect (OSTI)

    Tan, G.O.

    1993-06-01

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

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

    SciTech Connect (OSTI)

    Vaverka, A M

    2008-07-15

    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/SiO{sub 2} 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.

  14. Absorption experiments on x-ray-heated mid-{ital Z} constrained samples

    SciTech Connect (OSTI)

    Perry, T.S.; Springer, P.T.; Fields, D.F.; Bach, D.R.; Serduke, F.J.; Iglesias, C.A.; Rogers, F.J.; Nash, J.K.; Chen, M.H.; Wilson, B.G.; Goldstein, W.H.; Rozsynai, B.; Ward, R.A.; Kilkenny, J.D.; Doyas, R.; Da Silva, L.B.; Back, C.A.; Cauble, R.; Davidson, S.J.; Foster, J.M.; Smith, C.C.; Bar-Shalom, A.; Lee, R.W.

    1996-11-01

    Results of a niobium absorption experiment are presented that represent a major step in the development of techniques necessary for the quantitative characterization of hot, dense matter. The general requirements for performing quantitative analyses of absorption spectra are discussed. Hydrodynamic simulations are used to illustrate the behavior of tamped x-ray-heated matter and to indicate potential two-dimensional problems inherent in the technique. The absorption spectrum of a low-{ital Z} material, in this case aluminum, mixed with niobium provides a temperature diagnostic, which together with radiography as a density diagnostic fully characterizes the sample. A discussion is presented of opacity calculations and a comparison to the measurements is given that illustrates the need for experiments to provide a critical test of theory. The experimental technique is placed in context with a review of previous measurements using absorption spectroscopy to probe hot, dense matter. It is shown that the overall experimental concepts, although understood, were not always achieved in previous experiments. {copyright} {ital 1996 The American Physical Society.}

  15. Johann Spectrometer for High Resolution X-ray Spectroscopy

    SciTech Connect (OSTI)

    Machek, Pavel; Froeba, Michael; Welter, Edmund; Caliebe, Wolfgang; Brueggmann, Ulf; Draeger, Guenter

    2007-01-19

    A newly designed vacuum Johann spectrometer with a large focusing analyzer crystal for inelastic x-ray scattering and high resolution fluorescence spectroscopy has been installed at the DORIS III storage ring. Spherically bent crystals with a maximum diameter of 125 mm, and cylindrically bent crystals are employed as dispersive optical elements. Standard radius of curvature of the crystals is 1000 mm, however, the design of the mechanical components also facilitates measurements with smaller and larger bending radii. Up to four crystals are mounted on a revolving crystal changer which enables crystal changes without breaking the vacuum. The spectrometer works at fixed Bragg angle. It is preferably designed for the measurements in non-scanning mode with a broad beam spot, and offers a large flexibility to set the sample to the optimum position inside the Rowland circle. A deep depletion CCD camera is employed as a position sensitive detector to collect the energy-analyzed photons on the circumference of the Rowland circle. The vacuum in the spectrometer tank is typically 10-6 mbar. The sample chamber is separated from the tank either by 25 {mu}m thick Kapton windows, which allows samples to be measured under ambient conditions, or by two gate valves. The spectrometer is currently installed at wiggler beamline W1 whose working range is 4-10.5 keV with typical flux at the sample of 5x1010photons/s/mm2. The capabilities of the spectrometer are illustrated by resonant inelastic experiments on 3d transition metals and rare earth compounds, and by chemical shift measurements on chromium compounds.

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

    SciTech Connect (OSTI)

    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.

  17. Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Lu, Qingquan; Zhang, Jian; Peng, Pan; Zhang, Guanghui; Huang, Zhiliang; Yi, Hong; Miller, Jeffrey T.; Lei, Aiwen

    2015-05-26

    An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(II) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(I) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(II) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfonesmore » are synthesized with good to excellent yields under mild conditions.« less

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

    SciTech Connect (OSTI)

    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.

  19. Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis

    SciTech Connect (OSTI)

    Lu, Qingquan; Zhang, Jian; Peng, Pan; Zhang, Guanghui; Huang, Zhiliang; Yi, Hong; Miller, Jeffrey T.; Lei, Aiwen

    2015-05-26

    An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(II) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(I) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(II) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions.

  20. Soft X-ray Spectroscopy Study of the Electronic Structure of Oxidized and Partially Oxidized Magnetite Nanoparticles

    SciTech Connect (OSTI)

    Gilbert, Benjamin; Katz, Jordan E.; Denlinger, Jonathan D.; Yin, Yadong; Falcone, Roger; Waychunas, Glenn A.

    2010-10-24

    The crystal structure of magnetite nanoparticles may be transformed to maghemite by complete oxidation, but under many relevant conditions the oxidation is partial, creating a mixed-valence material with structural and electronic properties that are poorly characterized. We used X-ray diffraction, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, and soft X-ray absorption and emission spectroscopy to characterize the products of oxidizing uncoated and oleic acid-coated magnetite nanoparticles in air. The oxidization of uncoated magnetite nanoparticles creates a material that is structurally and electronically indistinguishable from maghemite. By contrast, while oxidized oleic acid-coated nanoparticles are also structurally indistinguishable from maghemite, Fe L-edge spectroscopy revealed the presence of interior reduced iron sites even after a 2-year period. We used X-ray emission spectroscopy at the O K-edge to study the valence bands (VB) of the iron oxide nanoparticles, using resonant excitation to remove the contributions from oxygen atoms in the ligands and from low-energy excitations that obscured the VB edge. The bonding in all nanoparticles was typical of maghemite, with no detectable VB states introduced by the long-lived, reduced-iron sites in the oleic acid-coated sample. However, O K-edge absorption spectroscopy observed a 0.2 eV shift in the position of the lowest unoccupied states in the coated sample, indicating an increase in the semiconductor band gap relative to bulk stoichiometric maghemite that was also observed by optical absorption spectroscopy. The results show that the ferrous iron sites within ferric iron oxide nanoparticles coated by an organic ligand can persist under ambient conditions with no evidence of a distinct interior phase and can exert an effect on the global electronic and optical properties of the material. This phenomenon resembles the band gap enlargement caused by electron accumulation in the

  1. Finite temperature effects on the X-ray absorption spectra of lithium compounds: First-principles interpretation of X-ray Raman measurements

    SciTech Connect (OSTI)

    Pascal, Tod A.; Prendergast, David; Boesenberg, Ulrike; Kostecki, Robert; Richardson, Thomas J.; Weng, Tsu-Chien; Sokaras, Dimosthenis; Nordlund, Dennis; McDermott, Eamon; Moewes, Alexander; Cabana, Jordi

    2014-01-21

    We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li{sub 2}SO{sub 4}, Li{sub 2}O, Li{sub 3}N, and Li{sub 2}CO{sub 3} using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole approach. Based on thermodynamic sampling via ab initio molecular dynamics simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. The excellent agreement with high-resolution XRS measurements validates the accuracy of our first-principles approach to simulating XAS, and provides both accurate benchmarks for model compounds and a predictive theoretical capability for identification and characterization of multi-component systems, such as lithium-ion batteries, under working conditions.

  2. Magnetic circular dichroism in x-ray absorption and core-level photoemission

    SciTech Connect (OSTI)

    Tobin, J.G.; Waddill, G.D.; Gouder, T.H.; Colmenares, C.A.; Pappas, D.P.

    1993-03-17

    Here is reported observation of magnetic circular dichroism in both x-ray absorption and core-level photoemission of ultra thin magnetic films using circularly polarized x-rays. Iron films (1--4 ML) grown on a Cu(001) substrate at 150 K and magnetized perpendicular to the surface show dramatic changes in the L{sub 2,3} branching ratio for different x-ray polarizations. For linearly-polarized x-rays perpendicular to the magnetic axis of the sample the branching ratio was 0.75. For films {ge} 2 ML, this ratio varied from 0.64 to 0.85 for photon spin parallel and anti-parallel, respectively, to the magnetic axis. This effect was observed either by changing the x-ray helicity for a fixed magnetic axis, or by reversing the magnetic axis for a fixed x-ray helicity. Our observation can be analyzed within a simple one-electron picture, if the raw branching ratios are no so that the linear value becomes statistical Furthermore, warming the films to {approximately}300 K eliminated this effect, indicating a loss of magnetization in the film over a temperature range of {approximately}30 K. Finally, reversing the relative orientation of the photon spin and the magnetic axis from parallel to anti-parallel allowed measurement of the exchange splitting of the Fe 2p and 3p core levels which were found to be 0.3 eV and 0.2 eV. respectively. These results are consistent with earlier studies, but the use of off-plane circularly-polarized x-rays from a bending magnet monochromator offers {approximately}2 orders of magnitude greater intensity than typical spin-polarization measurements. Finally, we have performed preliminary x-ray absorption studies of UFe{sub 2}, demonstrating the feasibilty of MCD measurements in 5f as well as 3d materials.

  3. X-Ray Spectroscopy of the Mn(4) Ca Cluster in the Water-Oxidation...

    Office of Scientific and Technical Information (OSTI)

    Ca Cluster in the Water-Oxidation Complex of Photosystem II Citation Details In-Document Search Title: X-Ray Spectroscopy of the Mn(4) Ca Cluster in the Water-Oxidation Complex ...

  4. Probing hot-electron effects in wide area plasmonic surfaces using X-ray photoelectron spectroscopy

    SciTech Connect (OSTI)

    Ayas, Sencer; Cupallari, Andi; Dana, Aykutlu

    2014-12-01

    Plasmon enhanced hot carrier formation in metallic nanostructures increasingly attracts attention due to potential applications in photodetection, photocatalysis, and solar energy conversion. Here, hot-electron effects in nanoscale metal-insulator-metal (MIM) structures are investigated using a non-contact X-ray photoelectron spectroscopy based technique using continuous wave X-ray and laser excitations. The effects are observed through shifts of the binding energy of the top metal layer upon excitation with lasers of 445, 532, and 650?nm wavelength. The shifts are polarization dependent for plasmonic MIM grating structures fabricated by electron beam lithography. Wide area plasmonic MIM surfaces fabricated using a lithography free route by the dewetting of evaporated Ag on HfO{sub 2} exhibit polarization independent optical absorption and surface photovoltage. Using a simple model and making several assumptions about the magnitude of the photoemission current, the responsivity and external quantum efficiency of wide area plasmonic MIM surfaces are estimated as 500?nA/W and 11 10{sup ?6} for 445?nm illumination.

  5. Design of Molecular Solar Cells via Feedback from Soft X-ray Spectroscopy

    SciTech Connect (OSTI)

    Himpsel, Franz J.

    2015-06-12

    Spectroscopy with soft X-rays was used to develop new materials and novel designs for solar cells and artificial photosynthesis. In order to go beyond the widely-used trial-and-error approach of gradually improving a particular design, we started from the most general layout of a solar cell (or a photo-electrochemical device) and asked which classes of materials are promising for best performance. For example, the most general design of a solar cell consists of a light absorber, an electron donor, and an electron acceptor. These are characterized by four energy levels, which were measured by a combination of spectroscopic X-ray techniques. Tuning synchrotron radiation to the absorption edges of specific elements provided element- and bond-selectivity. The spectroscopic results were complemented by state-of-the-art calculations of the electronic states. These helped explaining the observed energy levels and the orbitals associated with them. The calculations were extended to a large class of materials (for example thousands of porphyrin dye complexes) in order to survey trends in the energy level structure. A few highlights serve as examples: 1) Organic molecules combining absorber, donor, and acceptor with atomic precision. 2) Exploration of highly p-doped diamond films as inert, transparent electron donors. 3) Surface-sensitive characterization of nanorod arrays used as photoanodes in water splitting. 4) Computational design of molecular complexes for efficient solar cells using two photons.

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

    SciTech Connect (OSTI)

    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.

  7. Observing heme doming in myoglobin with femtosecond X-ray absorption spectroscopya)

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Levantino, M.; Lemke, H. T.; Schir, G.; Glownia, M.; Cupane, A.; Cammarata, M.

    2015-07-01

    We report time-resolved X-ray absorption measurements after photolysis of carbonmonoxy myoglobin performed at the LCLS X-ray free electron laser with nearly 100 fs (FWHM) time resolution. Data at the Fe K-edge reveal that the photoinduced structural changes at the heme occur in two steps, with a faster (~70 fs) relaxation preceding a slower (~400 fs) one. We tentatively attribute the first relaxation to a structural rearrangement induced by photolysis involving essentially only the heme chromophore and the second relaxation to a residual Fe motion out of the heme plane that is coupled to the displacement of myoglobin F-helix.

  8. ISMabs: A COMPREHENSIVE X-RAY ABSORPTION MODEL FOR THE INTERSTELLAR MEDIUM

    SciTech Connect (OSTI)

    Gatuzz, E.; Mendoza, C.; García, J.; Kallman, T. R.; Gorczyca, T. W. E-mail: claudio@ivic.gob.ve E-mail: timothy.r.kallman@nasa.gov

    2015-02-10

    We present an X-ray absorption model for the interstellar medium, to be referred to as ISMabs, that takes into account both neutral and ionized species of cosmically abundant elements, and includes the most accurate atomic data available. Using high-resolution spectra from eight X-ray binaries obtained with the Chandra High Energy Transmission Grating Spectrometer, we proceed to benchmark the atomic data in the model particularly in the neon K-edge region. Compared with previous photoabsorption models, which solely rely on neutral species, the inclusion of ions leads to improved spectral fits. Fit parameters comprise the column densities of abundant contributors that allow direct estimates of the ionization states. ISMabs is provided in the appropriate format to be implemented in widely used X-ray spectral fitting packages such as XSPEC, ISIS, and SHERPA.

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

    SciTech Connect (OSTI)

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

    2012-01-01

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

  10. X-ray Spectroscopy for Quality Control of Chemotherapy Drugs

    SciTech Connect (OSTI)

    Greaves, E. D.; Barros, H.; Bermudez, J.; Sajo-Bohus, L.; Angeli-Greaves, M.

    2007-10-26

    We develop a method, employing Compton peak standardization and the use of matrix-matched spiked samples with Total Reflection X-ray Fluorescence (TXRF), for the determination of platinum plasma concentrations of patients undergoing chemotherapy with Pt-bearing drugs. Direct blood plasma analysis attains Pt detection limits of 70 ng/ml. Measurement results of prescribed drug doses are compared to achieved blood Pt concentrations indicating a lack of expected correlations. Direct analysis of Pt-containing infused drugs from a variety of suppliers indicates cases of abnormal concentrations which raises quality control issues. We demonstrate the potential usefulness of the method for pharmacokinetic studies or for routine optimization and quality control of Pt chemotherapy treatments.

  11. Synchrotron x-ray spectroscopy studies of valence and magnetic state in europium metal to extreme pressures

    SciTech Connect (OSTI)

    Bi, W.; Souza-Neto, N.M.; Haskel, D.; Fabbris, G.; Alp, E.E.; Zhao, J.; Hennig, R.G.; Abd-Elmeguid, M.M.; Meng, Y.; McCallum, Ralph W.; Dennis, Kevin; Schilling, J.S.

    2012-05-22

    In order to probe the changes in the valence state and magnetic properties of Eu metal under extreme pressure, x-ray absorption near-edge spectroscopy, x-ray magnetic circular dichroism, and synchrotron Mössbauer spectroscopy experiments were carried out. The Mössbauer isomer shift exhibits anomalous pressure dependence, passing through a maximum near 20 GPa. Density functional theory has been applied to give insight into the pressure-induced changes in both Eu's electronic structure and Mössbauer isomer shift. Contrary to previous reports, Eu is found to remain nearly divalent to the highest pressures reached (87 GPa) with magnetic order persisting to at least 50 GPa. These results should lead to a better understanding of the nature of the superconducting state found above 75 GPa and of the sequence of structural phase transitions observed to 92 GPa.

  12. The X-ray correlation spectroscopy instrument at the Linac Coherent Light Source

    SciTech Connect (OSTI)

    Alonso-Mori, Roberto; Caronna, Chiara; Chollet, Matthieu; Curtis, Robin; Damiani, Daniel S.; Defever, Jim; Feng, Yiping; Flath, Daniel L.; Glownia, James M.; Lee, Sooheyong; Lemke, Henrik T.; Nelson, Silke; Bong, Eric; Sikorski, Marcin; Song, Sanghoon; Srinivasan, Venkat; Stefanescu, Daniel; Zhu, Diling; Robert, Aymeric

    2015-03-03

    The X-ray Correlation Spectroscopy instrument is dedicated to the study of dynamics in condensed matter systems using the unique coherence properties of free-electron lasers. It covers a photon energy range of 4–25 keV. The intrinsic temporal characteristics of the Linac Coherent Light Source, in particular the 120 Hz repetition rate, allow for the investigation of slow dynamics (milliseconds) by means of X-ray photon correlation spectroscopy. Double-pulse schemes could probe dynamics on the picosecond timescale. In addition, a description of the instrument capabilities and recent achievements is presented.

  13. The X-ray correlation spectroscopy instrument at the Linac Coherent Light Source

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Alonso-Mori, Roberto; Caronna, Chiara; Chollet, Matthieu; Curtis, Robin; Damiani, Daniel S.; Defever, Jim; Feng, Yiping; Flath, Daniel L.; Glownia, James M.; Lee, Sooheyong; et al

    2015-03-03

    The X-ray Correlation Spectroscopy instrument is dedicated to the study of dynamics in condensed matter systems using the unique coherence properties of free-electron lasers. It covers a photon energy range of 4–25 keV. The intrinsic temporal characteristics of the Linac Coherent Light Source, in particular the 120 Hz repetition rate, allow for the investigation of slow dynamics (milliseconds) by means of X-ray photon correlation spectroscopy. Double-pulse schemes could probe dynamics on the picosecond timescale. In addition, a description of the instrument capabilities and recent achievements is presented.

  14. Temperature dependence of the Pd [ital K]-edge extended x-ray-absorption fine structure of PdC[sub [ital x

    SciTech Connect (OSTI)

    McCaulley, J.A. (Hoechst Celanese Research Division, Robert L. Mitchell Technical Center, 86 Morris Avenue, Summit, New Jersey 07901 (United States))

    1993-03-01

    Pd [ital K]-edge extended x-ray-absorption fine-structure (EXAFS) and x-ray-absorption near-edge-structure (XANES) measurements were performed on a Pd carbide phase, PdC[sub [ital x

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

    SciTech Connect (OSTI)

    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.

  16. Absorption and Phase Contrast X-Ray Imaging in Paleontology Using Laboratory and Synchrotron Sources

    SciTech Connect (OSTI)

    Bidola, Pidassa; Stockmar, Marco; Achterhold, Klaus; Pfeiffer, Franz; Pacheco, Mirian L.A.F.; Soriano, Carmen; Beckmann, Felix; Herzen, Julia

    2015-10-01

    X-ray micro-computed tomography (CT) is commonly used for imaging of samples in biomedical or materials science research. Owing to the ability to visualize a sample in a nondestructive way, X-ray CT is perfectly suited to inspect fossilized specimens, which are mostly unique or rare. In certain regions of the world where important sedimentation events occurred in the Precambrian geological time, several fossilized animals are studied to understand questions related to their origin, environment, and life evolution. This article demonstrates the advantages of applying absorption and phase-contrast CT on the enigmatic fossil Corumbella werneri, one of the oldest known animals capable of building hard parts, originally discovered in Corumba (Brazil). Different tomographic setups were tested to visualize the fossilized inner structures: a commercial laboratory-based CT device, two synchrotron-based imaging setups using conventional absorption and propagation-based phase contrast, and a commercial X-ray microscope with a lens-coupled detector system, dedicated for radiography and tomography. Based on our results we discuss the strengths and weaknesses of the different imaging setups for paleontological studies.

  17. X-ray absorption and electrochemical studies of direct methanol fuel cell catalysts

    SciTech Connect (OSTI)

    Zurawski, D.J.; Aldykiewicz, A.J. Jr.; Baxter, S.F.; Krumpelt, M.

    1996-12-31

    In order for polymer electrolyte fuel cells to operate directly on methanol instead of hydrogen, a distinct advantage for portable applications, methanol oxidation must be catalyzed effectively in the acidic environment of the cell. Platinum-ruthenium and platinum-ruthenium oxide are generally considered to be the most active catalysts for this purpose. The presence of ruthenium significantly enhances the activity of platinum in these catalysts, for reasons not yet fully understood. We are using X-ray absorption spectroscopy (XAS) and electrochemical techniques to evaluate the mechanisms proposed to account for this enhancement in order to further improve the catalyst`s activity. We are considering three enhancement mechanisms. An intermediate in the oxidation of methanol on platinum is carbon monoxide and its oxidation is the rate-determining step in the overall oxidation mechanism. It has been proposed that ruthenium facilitates the removal of carbon monoxide from the platinum surface. First, it has been proposed that ruthenium decreases the strength of the platinum-carbon monoxide bond. Carbon monoxide bonds to the catalyst by interacting with the d-band of platinum, therefore a change in the d-band occupancy of platinum as a result of alloying may influence the bond strength of carbon monoxide. Another proposed enhancement mechanism involves lowering of the potential for the formation of the CO-oxidizing species. Finally, the binary catalysts may have a structure which is more conducive to the methanol dehydrogenation and carbon monoxide reactions. Based on these three proposed enhancement mechanisms, a goal of this study is to correlate catalyst electronic properties, structure, and oxidation state with the performance of proton-exchange membrane (Nafion) direct methanol fuel cells.

  18. Passive Spectroscopy Bolometers, Grating- And X-Ray Imaging Crystal Spectrometers

    SciTech Connect (OSTI)

    Bitter, M; Hill, K W; Scott, S; Paul, S; Ince-Cushmann, A; Reinke, M; Rice, J; Beiersdorfer, P; Gu, M F; Lee, S G; Broennimann, C; Eikenberry, E F

    2007-11-07

    This tutorial gives a brief introduction into passive spectroscopy and describes the working principles of bolometers, a high-resolution grating spectrometer, and a novel X-ray imaging crystal spectrometer, which is of particular interest for profile measurements of the ion temperature and plasma rotation velocity on ITER and future burning plasma experiments.

  19. X-Ray Absorption Studies of Vanadium-Containing Metal Oxide Nanocrystals

    SciTech Connect (OSTI)

    Hohn, Keith, L.

    2006-01-09

    Metal oxide nanocrystals offer significant potential for use as catalysts or catalyst supports due to their high surface areas and unique chemical properties that result from the high number of exposed corners and edges. However, little is known about the catalytic activity of these materials, especially as oxidation catalysts. This research focused on the preparation, characterization and use of vanadium-containing nanocrystals as selective oxidation catalysts. Three vanadium-containing nanocrystals were prepared using a modified sol-gel procedure: V/MgO, V/SiO2, and vanadium phosphate (VPO). These represent active oxidation catalysts for a number of industrially relevant reactions. The catalysts were characterized by x-ray diffraction and Raman, UV-VIS, infrared and x-ray absorption spectroscopies with the goal of determining the primary structural and chemical differences between nanocrystals and microcrystals. The catalytic activity of these catalysts was also studied in oxidative dehydrogenation of butane and methanol oxidation to formaldehyde. V/MgO nanocrystals were investigated for activity in oxidative dehydrogenation of butane and compared to conventional V/MgO catalysts. Characterization of V/MgO catalysts using Raman spectroscopy and x-ray absorption spectroscopy showed that both types of catalysts contained magnesium orthovanadate at vanadium loadings below 15 weight%, but above that loading, magnesium pyrovanadate may have been present. In general, MgO nanocrystals had roughly half the crystal size and double the surface area of the conventional MgO. In oxidative dehydrogenation of butane, nanocrystalline V/MgO gave higher selectivity to butene than conventional V/MgO at the same conversion. This difference was attributed to differences in vanadium domain size resulting from the higher surface areas of the nanocrystalline support, since characterization suggested that similar vanadium phases were present on both types of catalysts. Experiments in

  20. Probing Reaction Dynamics of Transition-Metal Complexes in Solution via Time-Resolved X-ray Spectroscopy

    SciTech Connect (OSTI)

    Huse, Nils; Khalil, Munira; Kim, Tae Kyu; Smeigh, Amanda L.; Jamula, Lindsey; McCusker, James K.; Schoenlein, Robert W.

    2009-05-24

    We report measurements of the photo-induced Fe(II) spin crossover reaction dynamics in solution via time-resolved x-ray absorption spectroscopy. EXAFS measurements reveal that the iron?nitrogen bond lengthens by 0.21+-0.03 Angstrom in the high-spin transient excited state relative to the ground state. XANES measurements at the Fe L-edge show directly the influence of the structural change on the ligand-field splitting of the Fe(II) 3d orbitals associated with the spin transition.

  1. ALS X-Rays Shine a New Light on Catalysis

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    were able to directly observe redox processes in thin-film iron and cobalt perovskite oxide electrocatalysts using surface-sensitive, x-ray absorption spectroscopy while...

  2. X-ray-absorption study of CuBr at high pressure

    SciTech Connect (OSTI)

    Tranquada, J.M.; Ingalls, R.

    1986-09-15

    The x-ray-absorption spectrum of cuprous bromide has been measured as a function of pressure. The x-ray-absorption near-edge structure proved to be an excellent indicator of high-pressure phase transitions in this material. The normalized ''white-line'' peak heights at both the Cu and Br K-italic edges decreased on entering the tetragonal phase and increased in going to the NaCl structure. The zinc-blende to tetragonal phase transition took place over a very narrow pressure range centered at 46 +- 5 kbar. The transformation from the tetragonal to the NaCl structure, on the other hand, showed a broad mixed-phase region, suggesting a nucleation-and-growth mechanism for the transition. The mixed-phase region was centered at 75 +- 6 kbar. No evidence of a phase between the zinc-blende and tetragonal phases was observed, presumably because it does not exist. Analysis of the extended x-ray-absorption fine-structure (EXAFS) clearly showed that there is no change in coordination in going from the zinc-blende to the tetragonal phase although the nearest-neighbor distance increases slightly. A much larger increase in R-italic/sub 1/ occurs at the transition to the NaCl structure, where the coordination increases from 4 to 6. The mean-square deviation in the nearest-neighbor bond length, sigma/sub 1//sup 2/, appears to be a fairly smooth function of nearest-neighbor distance, decreasing (or increasing) as R-italic/sub 1/ decreases (or increases) more or less independent of structure. Evidence from the literature was presented to suggest that the zinc-blende to tetragonal transition in CuBr (and also CuCl) should occur by shear deformation.

  3. Sequential single shot X-ray photon correlation spectroscopy at the SACLA free electron laser

    SciTech Connect (OSTI)

    Lehmkühler, Felix; Kwaśniewski, Paweł; Roseker, Wojciech; Fischer, Birgit; Schroer, Martin A.; Tono, Kensuke; Katayama, Tetsuo; Sprung, Michael; Sikorski, Marcin; Song, Sanghoon; Glownia, James; Chollet, Matthieu; Nelson, Silke; Robert, Aymeric; Gutt, Christian; Yabashi, Makina; Ishikawa, Tetsuya; Grübel, Gerhard

    2015-11-27

    In this study, hard X-ray free electron lasers allow for the first time to access dynamics of condensed matter samples ranging from femtoseconds to several hundred seconds. In particular, the exceptional large transverse coherence of the X-ray pulses and the high time-averaged flux promises to reach time and length scales that have not been accessible up to now with storage ring based sources. However, due to the fluctuations originating from the stochastic nature of the self-amplified spontaneous emission (SASE) process the application of well established techniques such as X-ray photon correlation spectroscopy (XPCS) is challenging. Here we demonstrate a single-shot based sequential XPCS study on a colloidal suspension with a relaxation time comparable to the SACLA free-electron laser pulse repetition rate. High quality correlation functions could be extracted without any indications for sample damage. This opens the way for systematic sequential XPCS experiments at FEL sources.

  4. Combining X-ray Absorption and X-ray Diffraction Techniques for in Situ Studies of Chemical Transformations in Heterogeneous Catalysis: Advantages and Limitations

    SciTech Connect (OSTI)

    Frenkel, A.I.; Hanson, J.; Wang, Q.; Marinkovic, N.; Chen, J.G.; Barrio, L.; Si, R.; Lopez Camara, A.; Estrella, A.M.; Rodriguez, J.A.

    2011-08-05

    Recent advances in catalysis instrumentations include synchrotron-based facilities where time-resolved X-ray scattering and absorption techniques are combined in the same in situ or operando experiment to study catalysts at work. To evaluate the advances and limitations of this method, we performed a series of experiments at the new XAFS/XRD instrument in the National Synchrotron Light Source. Nearly simultaneous X-ray diffraction (XRD) and X-ray absorption fine-structure (XAFS) measurements of structure and kinetics of several catalysts under reducing or oxidizing conditions have been performed and carefully analyzed. For CuFe{sub 2}O{sub 4} under reducing conditions, the combined use of the two techniques allowed us to obtain accurate data on kinetics of nucleation and growth of metallic Cu. For the inverse catalyst CuO/CeO{sub 2} that underwent isothermal reduction (with CO) and oxidation (with O{sub 2}), the XAFS data measured in the same experiment with XRD revealed strongly disordered Cu species that went undetected by diffraction. These and other examples emphasize the unique sensitivity of these two complementary methods to follow catalytic processes in the broad ranges of length and time scales.

  5. Combining X-ray Absorption and X-ray Diffraction Techniques for in Situ Studies of Chemical Transformations in Heterogeneous Catalysis:Advantages and Limitations

    SciTech Connect (OSTI)

    A Frenkel; Q Wang; N Marinkovic; J Chen; L Barrio; R Si; A Lopez Camara; A Estella; J Rodriquez; J Hanson

    2011-12-31

    Recent advances in catalysis instrumentations include synchrotron-based facilities where time-resolved X-ray scattering and absorption techniques are combined in the same in situ or operando experiment to study catalysts at work. To evaluate the advances and limitations of this method, we performed a series of experiments at the new XAFS/XRD instrument in the National Synchrotron Light Source. Nearly simultaneous X-ray diffraction (XRD) and X-ray absorption fine-structure (XAFS) measurements of structure and kinetics of several catalysts under reducing or oxidizing conditions have been performed and carefully analyzed. For CuFe{sub 2}O{sub 4} under reducing conditions, the combined use of the two techniques allowed us to obtain accurate data on kinetics of nucleation and growth of metallic Cu. For the inverse catalyst CuO/CeO{sub 2} that underwent isothermal reduction (with CO) and oxidation (with O{sub 2}), the XAFS data measured in the same experiment with XRD revealed strongly disordered Cu species that went undetected by diffraction. These and other examples emphasize the unique sensitivity of these two complementary methods to follow catalytic processes in the broad ranges of length and time scales.

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

    SciTech Connect (OSTI)

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

    2015-01-26

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

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

    SciTech Connect (OSTI)

    Kaspar, Tiffany C.; Ney, A.; Mangham, Andrew N.; Heald, Steve M.; Joly, Yves; Ney, V.; Wilhelm, F.; Rogalev, A.; Yakou, Flora; Chambers, Scott A.

    2012-07-23

    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, O K-edge, N K-edge, and Ti K-edge. No evidence of structural disorder associated with a high concentration of oxygen vacancies is observed. Substitution of Fe for Ti could not be confirmed, although secondary phase Fe2O3 and metallic Fe can be ruled out. The similarity of the N K-edge spectra to O, and the presence of a strong x-ray linear dichroism (XLD) 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 qualitatively 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 valence Fe(II)/Fe(III) in the reduced (Fe,N):TiO2 film.

  8. Applying Kβ Valence-to-Core X-ray Emission Spectroscopy to Cu(I) Binding

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Proteins with Relevance to Peptidylglycine Monooxygenase Reactivity | Stanford Synchrotron Radiation Lightsource Applying Kβ Valence-to-Core X-ray Emission Spectroscopy to Cu(I) Binding Proteins with Relevance to Peptidylglycine Monooxygenase Reactivity Thursday, June 30, 2016 Copper serves as a redox center in metalloproteins, often cycling between the +1 and +2 oxidation states. Oxidases, such as petidylglycine monooxygenase (PHM), bind oxygen at Cu(I) sites giving rise to "oxo"

  9. Characterization of Gas Shales by X-ray Raman Spectroscopy | Stanford

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Synchrotron Radiation Lightsource Characterization of Gas Shales by X-ray Raman Spectroscopy Thursday, February 23, 2012 - 10:30am SSRL Third Floor Conference Room 137-322 Drew Pomerantz, Schlumberger Unconventional hydrocarbon resources such as gas shale and oil-bearing shale have emerged recently as economically viable sources of energy, dramatically altering America's energy landscape. Despite their importance, the basic chemistry and physics of shales are not understood as well as

  10. Characterization of Gas Shales by X-ray Raman Spectroscopy | Stanford

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Synchrotron Radiation Lightsource Characterization of Gas Shales by X-ray Raman Spectroscopy Monday, May 14, 2012 - 3:30pm SSRL Conference Room 137-322 Drew Pomerantz, Schlumberger Unconventional hydrocarbon resources such as gas shale and oil-bearing shale have emerged recently as economically viable sources of energy, dramatically altering America's energy landscape. Despite their importance, the basic chemistry and physics of shales are not understood as well as conventional reservoirs.

  11. In-situ X-ray Photoelectron Spectroscopy of a Catalyst for Artificial

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Photosynthesis | Stanford Synchrotron Radiation Lightsource In-situ X-ray Photoelectron Spectroscopy of a Catalyst for Artificial Photosynthesis Monday, June 30, 2014 Plants and other organisms use a process called photosynthesis to produce carbohydrates and oxygen from water and carbon dioxide using sunlight. Artificial photosynthesis replicates this process to produce energy in the form of usable fuels for human needs. Researches have been developing devices for artificial photosynthesis,

  12. Deciphering Ni sequestration in soil ferromanganese nodules by combining x-ray fluorescence, absorption and diffraction at micrometer scales of resolution

    SciTech Connect (OSTI)

    Manceau, Alain; Tamura, Nobumichi; Marcus, Matthew A.; MacDowell, Alastair A.; Celestre, Richard S.; Sublett, Robert E.; Sposito, Garrison; Padmore, Howard A.

    2002-11-06

    X-ray microprobes are among the most important new analytical techniques to emerge from third generation synchrotron facilities. Here we show how X-ray fluorescence, diffraction, and absorption can be used in parallel to determine the structural form of trace elements in heterogeneous matrices at the micrometer-scale of resolution. Scanning X-ray microfluorescence (microSXRF) and microdiffraction (microSXRD) first are used to identify the host solid phase by mapping the distributions of elements and solid species, respectively. Micro-extended X-ray absorption fine structure (microEXAFS) spectroscopy is then used to determine the mechanism of trace element binding by the host phase at the molecular scale. To illustrate the complementary application of these three techniques, we studied how nickel is sequestered in soil ferromanganese nodules, an overwhelmingly complex natural matrix consisting of submicrometer to nanometer sized particles with varying structures and chemical composition s. We show that nickel substitutes for Mn3+ in the manganese layer of the MnO2-Al(OH)3 mixed-layer oxide lithiophorite. The affinity of Ni for lithiophorite was characteristic of micromodules sampled from soils across the U.S.A. and Europe. Since many natural and synthetic materials are heterogeneous at nanometer to micrometer scales, the synergistic use of microSXRF, microSXRD and microEXAFS is expected to have broad applications to earth and materials science.

  13. Vertical dispersion methods in x-ray spectroscopy of high temperature plasmas

    SciTech Connect (OSTI)

    Renner, O.; Missalla, T.; Foerster, E.

    1995-12-31

    General formulae for the applying the vertical dispersion principle in x-ray spectroscopy of multiple charged ions are summarized, the characteristics of the experimental schemes based on flat and bent crystals are discussed. The unique properties of the novel spectroscopic methods, i.e., their extremely high dispersion, high spectral and 1-D spatial resolution and good collection efficiency, make them very attractive for ultrahigh-resolution spectroscopy. The examples of successful use of the vertical dispersion modifications of the double-crystal and the Johann spectrometer in diagnostics of several types of laser-generated plasma are presented.

  14. Hard x-ray photoelectron spectroscopy using an environmental cell with silicon nitride membrane windows

    SciTech Connect (OSTI)

    Tsunemi, Eika; Watanabe, Yoshio; Oji, Hiroshi; Cui, Yi-Tao; Son, Jin-Young

    2015-06-21

    We applied hard x-ray photoelectron spectroscopy (HAXPES) to a sample under ambient pressure conditions using an environmental cell with an approximately 24 nm-thick SiN{sub x} membrane window. As a model chemical substance, europium (II) iodide (EuI{sub 2}) sealed in the cell with argon gas was investigated with HAXPES to identify the chemical species present inside the cell. The optical and morphological properties of the sample within the cell were measured with optical and fluorescent microscopy, scanning electron microscopy, cathodoluminescence, and energy dispersive x-ray spectrometry. We confirmed the effectiveness of the gas barrier properties of the cell with the SiN{sub x} window and demonstrated its applicability to various other optical and electron measurements as well as HAXPES.

  15. In situ x-ray photoelectron spectroscopy for electrochemical reactions in ordinary solvents

    SciTech Connect (OSTI)

    Masuda, Takuya; PRESTO, Japan Science and Technology Agency , 4-1-8 Honcho, Kawaguchi, Saitama 333-0012 ; Yoshikawa, Hideki; Kobata, Masaaki; Kobayashi, Keisuke; Noguchi, Hidenori; PRESTO, Japan Science and Technology Agency , 4-1-8 Honcho, Kawaguchi, Saitama 333-0012; Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido 060-0810; International Center for Materials Nanoarchitectonics , National Institute for Materials Science , Tsukuba, Ibaraki 305-0044 ; Kawasaki, Tadahiro; Uosaki, Kohei; Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido 060-0810; International Center for Materials Nanoarchitectonics , National Institute for Materials Science , Tsukuba, Ibaraki 305-0044

    2013-09-09

    In situ electrochemical X-ray photoelectron spectroscopy (XPS) apparatus, which allows XPS at solid/liquid interfaces under potential control, was constructed utilizing a microcell with an ultra-thin Si membrane, which separates vacuum and a solution. Hard X-rays from a synchrotron source penetrate into the Si membrane surface exposed to the solution. Electrons emitted at the Si/solution interface can pass through the membrane and be analyzed by an analyzer placed in vacuum. Its operation was demonstrated for potential-induced Si oxide growth in water. Effect of potential and time on the thickness of Si and Si oxide layers was quantitatively determined at sub-nanometer resolution.

  16. Probing the hydrogen-bond network of water via time-resolved soft x-ray spectroscopy

    SciTech Connect (OSTI)

    Huse, Nils; Wen, Haidan; Nordlund, Dennis; Szilagyi, Erzsi; Daranciang, Dan; Miller, Timothy A.; Nilsson, Anders; Schoenlein, Robert W.; Lindenberg, Aaron M.

    2009-04-24

    We report time-resolved studies of hydrogen bonding in liquid H2O, in response to direct excitation of the O-H stretch mode at 3 mu m, probed via soft x-ray absorption spectroscopy at the oxygen K-edge. This approach employs a newly developed nanofluidic cell for transient soft x-ray spectroscopy in liquid phase. Distinct changes in the near-edge spectral region (XANES) are observed, and are indicative of a transient temperature rise of 10K following transient laser excitation and rapid thermalization of vibrational energy. The rapid heating occurs at constant volume and the associated increase in internal pressure, estimated to be 8MPa, is manifest by distinct spectral changes that differ from those induced by temperature alone. We conclude that the near-edge spectral shape of the oxygen K-edge is a sensitive probe of internal pressure, opening new possibilities for testing the validity of water models and providing new insight into the nature of hydrogen bonding in water.

  17. Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory

    SciTech Connect (OSTI)

    Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan

    2015-11-09

    Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a power- ful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with con- ventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We con- sider seven low- and high-spin model complexes involving chromium, manganese and iron transition metal centers. Our results are in good agreement with experiment.

  18. Sequential single shot X-ray photon correlation spectroscopy at the SACLA free electron laser

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Lehmkühler, Felix; Kwaśniewski, Paweł; Roseker, Wojciech; Fischer, Birgit; Schroer, Martin A.; Tono, Kensuke; Katayama, Tetsuo; Sprung, Michael; Sikorski, Marcin; Song, Sanghoon; et al

    2015-11-27

    In this study, hard X-ray free electron lasers allow for the first time to access dynamics of condensed matter samples ranging from femtoseconds to several hundred seconds. In particular, the exceptional large transverse coherence of the X-ray pulses and the high time-averaged flux promises to reach time and length scales that have not been accessible up to now with storage ring based sources. However, due to the fluctuations originating from the stochastic nature of the self-amplified spontaneous emission (SASE) process the application of well established techniques such as X-ray photon correlation spectroscopy (XPCS) is challenging. Here we demonstrate a single-shotmore » based sequential XPCS study on a colloidal suspension with a relaxation time comparable to the SACLA free-electron laser pulse repetition rate. High quality correlation functions could be extracted without any indications for sample damage. This opens the way for systematic sequential XPCS experiments at FEL sources.« less

  19. HELIUM IN NATAL H II REGIONS: THE ORIGIN OF THE X-RAY ABSORPTION IN GAMMA-RAY BURST AFTERGLOWS

    SciTech Connect (OSTI)

    Watson, Darach; Andersen, Anja C.; Fynbo, Johan P. U.; Hjorth, Jens; Kruehler, Thomas; Laursen, Peter; Leloudas, Giorgos; Malesani, Daniele [Dark Cosmology Centre, Niels Bohr Institute, University of Copenhagen, Juliane Maries Vej 30, DK-2100 Copenhagen O (Denmark); Zafar, Tayyaba [Laboratoire d'Astrophysique de Marseille - LAM, Universite Aix-Marseille and CNRS, UMR 7326, 38 rue F. Joliot-Curie, F-13388, Marseille Cedex 13 (France); Gorosabel, Javier [Instituto de Astrofisica de Andalucia (IAA-CSIC), Glorieta de la Astronomia s/n, E-18008, Granada (Spain); Jakobsson, Pall, E-mail: darach@dark-cosmology.dk [Centre for Astrophysics and Cosmology, Science Institute, University of Iceland, Dunhagi 5, 107 Reykjavik (Iceland)

    2013-05-01

    Soft X-ray absorption in excess of Galactic is observed in the afterglows of most gamma-ray bursts (GRBs), but the correct solution to its origin has not been arrived at after more than a decade of work, preventing its use as a powerful diagnostic tool. We resolve this long-standing problem and find that absorption by He in the GRB's host H II region is responsible for most of the absorption. We show that the X-ray absorbing column density (N{sub H{sub X}}) is correlated with both the neutral gas column density and with the optical afterglow's dust extinction (A{sub V} ). This correlation explains the connection between dark bursts and bursts with high N{sub H{sub X}} values. From these correlations, we exclude an origin of the X-ray absorption which is not related to the host galaxy, i.e., the intergalactic medium or intervening absorbers are not responsible. We find that the correlation with the dust column has a strong redshift evolution, whereas the correlation with the neutral gas does not. From this, we conclude that the column density of the X-ray absorption is correlated with the total gas column density in the host galaxy rather than the metal column density, in spite of the fact that X-ray absorption is typically dominated by metals. The strong redshift evolution of N{sub H{sub X}}/A{sub V} is thus a reflection of the cosmic metallicity evolution of star-forming galaxies and we find it to be consistent with measurements of the redshift evolution of metallicities for GRB host galaxies. We conclude that the absorption of X-rays in GRB afterglows is caused by He in the H II region hosting the GRB. While dust is destroyed and metals are stripped of all of their electrons by the GRB to great distances, the abundance of He saturates the He-ionizing UV continuum much closer to the GRB, allowing it to remain in the neutral or singly-ionized state. Helium X-ray absorption explains the correlation with total gas, the lack of strong evolution with redshift, as well

  20. X-ray Imaging Workshop

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    microscopy (PEEM), angle resolved photoemission spectroscopy (ARPES), coherent diffraction imaging, x-ray microscopy, micro-tomography, holographic imaging, and x-ray...

  1. High-Resolution Spectroscopy with the Chandra X-ray Observatory

    ScienceCinema (OSTI)

    Canizares, Claude R. [MIT, Cambridge, Massachusetts, United States

    2010-01-08

    The capabilities of the Chandra X-ray Observatory and XMM-Newton for high-resolution spectroscopy have brought tradition plasma diagnostic techniques to the study of cosmic plasma. Observations have probed nearly every class of astronomical object, from young proto-starts through massive O starts and black hole binaries, supernova remnants, active galactic nuclei, and the intergalactic medium. Many of these sources show remarkable rich spectra that reveal new physical information, such as emission measure distributions, elemental abundances, accretion disk and wind signatures, and time variability. This talk will present an overview of the Chandra instrumentaton and selected examples of spectral observations of astrophysical and cosmological importance.

  2. Contact-free pyroelectric measurements using x-ray photoelectron spectroscopy

    SciTech Connect (OSTI)

    Ehre, D.; Cohen, H.

    2013-07-29

    Non-contact pyroelectricity measurements based on x-ray photoelectron spectroscopy (XPS) are presented. Applied to Lithium Tantalate crystals, we demonstrate how the XPS-derived surface potential provides a simple probe of the desired property, free of all top-contact related difficulties. In particular, the increase in Lithium Tantalate spontaneous polarization under cooling, an experimentally challenging feature, is evaluated. We further inspect the roll of surface contaminants and the control over trapped surface charge in the XPS vacuum environment. Our approach can be extended to other non-contact probes, as well as to measuring additional electrical properties, such as piezoelectricity and ferroelectricity.

  3. Slow dynamics of nanocomposite polymer aerogels as revealed by X-ray photocorrelation spectroscopy (XPCS)

    SciTech Connect (OSTI)

    Hernndez, Rebeca, E-mail: rhernandez@ictp.csic.es, E-mail: aurora.nogales@csic.es; Mijangos, Carmen [Instituto de Ciencia y Tecnologa de Polmeros, ICTP-CSIC, Juan de la Cierva, 3, 28006 Madrid (Spain)] [Instituto de Ciencia y Tecnologa de Polmeros, ICTP-CSIC, Juan de la Cierva, 3, 28006 Madrid (Spain); Nogales, Aurora, E-mail: rhernandez@ictp.csic.es, E-mail: aurora.nogales@csic.es; Ezquerra, Tiberio A. [Instituto de Estructura de la Materia, IEM-CSIC, Serrano 121, 28006 Madrid (Spain)] [Instituto de Estructura de la Materia, IEM-CSIC, Serrano 121, 28006 Madrid (Spain); Sprung, Michael [Petra III at DESY, Notkestr. 85, 22607 Hamburg (Germany)] [Petra III at DESY, Notkestr. 85, 22607 Hamburg (Germany)

    2014-01-14

    We report on a novel slow dynamics of polymer xerogels, aerogels, and nanocomposite aerogels with iron oxide nanoparticles, as revealed by X-ray photon correlation spectroscopy. The polymer aerogel and its nanocomposite aerogels, which are porous in nature, exhibit hyper-diffusive dynamics at room temperature. In contrast, non-porous polymer xerogels exhibit an absence of this peculiar dynamics. This slow dynamical process has been assigned to a relaxation of the characteristic porous structure of these materials and not to the presence of nanoparticles.

  4. X-ray and vibrational spectroscopy of manganese complexes relevant to the oxygen-evolving complex of photosynthesis

    SciTech Connect (OSTI)

    Visser, Hendrik

    2001-05-16

    Manganese model complexes, relevant to the oxygen-evolving complex (OEC) in photosynthesis, were studied with Mn K-edge X-ray absorption near-edge spectroscopy (XANES), Mn Kb X-ray emission spectroscopy (XES), and vibrational spectroscopy. A more detailed understanding was obtained of the influence of nuclearity, overall structure, oxidation state, and ligand environment of the Mn atoms on the spectra from these methods. This refined understanding is necessary for improving the interpretation of spectra of the OEC. Mn XANES and Kb XES were used to study a di-(mu)-oxo and a mono-(mu)-oxo di-nuclear Mn compound in the (III,III), (III,IV), and (IV,IV) oxidation states. XANES spectra show energy shifts of 0.8 - 2.2 eV for 1-electron oxidation-state changes and 0.4 - 1.8 eV for ligand-environment changes. The shifts observed for Mn XES spectra were approximately 0.21 eV for oxidation state-changes and only approximately 0.04 eV for ligand-environment changes. This indicates that Mn Kb XES i s more sensitive to the oxidation state and less sensitive to the ligand environment of the Mn atoms than XANES. These complimentary methods provide information about the oxidation state and the ligand environment of Mn atoms in model compounds and biological systems. A versatile spectroelectrochemical apparatus was designed to aid the interpretation of IR spectra of Mn compounds in different oxidation states. The design, based on an attenuated total reflection device, permits the study of a wide spectral range: 16,700 (600 nm) - 225

  5. Soliton absorption spectroscopy

    SciTech Connect (OSTI)

    Kalashnikov, V. L.; Sorokin, E.

    2010-03-15

    We analyze optical soliton propagation in the presence of weak absorption lines with much narrower linewidths as compared to the soliton spectrum width by using a perturbation analysis technique based on an integral representation in the spectral domain. The stable soliton acquires a spectral modulation that follows the associated index of refraction of the absorber. The model can be applied to ordinary soliton propagation and to an absorber inside a passively mode-locked laser. In the latter case, a comparison with water vapor absorption in a femtosecond Cr:ZnSe laser yields a very good agreement with experiment. Compared to the conventional absorption measurements in a cell of the same length, the signal is increased by an order of magnitude. The obtained analytical expressions allow further improvement in the sensitivity and spectroscopic accuracy, which makes soliton absorption spectroscopy a promising measurement technique.

  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 (OSTI)

    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. Photon-in photon-out hard X-ray spectroscopy at the Linac Coherent...

    Office of Scientific and Technical Information (OSTI)

    different source characteristics and its resulting impact on sample delivery, X-ray optics, X-ray detection and data acquisition. Here it is described how photon-in photon-out...

  8. First-principles calculation of principal Hugoniot and K-shell X-ray absorption spectra for warm dense KCl

    SciTech Connect (OSTI)

    Zhao, Shijun; Zhang, Shen; Kang, Wei; Li, Zi; Zhang, Ping; He, Xian-Tu

    2015-06-15

    Principal Hugoniot and K-shell X-ray absorption spectra of warm dense KCl are calculated using the first-principles molecular dynamics (FPMD) method. Evolution of electronic structures as well as the influence of the approximate description of ionization on pressure (caused by the underestimation of the energy gap between conduction bands and valence bands) in the first-principles method are illustrated by the calculation. It is shown that approximate description of ionization in FPMD has small influence on Hugoniot pressure due to mutual compensation of electronic kinetic pressure and virial pressure. The calculation of X-ray absorption spectra shows that the band gap of KCl persists after the pressure ionization of the 3p electrons of Cl and K taking place at lower energy, which provides a detailed understanding to the evolution of electronic structures of warm dense matter.

  9. X-ray absorption and resonant inelastic x-ray scattering (RIXS) show the presence of Cr{sup +} at the surface and in the bulk of CrF{sub 2}

    SciTech Connect (OSTI)

    Jiménez-Mier, J.; Olalde-Velasco, P.; Yang, W.-L.; Denlinger, J.

    2015-07-23

    X-Ray absorption and resonant inelastic x-ray scattering (RIXS) spectra of CrF{sub 2} recorded at the chromium L{sub 2,3} are presented. An atomic multiplet crystal field calculation is compared with the experimental data. Experiment and theory are in agreement once the calculation includes three chromium oxidation states, namely Cr{sup +}, Cr{sup 2+}, and Cr{sup 3+}. X-Ray absorption allows a direct determination of the surface oxidation, while the RIXS spectra shows the presence of these three oxidation states in the sample bulk. To give a quantitative interpretation of the RIXS data the effect of the incomming and outgoing photon penetration depth and self-absorption must be considered. For the much simpler case of MnF{sub 2}, with only one metal oxidation state, the measured RIXS spectra relative intensities are found to be proportional to the square of the sample attenuation length.

  10. THREE NEW GALACTIC CENTER X-RAY SOURCES IDENTIFIED WITH NEAR-INFRARED SPECTROSCOPY

    SciTech Connect (OSTI)

    DeWitt, Curtis; Bandyopadhyay, Reba M.; Eikenberry, Stephen S.; Sarajedini, Ata; Sellgren, Kris; Blum, Robert; Olsen, Knut; Bauer, Franz E.

    2013-11-01

    We have conducted a near-infrared spectroscopic survey of 47 candidate counterparts to X-ray sources discovered by the Chandra X-Ray Observatory near the Galactic center (GC). Though a significant number of these astrometric matches are likely to be spurious, we sought out spectral characteristics of active stars and interacting binaries, such as hot, massive spectral types or emission lines, in order to corroborate the X-ray activity and certify the authenticity of the match. We present three new spectroscopic identifications, including a Be high-mass X-ray binary (HMXB) or a ? Cassiopeiae (Cas) system, a symbiotic X-ray binary, and an O-type star of unknown luminosity class. The Be HMXB/? Cas system and the symbiotic X-ray binary are the first of their classes to be spectroscopically identified in the GC region.

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

    SciTech Connect (OSTI)

    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.

  12. The Structure of Interfacial Water on Gold Electrodes Studied by X-ray

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Absorption Spectroscopy - Joint Center for Energy Storage Research October 23, 2014, Research Highlights The Structure of Interfacial Water on Gold Electrodes Studied by X-ray Absorption Spectroscopy Schematic representation of X-ray absorption measurements at the biased gold water interface. X-rays arrive from the left and transmit through a thin silicon nitride window plated with gold. Fluorescence provides information far from the interface while it was discovered that electron yield is

  13. Photon-in photon-out hard X-ray spectroscopy at the Linac Coherent Light Source

    SciTech Connect (OSTI)

    Alonso-Mori, Roberto; Sokaras, Dimosthenis; Zhu, Diling; Kroll, Thomas; Chollet, Mathieu; Feng, Yiping; Glownia, James M.; Kern, Jan; Lemke, Henrik T.; Nordlund, Dennis; Robert, Aymeric; Sikorski, Marcin; Song, Sanghoon; Weng, Tsu -Chien; Bergmann, Uwe

    2015-04-15

    X-ray free-electron lasers (FELs) have opened unprecedented possibilities to study the structure and dynamics of matter at an atomic level and ultra-fast timescale. Many of the techniques routinely used at storage ring facilities are being adapted for experiments conducted at FELs. In order to take full advantage of these new sources several challenges have to be overcome. They are related to the very different source characteristics and its resulting impact on sample delivery, X-ray optics, X-ray detection and data acquisition. Here it is described how photon-in photon-out hard X-ray spectroscopy techniques can be applied to study the electronic structure and its dynamics of transition metal systems with ultra-bright and ultra-short FEL X-ray pulses. In particular, some of the experimental details that are different compared with synchrotron-based setups are discussed and illustrated by recent measurements performed at the Linac Coherent Light Source.

  14. Photon-in photon-out hard X-ray spectroscopy at the Linac Coherent Light Source

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Alonso-Mori, Roberto; Sokaras, Dimosthenis; Zhu, Diling; Kroll, Thomas; Chollet, Mathieu; Feng, Yiping; Glownia, James M.; Kern, Jan; Lemke, Henrik T.; Nordlund, Dennis; et al

    2015-04-15

    X-ray free-electron lasers (FELs) have opened unprecedented possibilities to study the structure and dynamics of matter at an atomic level and ultra-fast timescale. Many of the techniques routinely used at storage ring facilities are being adapted for experiments conducted at FELs. In order to take full advantage of these new sources several challenges have to be overcome. They are related to the very different source characteristics and its resulting impact on sample delivery, X-ray optics, X-ray detection and data acquisition. Here it is described how photon-in photon-out hard X-ray spectroscopy techniques can be applied to study the electronic structure andmore » its dynamics of transition metal systems with ultra-bright and ultra-short FEL X-ray pulses. In particular, some of the experimental details that are different compared with synchrotron-based setups are discussed and illustrated by recent measurements performed at the Linac Coherent Light Source.« less

  15. Slow dynamics in an azopolymer molecular layer studied by x-ray photon correlation spectroscopy

    SciTech Connect (OSTI)

    Orsi, D.; Fluerasu, A.; Cristofolini, L.; Fontana, M.P.; Pontecorvo, E.; Caronna, C.; Zontone, F.; Madsen, A.

    2010-09-23

    We report the results of x-ray photon correlation spectroscopy (XPCS) experiments on multilayers of a photosensitive azo-polymer which can be softened by photoisomerization. Time correlation functions have been measured at different temperatures and momentum transfers (q) and under different illumination conditions (dark, UV or visible). The correlation functions are well described by the Kohlrausch-Williams-Watts (KWW) form with relaxation times that are proportional to q{sup -1}. The characteristic relaxation times follow the same Vogel-Fulcher-Tammann law describing the bulk viscosity of this polymer. The out-of-equilibrium relaxation dynamics following a UV photoperturbation are accelerated, which is in agreement with a fluidification effect previously measured by rheology. The transient dynamics are characterized by two times correlation function, and dynamical heterogeneity is evidenced by calculating the variance {chi} of the degree of correlation as a function of ageing time. A clear peak in {chi} appears at a well defined time {tau}{sub C} which scales with q{sup -1} and with the ageing time, in a similar fashion as previously reported in colloidal suspensions [O. Dauchot et al. Phys. Rev. Lett. 95 265701 (2005)]. From an accurate analysis of the correlation functions we could demonstrate a temperature and light dependent cross-over from compressed KWW to simple exponential behavior.

  16. Scanning electron microscopy and x-ray photoelectron spectroscopy evaluation of MHD channel electrodes

    SciTech Connect (OSTI)

    Martello, D.V.; Baltrus, J.P.; Diehl, J.R.; Makovsky, L.E.

    1994-12-31

    Anode elements from the coal-fired Magnetohydrodynamic (MHD) channel at the Component Development and Integration Facility (CDIF) in Butte, Montana have been selected for study of the effects of localized phase morphology and chemistry on anode degradation. The platinum/tungsten/copper anode elements from the 1A{sub 4} channel were examined with scanning electron microscopy and X-ray photoelectron spectroscopy following testing in the MHD channel, and the results compared to those for unexposed anodes. Evidence suggests that the surface of the tungsten anode is chemically attacked by a potassium-rich slag to form a fine-grained crystalline reaction product layer that is covered by a fused, glassy slag during channel operation. Examination of a mechanically separated, partially delaminated platinum cap and polished cross-sections of anode segments showed evidence of chemical attack along the braze used to join the two caps. Interface porosity may provide a path for slag penetration and diffusion of corrosive gases and liquids during channel operation, leading to delamination. The microstructure of the brazed joint cross-sections were similar, independent of exposure severity in the MHD channel. The primary mechanism of tungsten degradation appears to be grain exfoliation due to severe grain boundary attack.

  17. Adsorption of 2-propanol on ice probed by ambient pressure X-ray photoelectron spectroscopy

    SciTech Connect (OSTI)

    Newberg, John T.; Bluhm, Hendrik

    2015-08-18

    The interaction of 2-propanol with ice was examined via ambient pressure X-ray photoelectron spectroscopy (APXPS), a surface sensitive technique that probes the adsorbed 2-propanol directly with submonolayer resolution. Isothermal uptake experiments were performed on vapor deposited ice at 227 K in the presence of the equilibrium water vapor pressure of 0.05 Torr and 2-propanol partial pressures ranging from 5 × 10-5 to 2 × 10-3 Torr. The C 1s APXPS spectra of adsorbed 2-propanol showed two characteristic peaks associated with the COH alcohol group and CMe methyl groups in a 1 : 2 ratio, respectively. Coverage increased with 2-propanol partial pressure and followed first order Langmuir kinetics with a Langmuir constant of K = 6.3 × 103 Torr-1. The 1 : 2 ratio of COH : CMe remained constant with increasing coverage, indicating there is no chemical reaction upon adsorption. The observed Langmuir kinetics using APXPS is consistent with previous observations of other small chain alcohols via indirect adsorption methods using, e.g., Knudsen cell and coated wall flow tube reactors.

  18. Adsorption of 2-propanol on ice probed by ambient pressure X-ray photoelectron spectroscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Newberg, John T.; Bluhm, Hendrik

    2015-08-18

    The interaction of 2-propanol with ice was examined via ambient pressure X-ray photoelectron spectroscopy (APXPS), a surface sensitive technique that probes the adsorbed 2-propanol directly with submonolayer resolution. Isothermal uptake experiments were performed on vapor deposited ice at 227 K in the presence of the equilibrium water vapor pressure of 0.05 Torr and 2-propanol partial pressures ranging from 5 × 10-5 to 2 × 10-3 Torr. The C 1s APXPS spectra of adsorbed 2-propanol showed two characteristic peaks associated with the COH alcohol group and CMe methyl groups in a 1 : 2 ratio, respectively. Coverage increased with 2-propanol partialmore » pressure and followed first order Langmuir kinetics with a Langmuir constant of K = 6.3 × 103 Torr-1. The 1 : 2 ratio of COH : CMe remained constant with increasing coverage, indicating there is no chemical reaction upon adsorption. The observed Langmuir kinetics using APXPS is consistent with previous observations of other small chain alcohols via indirect adsorption methods using, e.g., Knudsen cell and coated wall flow tube reactors.« less

  19. Microscopic Dynamics in Nanocomposite Photosensitive Films Studies by X-ray Photon Correlation Spectroscopy

    SciTech Connect (OSTI)

    D Orsi; L Cristofolini; M Fontant; E Pontecorvo; C Caronna; A Fluerasu; F Zontone; A Madsen

    2011-12-31

    X-ray photon correlation spectroscopy measurements are reported of microscale dynamics in Langmuir-Schaeffer deposited multilayers of a photosensitive azopolymer with a low concentration of gold nanoparticles embedded. Correlation functions were measured as a function of exchanged momentum and illumination conditions (dark and UV light) and fitted with the Kohlrausch-Williams-Watts (KWW) exponential form. The microscopic dynamic of the nanoparticles was quantified, evidencing a non-Brownian superdiffusive behavior with relaxation times {tau} {approx} q{sup -1}, a result analogous to what previously had been observed in the pure azopolymer. Such behavior has been related to intermittent rearrangements or random dipolar interactions within an elastic medium. Photoperturbation with UV light makes the dynamics faster, in accordance with the reduction of the viscosity of the polymer found by shear rheology, but the KWW form of the correlation functions persists. At constant temperature, the dynamics of the nanoparticles embedded in the polymeric matrix is sensibly faster than the slow microscopic dynamic of the polymer. At the same time, the Vogel-Fulcher-Tammann law for the relaxation times indicates a less pronounced temperature dependence than for the pure polymer, resulting in a slightly lower activation temperature T{sub A}.

  20. Closing the pressure gap in x-ray photoelectron spectroscopy by membrane hydrogenation

    SciTech Connect (OSTI)

    Delmelle, Renaud; Borgschulte, Andreas; Probst, Benjamin; Alberto, Roger; Zttel, Andreas; Bleiner, Davide

    2015-05-15

    Comprehensive studies of gas-solid reactions require the in-situ interaction of the gas at a pressure beyond the operating pressure of ultrahigh vacuum (UHV) X-ray photoelectron spectroscopy (XPS). The recent progress of near ambient pressure XPS allows to dose gases to the sample up to a pressure of 20 mbar. The present work describes an alternative to this experimental challenge, with a focus on H{sub 2} as the interacting gas. Instead of exposing the sample under investigation to gaseous hydrogen, the sample is in contact with a hydrogen permeation membrane, through which hydrogen is transported from the outside to the sample as atomic hydrogen. Thereby, we can reach local hydrogen concentrations at the sample inside an UHV chamber, which is equipped with surface science tools, and this corresponds to a hydrogen pressure up to 1 bar without affecting the sensitivity or energy resolution of the spectrometer. This experimental approach is validated by two examples, that is, the reduction of a catalyst precursor for CO{sub 2} hydrogenation and the hydrogenation of a water reduction catalyst for photocatalytic H{sub 2} production, but it opens the possibility of the new in situ characterisation of energy materials and catalysts.

  1. Resonant Soft X-Ray Scattering - Combining Structural with Spectroscop...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    28, 2012 - 10:00am SLAC, Bldg. 137, Room 322 SSRL Presents Kevin Stone X-ray absorption spectroscopy has become an important tool in understanding the electronic structure...

  2. The X-ray correlation spectroscopy instrument at the Linac Coherent...

    Office of Scientific and Technical Information (OSTI)

    characteristics of the Linac Coherent Light Source, in particular the 120 Hz repetition rate, allow for the investigation of slow dynamics (milliseconds) by means of X-ray photon...

  3. Low-level determination of plutonium by gamma and L x-ray spectroscopy

    SciTech Connect (OSTI)

    Nitsche, H.; Gatti, R.C.; Lee, S.C.

    1991-04-01

    we have developed an analytical method for detection of {sup 239}Pu in aqueous samples at concentrations as low as 10{sup {minus}10} M. This nuclear counting technique utilizes the uranium L X-rays, which follow the alpha decay of plutonium. Because L X-rays are specific for the element and not for the individual isotopes, the isotopic composition of the plutonium sample must be known. The counting efficiency in the 11--23 keV range is determined from a plutonium standard, and the concentration of the sample is then calculated from the L X-ray count and the isotopic composition. The total L X-ray count is corrected for possible contributions from other radionuclides present as impurities by measuring the low-energy gamma spectrum for each contaminant to establish specific photon/X-ray ratios. The ratios are important when {sup 241}Pu and {sup 242}Pu are measured, because the respective decay chain members produce non-U L X-rays. This new method can replace the use of labor-intensive radiochemical separation techniques and elaborate activation methods for analysis of {sup 239}Pu in aqueous samples. It is also applicable for assaying plutonium in liquid wastes that pose possible hazards to the environment.

  4. Quantitative x-ray photoelectron spectroscopy: Quadrupole effects, shake-up, Shirley background, and relative sensitivity factors from a database of true x-ray photoelectron spectra

    SciTech Connect (OSTI)

    Seah, M. P.; Gilmore, I. S.

    2006-05-01

    An analysis is provided of the x-ray photoelectron spectroscopy (XPS) intensities measured in the National Physical Laboratory (NPL) XPS database for 46 solid elements. This present analysis does not change our previous conclusions concerning the excellent correlation between experimental intensities, following deconvolving the spectra with angle-averaged reflection electron energy loss data, and the theoretical intensities involving the dipole approximation using Scofield's cross sections. Here, more recent calculations for cross sections by Trzhaskovskaya et al. involving quadrupole terms are evaluated and it is shown that their cross sections diverge from the experimental database results by up to a factor of 5. The quadrupole angular terms lead to small corrections that are close to our measurement limit but do appear to be supported in the present analysis. Measurements of the extent of shake-up for the 46 elements broadly agree with the calculations of Yarzhemsky et al. but not in detail. The predicted constancy in the shake-up contribution by Yarzhemsky et al. implies that the use of the Shirley background will lead to a peak area that is a constant fraction of the true peak area including the shake-up intensities. However, the measured variability of the shake-up contribution makes the Shirley background invalid for quantification except for situations where the sensitivity factors are from reference samples similar to those being analyzed.

  5. An ultra-high vacuum electrochemical flow cell for in situ/operando soft X-ray spectroscopy study

    SciTech Connect (OSTI)

    Bora, Debajeet K. E-mail: jguo@lbl.gov; Glans, Per-Anders; Pepper, John; Liu, Yi-Sheng; Guo, J.-H. E-mail: jguo@lbl.gov; Du, Chun; Wang, Dunwei

    2014-04-15

    An in situ flow electrochemical cell has been designed and fabricated to allow better seal under UHV chamber thus to achieve a good signal to noise ratio in fluorescence yield detection of X-ray absorption spectra for spectroelectrochemical study. The cell also stabilizes the thin silicon nitride membrane window in an effective manner so that the liquid cell remains intact during X-ray absorption experiments. With the improved design of the liquid cell, electrochemical experiments such as cyclic voltammetry have been performed for 10 cycles with a good stability of sample window. Also an operando electrochemical experiment during photoelectrochemistry has been performed on n-type hematite electrode deposited on silicon nitride window. The experiment allows us to observe the formation of two extra electronic transitions before pre edge of O K-edge spectra.

  6. Band bending at ferroelectric surfaces and interfaces investigated by x-ray photoelectron spectroscopy

    SciTech Connect (OSTI)

    Apostol, Nicoleta Georgiana

    2014-11-24

    This work reports on the use of X-ray photoelectron spectroscopy to quantify band bending at ferroelectric free surfaces and at their interfaces with metals. Surfaces exhibiting out-of-plane ferroelectric polarization are characterized by a band bending, due to the formation of a dipole layer at the surface, composed by the uncompensated polarization charges (due to ionic displacement) and to the depolarization charge sheet of opposite sign, composed by mobile charge carriers, which migrate near surface, owing to the depolarization electric field. To this surface band bending due to out-of-plane polarization states, metal-semiconductor Schottky barriers must be considered additionally when ferroelectrics are covered by metal layers. It is found that the net band bending is not always an algebraic sum of the two effects discussed above, since sometimes the metal is able to provide additional charge carriers, which are able to fully compensate the surface charge of the ferroelectric, up to the vanishing of the ferroelectric band bending. The two cases which will be discussed in more detail are Au and Cu deposited by molecular beam epitaxy on PbZr{sub 0.2}Ti{sub 0.8}O{sub 3}(001) single crystal thin layers, prepared by pulsed laser deposition. Gold forms unconnected nanoparticles, and their effect on the band bending is the apparition of a Schottky band bending additional to the band bending due to the out-of-plane polarization. Copper, starting with a given thickness, forms continuous metal layers connected to the ground of the system, and provide electrons in sufficient quantity to compensate the band bending due to the out-of-plane polarization.

  7. Near-edge X-ray Absorption Fine Structure Study of Disordering in Gd₂(Ti1-yZry)₂O₇ Pyrochlores

    SciTech Connect (OSTI)

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

    2005-02-03

    Disorder in Gd₂(Ti1-yZry)₂O₇ pyrochlores, for y=0.0-1.0, is investigated by Ti 2p and O 1s near-edge x-ray absorption fine structure spectroscopy. Ti⁴⁺ 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.

  8. X-ray Photoelectron Spectroscopy study of the compatibility of the explosive PETN with candidate plastic bonding materials

    SciTech Connect (OSTI)

    Vannet, M.D.; Wang, P.S.; Moddeman, W.E.; Bowling, W.C.

    1985-01-01

    The compatibility of the explosive PETN with two plastic bonding materials, ethyl cellulose and a halogenated vinyl polymer (FPC 461), was determined by X-ray Photoelectron Spectroscopy (XPS). Both were found to coat the PETN crystals, and no change in chemical composition was found in the PETN or the plastic due to either the process or their mutual presence. 3 refs., 1 fig., 1 tab.

  9. Runaway electron energy measurement using hard x-ray spectroscopy in 'Damavand' tokamak

    SciTech Connect (OSTI)

    Rasouli, C.; Farahbod, A. H.; Rasouli, H.; Lamehi, M.; Iraji, D.; Akhtari, K.; Modarresi, H.

    2009-01-15

    Set of experiments has been developed to study existing runaway electrons in ''Damavand'' tokamak plasma upon characteristics of hard x-ray emissions produced by collision of the runaway electrons with the plasma particles and limiters. As a first step, spatial distribution of hard x-ray emissions on the equatorial plane of the torus was considered. Obtained spectra of hard x-ray emissions for different alignments of shielded detector indicate isotropic emissivity in the equatorial plane. This is in agreement with wide angle cone of bremsstrahlung radiations, deduced from the mean value of energy of the runaway electrons. The mean energy was calculated from the slope of the energy spectrum of hard x-ray photons. In the second stage in order to investigate time evolution of energy of the runaway electrons, similar technique were applied to obtain hard x-ray energy in every 3 ms intervals, from the beginning to the end of plasma. The mean energy of the runaway electrons increases during the ramp up phase and reaches its maximum between 3 and 9 ms after plasma formation. Also considering the time dependence of the counted photons in each energy range shows that energetic photons are emitted during the ramp up phase of the plasma current in Damavand tokamak.

  10. An X-ray photoelectron spectroscopy study of the hydration of C{sub 2}S thin films

    SciTech Connect (OSTI)

    Rheinheimer, Vanessa; Casanova, Ignasi

    2014-06-01

    Electron-beam evaporation was used to produce thin films of ?-dicalcium silicate. Chemical and mineralogical compositions were characterized by X-ray photoelectron spectroscopy (XPS) and grazing-angle X-ray diffraction (GAXRD), respectively. Results show that no fractionation occurs during evaporation and isostructural condensation of the material as synthesized films have the same composition as the initial bulk material. Samples were gradually hydrated under saturated water spray conditions and analyzed with XPS. Polymerization of the silicate chains due to hydration, and subsequent formation of C-S-H, has been monitored through evaluation of energy shifts on characteristic silicon peaks. Quantitative analyses show changes on the surface by the reduction of the Ca/Si ratio and an increase on the difference between binding energies of bridging and non-bridging oxygen. Finally, SEM/FIB observation shows clear differences between the surface and cross section of the initial sample and the reacted sample.

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

    SciTech Connect (OSTI)

    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.

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

    SciTech Connect (OSTI)

    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.

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

    SciTech Connect (OSTI)

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

    2006-04-01

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

  14. Effects of Plant Cell Wall Matrix Polysaccharides on Bacterial Cellulose Structure Studied with Vibrational Sum Frequency Generation Spectroscopy and X-ray Diffraction

    SciTech Connect (OSTI)

    Park, Yong Bum; Lee, Christopher M; Kafle, Kabindra; Park, Sunkyu; Cosgrove, Daniel; Kim, Seong H

    2014-07-14

    The crystallinity, allomorph content, and mesoscale ordering of cellulose produced by Gluconacetobacter xylinus cultured with different plant cell wall matrix polysaccharides were studied with vibrational sum frequency generation (SFG) spectroscopy and X-ray diffraction (XRD).

  15. Neutral hydrogen absorption by galaxies and implications for the soft X-ray background

    SciTech Connect (OSTI)

    Corbelli, E.; Schneider, S.E. Massachusetts Univ., Amherst )

    1990-06-01

    Results are presented from a search for neutral hydrogen absorption in the 21-cm spectra of 59 radio continuum sources in the proximity of spiral and lenticular galaxies using the Arecibo radio telescope. Five galaxies showed possible but uncertain absorption. For the 54 other sources, the column density of the neutral hydrogen in the intervening material is well below 2 x 10 to the 19th/cu cm or the spin temperature is at least one order of magnitude above the microwave background temperature. For these cases, subthermal effects are not hiding appreciable amounts of neutral hydrogen. 47 refs.

  16. Magnetic properties of GdT2Zn20 (T = Fe, Co) investigated by x-ray diffraction and spectroscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    J. R. L. Mardegan; Fabbris, G.; Francoual, S.; Veiga, L. S. I.; Strempfer, J.; Haskel, D.; Ribeiro, R. A.; Avila, M. A.; Giles, C.

    2016-01-26

    In this study, we investigate the magnetic and electronic properties of the GdT2Zn20 (T=Fe and Co) compounds using x-ray resonant magnetic scattering (XRMS), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD). The XRMS measurements reveal that GdCo2Zn20 has a commensurate antiferromagnetic spin structure with a magnetic propagation vector →/τ = (12,12,12) below the Néel temperature (TN ~ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation Γ6. For the ferromagnetic GdFe2Zn20 compound, an extensive investigation was performed at low temperature and under magnetic field using XANES and XMCD. Amore » strong XMCD signal of about 12.5% and 9.7% is observed below the Curie temperature (TC ~ 85K) at the Gd L2 and L3 edges, respectively. In addition, a small magnetic signal of about 0.06% of the jump is recorded at the Zn K edge, suggesting that the Zn 4p states are spin polarized by the Gd 5d extended orbitals.« less

  17. Investigating inertial confinement fusion target fuel conditions through x-ray spectroscopy

    SciTech Connect (OSTI)

    Hansen, Stephanie B.

    2012-05-15

    Inertial confinement fusion (ICF) targets are designed to produce hot, dense fuel in a neutron-producing core that is surrounded by a shell of compressing material. The x-rays emitted from ICF plasmas can be analyzed to reveal details of the temperatures, densities, gradients, velocities, and mix characteristics of ICF targets. Such diagnostics are critical to understand the target performance and to improve the predictive power of simulation codes.

  18. MAGNETOHYDRODYNAMIC MODELING OF THE ACCRETION SHOCKS IN CLASSICAL T TAURI STARS: THE ROLE OF LOCAL ABSORPTION IN THE X-RAY EMISSION

    SciTech Connect (OSTI)

    Bonito, R.; Argiroffi, C.; Peres, G. [Dip. di Fisica e Chimica, Universit di Palermo, P.zza del Parlamento 1, I-90134 Palermo (Italy); Orlando, S.; Miceli, M.; Ibgui, L. [INAF-Osservatorio Astronomico di Palermo, P.zza del Parlamento 1, I-90134 Palermo (Italy); Matsakos, T. [Department of Astronomy and Astrophysics, The University of Chicago, Chicago, IL 60637 (United States); Stehle, C., E-mail: sbonito@astropa.unipa.it [LERMA, Observatoire de Paris, Universit Pierre et Marie Curie, Ecole Normale Superieure, Universite Cergy-Pontoise, CNRS, F-75014 Paris (France)

    2014-11-10

    We investigate the properties of X-ray emission from accretion shocks in classical T Tauri stars (CTTSs), generated where the infalling material impacts the stellar surface. Both observations and models of the accretion process reveal several aspects that are still unclear: the observed X-ray luminosity in accretion shocks is below the predicted value, and the density versus temperature structure of the shocked plasma, with increasing densities at higher temperature, deduced from the observations, is at odds with that proposed in the current picture of accretion shocks. To address these open issues, we investigate whether a correct treatment of the local absorption by the surrounding medium is crucial to explain the observations. To this end, we describe the impact of an accretion stream on a CTTS by considering a magnetohydrodynamic model. From the model results, we synthesize the X-ray emission from the accretion shock by producing maps and spectra. We perform density and temperature diagnostics on the synthetic spectra, and we directly compare the results with observations. Our model shows that the X-ray fluxes inferred from the emerging spectra are lower than expected because of the complex local absorption by the optically thick material of the chromosphere and of the unperturbed stream. Moreover, our model, including the effects of local absorption, explains in a natural way the apparently puzzling pattern of density versus temperature observed in the X-ray emission from accretion shocks.

  19. Neutron diffraction and X-ray absorption study of Ag{sub 5}Pb{sub 2}O{sub 6}

    SciTech Connect (OSTI)

    Yoshii, K. Mizumaki, M.; Kato, K.; Uruga, T.; Abe, H.; Nakamura, A.; Shimojo, Y.; Ishii, Y.; Morii, Y.

    2007-01-15

    Neutron diffraction and X-ray absorption measurements were carried out for a silver-lead oxide Ag{sub 5}Pb{sub 2}O{sub 6}. The powder neutron diffraction patterns could be fitted to the trigonal P3-bar 1m structure, as was found by X-ray diffraction. From the bond-valence-sum (BVS) analysis, the valences of the Ag and Pb ions were estimated to be about 1+ and 3.7+, respectively. The X-ray absorption measurements indicated that the ionic state of Ag is close to 1+, while that of Pb stands between 3+ and 4+. The deviation of the valence of the Pb ion from 4+ suggests a contribution of Pb orbitals to the metallic conduction as well as the possible superconductivity of this material, consistently with a recent band-structure calculation.

  20. NUSTAR and SUZAKU X-ray spectroscopy of NGC 4151: Evidence for reflection from the inner accretion disk

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Keck, M. L.; Brenneman, L. W.; Ballantyne, D. R.; Bauer, F.; Boggs, S. E.; Christensen, F. E.; Craig, W. W.; Dauser, T.; Elvis, M.; Fabian, A. C.; et al

    2015-06-15

    We present X-ray timing and spectral analyses of simultaneous 150 ks Nuclear Spectroscopic Telescope Array (NuSTAR) and Suzaku X-ray observations of the Seyfert 1.5 galaxy NGC 4151. We disentangle the continuum emission, absorption, and reflection properties of the active galactic nucleus (AGN) by applying inner accretion disk reflection and absorption-dominated models. With a time-averaged spectral analysis, we find strong evidence for relativistic reflection from the inner accretion disk. We find that relativistic emission arises from a highly ionized inner accretion disk with a steep emissivity profile, which suggests an intense, compact illuminating source. We find a preliminary, near-maximal black hole spinmore » $$a\\gt 0.9$$ accounting for statistical and systematic modeling errors. We find a relatively moderate reflection fraction with respect to predictions for the lamp post geometry, in which the illuminating corona is modeled as a point source. Through a time-resolved spectral analysis, we find that modest coronal and inner disk reflection (IDR) flux variation drives the spectral variability during the observations. As a result, we discuss various physical scenarios for the IDR model and we find that a compact corona is consistent with the observed features.« less

  1. X-ray Spectroscopy with Elliptical Crystals and Face-On Framing Cameras

    SciTech Connect (OSTI)

    Heeter, R; Emig, J; Fournier, K; Hansen, S; May, M; Young, B

    2004-04-16

    X-ray spectrometers using elliptically bent crystals have desirable properties for applications requiring broad spectral coverage, good spectral resolution, and minimized source broadening. Previous work used custom-positioned film or microchannel plate detectors. They find it is also useful and cost-effective to field elliptical crystals in existing snouts on the face-on gated microchannel plate framing cameras commonly used at many facilities. they numerically explored the full design space (spectral range and resolution) of elliptical crystals compatible with the new MSPEC multipurpose spectrometer snout. They have tested at the Omega laser an elliptical RAP crystal with 174 mm focal length, 0.9885 eccentricity, and 4.6 degree inclination, viewing from 1.0 to at least 1.7 keV with E/dE of 300-500. A slit (2x mag) images 3 mm sources with 70 um spatial resolution.

  2. X-ray spectroscopy with elliptical crystals and face-on framing cameras

    SciTech Connect (OSTI)

    Heeter, R.F.; Emig, J.A.; Fournier, K.B.; Hansen, S.B.; May, M.J.; Young, B.K.F.

    2004-10-01

    X-ray spectrometers using elliptically bent crystals have desirable properties for applications requiring broad spectral coverage, good spectral resolution, and minimized source broadening. Previous work used custom-positioned film or microchannel plate detectors. We find it is also useful and cost-effective to field elliptical crystals in existing snouts on the face-on gated microchannel plate framing cameras commonly used at many facilities. We numerically explored the full design space (spectral range and resolution) of elliptical crystals compatible with the new multipurpose spectrometer snout. We have tested at the Omega laser an elliptical rubidium acid phthalate crystal with 174 mm focal length, 0.9885 eccentricity, and 4.6 deg. inclination, viewing from 1.0 to at least 1.7 keV with spectral resolution E/dE of 300-500. A slit (2xmagnification) images 3 mm sources with 70 {mu}m spatial resolution.

  3. In situ X-ray absorption spectroscopic investigation of the electrochemical conversion reactions of CuF{sub 2}-MoO{sub 3} nanocomposite

    SciTech Connect (OSTI)

    Mansour, A.N.; Badway, F.; Yoon, W.-S.; Chung, K.Y.; Amatucci, G.G.

    2010-12-15

    We have used X-ray absorption spectroscopy at the Cu K-edge to investigate the electrochemical conversion reaction of 20 nm size 85 wt% CuF{sub 2}-15 wt% MoO{sub 3} nanocomposite under in situ conditions. The nanocomposite was prepared by high energy milling. Upon discharge, the lithiation reaction with the nanocomposite resulted in the formation of nanophase metallic Cu, which is consistent with the conversion of CuF{sub 2} into Cu and LiF. Based on XANES and Fourier transforms of EXAFS spectra, we show that the discharge process proceeded via the formation of highly dispersed Cu particles. Based on the coordination number of the first shell of Cu, the average size of the Cu particles was estimated to be in the 1-3 nm range in the fully discharged state. -- Graphical Abstract: Comparison of Fourier transform of in situ Cu K-edge EXAFS spectra for a fully discharged CuF{sub 2{center_dot}}MoO{sub 3} nanocomposite in a nonaqueous Li cell with that of a Cu foil. Quantitative analysis of the Fourier transforms confirmed that the discharge mechanism for the nanocomposite proceeds via the reaction CuF{sub 2}+2Li{yields}Cu+2LiF. The discharge product of Cu is in the form of highly dispersed nanoparticles. Display Omitted

  4. In situ monitoring of the electrochemical absorption of deuterium into palladium by x-ray diffraction using synchrotron-wiggler radiation

    SciTech Connect (OSTI)

    Dominguez, D.D.; Hagans, P.L.; Skelton, E.F.; Qadri, S.B.; Nagel, D.J.

    1998-12-31

    With low energy x-rays, such as those from a Cu x-ray tube, only the outer few microns of a metallic sample can be probed. This low penetrating power prohibits structural studies from being carried out on the interior of an electrode in an electrochemical cell because of absorption by the cell material, electrodes and the electrolyte. The work described in this paper circumvents this problem by utilizing high energy, high brightness x-rays produced on the superconducting wiggler beam line, X-17C, at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory. The penetrating power of the higher energy x-rays allowed Pd diffraction spectra to be obtained in-situ on a 1 mm diameter Pd wire cathode during electrolysis of heavy water. Moreover, the beam (28 x 28 {micro}m in cross-section) allowed diffraction spectra to be acquired as a function of distance across the sample. Spectra were recorded in 50 {micro}m steps from the edge of the Pd wire to its core. This was done at 2 minute intervals as a function of electrolysis time. The {alpha}-{beta} phase transition induced in the Pd while deuterium was electrochemically absorbed was observed by monitoring the Pd-(422) diffraction peaks. Results allowed the diffusion rate and the diffusivity of deuterium atoms in the Pd wire to be determined. Other features of the structural changes associated with the absorption of deuterium into Pd are reported.

  5. Cavity-Enhanced Transient Absorption Spectroscopy: Ultrafast...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Cavity-Enhanced Transient Absorption Spectroscopy: Ultrafast Spectroscopy goes Ultra-Sensitive Wednesday, November 11, 2015 - 3:00pm SLAC, Redtail Hawk Conference Room 108A...

  6. Electronic structure of Al- and Ga-doped ZnO films studied by hard X-ray photoelectron spectroscopy

    SciTech Connect (OSTI)

    Gabás, M.; Ramos Barrado, José R.; Torelli, P.; Barrett, N. T.

    2014-01-01

    Al- and Ga-doped sputtered ZnO films (AZO, GZO) are semiconducting and metallic, respectively, despite the same electronic valence structure of the dopants. Using hard X-ray photoelectron spectroscopy we observe that both dopants induce a band in the electronic structure near the Fermi level, accompanied by a narrowing of the Zn 3d/O 2p gap in the valence band and, in the case of GZO, a substantial shift in the Zn 3d. Ga occupies substitutional sites, whereas Al dopants are in both substitutional and interstitial sites. The latter could induce O and Zn defects, which act as acceptors explaining the semiconducting character of AZO and the lack of variation in the optical gap. By contrast, mainly substitutional doping is consistent with the metallic-like behavior of GZO.

  7. Trace elemental analysis of school chalk using energy dispersive X-ray florescence spectroscopy (ED-XRF)

    SciTech Connect (OSTI)

    Maruthi, Y. A.; Das, N. Lakshmana; Ramprasad, S.; Ram, S. S.; Sudarshan, M.

    2015-08-28

    The present studies focus the quantitative analysis of elements in school chalk to ensure the safety of its use. The elements like Calcium (Ca), Aluminum (Al), Iron (Fe), Silicon (Si) and Chromium (Cr) were analyzed from settled chalk dust samples collected from five classrooms (CD-1) and also from another set of unused chalk samples collected from local market (CD-2) using Energy Dispersive X-Ray florescence(ED-XRF) spectroscopy. Presence of these elements in significant concentrations in school chalk confirmed that, it is an irritant and occupational hazard. It is suggested to use protective equipments like filtered mask for mouth, nose and chalk holders. This study also suggested using the advanced mode of techniques like Digital boards, marker boards and power point presentations to mitigate the occupational hazard for classroom chalk.

  8. X-ray photoelectron spectroscopy studies on Pd doped SnO{sub 2} liquid petroleum gas sensor

    SciTech Connect (OSTI)

    Phani, A.R.

    1997-10-01

    The present investigation deals with the electrical response of palladium doped tin oxide, as a means of improving the selectivity for liquid petroleum gas (LPG) in the presence of CO, CH{sub 4}. The sensor element with the composition of Pd(1.5 wt{percent}) in the base material SnO{sub 2} sintered at 800{degree}C, has shown a high sensitivity towards LPG with a negligible cross interference of CO and CH{sub 4} at an operating temperature of 350{degree}C. This greatly suggests the possibility of utilizing the sensor for the detection of LPG. X-ray photoelectron spectroscopy studies have been carried out to determine the possible chemical species involved in the gas-solid interaction and the enhancing mechanism of the Pd doped SnO{sub 2} sensor element, towards LPG sensitivity. {copyright} {ital 1997 American Institute of Physics.}

  9. Spectroscopic evidence for Ag(III) in highly oxidized silver films by x-ray photoelectron spectroscopy

    SciTech Connect (OSTI)

    Kaspar, Tiffany C.; Droubay, Timothy C.; Chambers, Scott A.; Bagus, Paul S.

    2010-12-16

    In situ x-ray photoelectron spectroscopy (XPS) was utilized to identify the chemical state of silver in a range of silver oxide thin films obtained by co-deposition of silver and atomic oxygen. A highly oxidized silver species was observed at an unexpectedly low Ag 3d5/2 binding energy (BE) of 366.8 eV with an associated broad satellite at 368.2 eV; this species was assigned as Ag(III). It was found to be highly unstable in vacuum, but could be regenerated by further exposure to atomic oxygen. Both BE shifts and intensity changes of the O 1s peak were found to correlate with changes in the silver oxidation state. Theoretical calculations of the expected XPS of high spin Ag(III) provide insight into the significance of satellite structure and shake features in the Ag 3d spectra.

  10. Annealing dependence of diamond-metal Schottky barrier heights probed by hard x-ray photoelectron spectroscopy

    SciTech Connect (OSTI)

    Gaowei, M.; Muller, E. M.; Rumaiz, A. K.; Weiland, C.; Cockayne, E.; Woicik, J. C.; Jordan-Sweet, J.; Smedley, J.

    2012-05-14

    Hard x-ray photoelectron spectroscopy was applied to investigate the diamond-metal Schottky barrier heights for several metals and diamond surface terminations. The position of the diamond valence-band maximum was determined by theoretically calculating the diamond density of states and applying cross section corrections. The diamond-platinum Schottky barrier height was lowered by 0.2 eV after thermal annealing, indicating annealing may increase carrier injection in diamond devices leading to photoconductive gain. The platinum contacts on oxygen-terminated diamond was found to provide a higher Schottky barrier and therefore a better blocking contact than that of the silver contact in diamond-based electronic devices.

  11. SSRL School 2008 on Hard X-ray Scattering Techniques in MES

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    May 20-22, 2008 SSRL School on Synchrotron X-ray Absorption Spectroscopy Techniques in Environmental and Materials Sciences: Theory and Application Group photo from the 2008 SSRL...

  12. Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua; Rani, Sana; Chang, Rui; Karlsson, Patrik G.; Edwards, Mårten O. M.; Lundqvist, Måns; Moberg, Robert; Ross, Phil; et al

    2015-05-07

    We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

  13. Proceedings of the eighth international colloquium on ultraviolet and x-ray spectroscopy of astrophysical and laboratory plasmas (IAU colloquium 86)

    SciTech Connect (OSTI)

    Not Available

    1984-01-01

    This volume represents the Proceedings of the Eighth International Colloquium on Ultraviolet and X-Ray Spectroscopy of Astrophysical and Laboratory Plasmas. The aim of this series of colloquia has been to bring together workers in the fields of astrophysical spectroscopy, laboratory spectroscopy and atomic physics in order to exchange ideas and results on problems which are common to these different disciplines. In addition to the presented papers there was a poster paper session. (WRF)

  14. ANALYSIS OF PASSIVATED SURFACES FOR MASS SPECTROMETER INLET SYSTEMS BY AUGER ELECTRON AND X-RAY PHOTOELECTRON SPECTROSCOPY

    SciTech Connect (OSTI)

    Ajo, H.; Clark, E.

    2010-09-01

    Stainless steel coupons approximately 0.5' in diameter and 0.125' thick were passivated with five different surface treatments and an untreated coupon was left as a control. These surface treatments are being explored for use in tritium storage containers. These coupons were made to allow surface analysis of the surface treatments using well-know surface analysis techniques. Depth profiles using Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were performed on these coupons to characterize the surface and near surface regions. Scanning electron microscope (SEM) images were collected as well. All of the surface treatments studied here appear to change the surface morphology dramatically, as evidenced by lack of tool marks on the treated samples. In terms of the passivation treatment, Vendors A-D appeared to have oxide layers that were very similar in thickness to each other (0.7-0.9 nm thick) as well as the untreated samples (the untreated sample oxide layers appeared to be somewhat larger). Vendor E's silicon coating appears to be on the order of 200 nm thick.

  15. Spatially resolved high-resolution x-ray spectroscopy of high-current plasma-focus discharges

    SciTech Connect (OSTI)

    ZajaPc, S.; Rzadkiewicz, J.; Scholz, M.; Paduch, M.; Zielinska, E.; Rosmej, O.; Yongtao, Zhao; Gojska, A.

    2010-10-15

    Soft x-ray emission from a Mather-type plasma-focus device (PF-1000) operated at {approx}400 kJ was measured. The high density and temperature plasma were generated by the discharge in the deuterium-argon gas mixture in the modified (high-current) plasma-focus configuration. A spherically bent mica crystal spectrograph viewing the axial output of the pinch region was used to measure the x-ray spectra. Spatially resolved spectra including the characteristic x-ray lines of highly ionized Ar and continua were recorded by means of an x-ray film. The x-ray emission of PF-1000 device was studied at different areas of the pinch.

  16. Toward the standard population synthesis model of the X-ray background: Evolution of X-ray luminosity and absorption functions of active galactic nuclei including Compton-thick populations

    SciTech Connect (OSTI)

    Ueda, Yoshihiro; Akiyama, Masayuki; Hasinger, Gnther; Miyaji, Takamitsu; Watson, Michael G.

    2014-05-10

    We present the most up to date X-ray luminosity function (XLF) and absorption function of active galactic nuclei (AGNs) over the redshift range from 0 to 5, utilizing the largest, highly complete sample ever available obtained from surveys performed with Swift/BAT, MAXI, ASCA, XMM-Newton, Chandra, and ROSAT. The combined sample, including that of the Subaru/XMM-Newton Deep Survey, consists of 4039 detections in the soft (0.5-2 keV) and/or hard (>2 keV) band. We utilize a maximum likelihood method to reproduce the count rate versus redshift distribution for each survey, by taking into account the evolution of the absorbed fraction, the contribution from Compton-thick (CTK) AGNs, and broadband spectra of AGNs, including reflection components from tori based on the luminosity- and redshift-dependent unified scheme. We find that the shape of the XLF at z ? 1-3 is significantly different from that in the local universe, for which the luminosity-dependent density evolution model gives much better description than the luminosity and density evolution model. These results establish the standard population synthesis model of the X-ray background (XRB), which well reproduces the source counts, the observed fractions of CTK AGNs, and the spectrum of the hard XRB. The number ratio of CTK AGNs to the absorbed Compton-thin (CTN) AGNs is constrained to be ?0.5-1.6 to produce the 20-50 keV XRB intensity within present uncertainties, by assuming that they follow the same evolution as CTN AGNs. The growth history of supermassive black holes is discussed based on the new AGN bolometric luminosity function.

  17. Elemental content of enamel and dentin after bleaching of teeth (a comparative study between laser-induced breakdown spectroscopy and x-ray photoelectron spectroscopy)

    SciTech Connect (OSTI)

    Imam, H.; Ahmed, Doaa; Eldakrouri, Ashraf; Department of Optometry and Vision Science, College of Applied Medical Science, King Saud University, Riyadh

    2013-06-21

    The elemental content of the superficial and inner enamel as well as that of dentin was analyzed using laser-induced breakdown spectroscopy (LIBS) and x-ray photoelectron spectroscopy (XPS) of bleached and unbleached tooth specimens. It is thus clear from the spectral analysis using both the LIBS and XPS technique that elemental changes (though insignificant within the scopes of this study) of variable intensities do occur on the surface of the enamel and extend deeper to reach dentin. The results of the LIBS revealed a slight reduction in the calcium levels in the bleached compared to the control specimens in all the different bleaching groups and in both enamel and dentin. The good correlation found between the LIBS and XPS results demonstrates the possibility of LIBS technique for detection of minor loss in calcium and phosphorus in enamel and dentin.

  18. Direct and quantitative broadband absorptance spectroscopy with...

    Office of Scientific and Technical Information (OSTI)

    Patent: Direct and quantitative broadband absorptance spectroscopy with multilayer ... DOE Contract Number: FG02-02ER45977 Resource Type: Patent Research Org: Massachusetts ...

  19. Combining Feedback Absorption Spectroscopy, Amplified Resonance...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Automotive Emissions Combining Feedback Absorption Spectroscopy, Amplified Resonance and Low Pressure Sampling for the Measurement of Nitrogen-Containing Compounds in Automotive ...

  20. Spectroscopy

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Spectroscopy Spectroscopy Print In spectroscopy experiments, a sample is illuminated with light and the various product particles (electrons, ions, or fluorescent photons) are detected and analyzed.The unifying feature is that some "property" of a material is measured as the x-ray (photon) energy is swept though a range of values. At the most basic level, one measures the absorption, transmission, or reflectivity of a sample as a function of photon energy. Probes that use the vacuum

  1. Surface study of stainless steel electrode deposition from soil electrokinetic (EK) treatment using X-ray photoelectron spectroscopy (XPS)

    SciTech Connect (OSTI)

    Embong, Zaidi; Johar, Saffuwan; Tajudin, Saiful Azhar Ahmad; Sahdan, Mohd Zainizan

    2015-04-29

    Electrokinetic (EK) remediation relies upon application of a low-intensity direct current through the soil between stainless steel electrodes that are divided into a cathode array and an anode array. This mobilizes charged species, causing ions and water to move toward the electrodes. Metal ions and positively charged organic compounds move toward the cathode. Anions such as chloride, fluoride, nitrate, and negatively charged organic compounds move toward the anode. Here, this remediation techniques lead to a formation of a deposition at the both cathode and anode surface that mainly contributed byanion and cation from the remediated soil. In this research, Renggam-Jerangau soil species (HaplicAcrisol + RhodicFerralsol) with a surveymeter reading of 38.0 ± 3.9 μR/hr has been investigation in order to study the mobility of the anion and cation under the influence electric field. Prior to the EK treatment, the elemental composition of the soil and the stainless steel electrode are measured using XRF analyses. Next, the soil sample is remediated at a constant electric potential of 30 V within an hour of treatment period. A surface study for the deposition layer of the cathode and anode using X-ray Photoelectron spectroscopy (XPS) revealed that a narrow photoelectron signal from oxygen O 1s, carbon, C 1s silica, Si 2p, aluminium, Al 2p and chromium, Cr 2p exhibited on the electrode surface and indicate that a different in photoelectron intensity for each element on both electrode surface. In this paper, the mechanism of Si{sup 2+} and Al{sup 2+} cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.

  2. Applications of x-ray synchrotron radiation techniques to the study of dispersed electrocatalysts in high area materials

    SciTech Connect (OSTI)

    McBreen, J.

    1991-12-31

    This report discusses work demonstrating that X-Ray Absorption Spectroscopy is a very powerful technique for the study of electrocatalysts. Results for a prototech catalyst, and platinum are presented. (JL)

  3. Applications of x-ray synchrotron radiation techniques to the study of dispersed electrocatalysts in high area materials

    SciTech Connect (OSTI)

    McBreen, J.

    1991-01-01

    This report discusses work demonstrating that X-Ray Absorption Spectroscopy is a very powerful technique for the study of electrocatalysts. Results for a prototech catalyst, and platinum are presented. (JL)

  4. X-ray polarization spectroscopy to study anisotropic velocity distribution of hot electrons produced by an ultra-high-intensity laser

    SciTech Connect (OSTI)

    Inubushi, Y.; Okano, Y.; Nishimura, H.; Cai, H.; Nagatomo, H.; Kai, T.; Fujioka, S.; Nakamura, T.; Johzaki, T.; Mima, K.; Kawamura, T.; Batani, D.; Morace, A.; Redaelli, R.; Fourment, C.; Santos, J. J.; Malka, G.

    2010-03-15

    The anisotropy of the hot-electron velocity distribution in ultra-high-intensity laser produced plasma was studied with x-ray polarization spectroscopy using multilayer planar targets including x-ray emission tracer in the middle layer. This measurement serves as a diagnostic for hot-electron transport from the laser-plasma interaction region to the overdense region where drastic changes in the isotropy of the electron velocity distribution are observed. These polarization degrees are consistent with analysis of a three-dimensional polarization spectroscopy model coupled with particle-in-cell simulations. Electron velocity distribution in the underdense region is affected by the electric field of the laser and that in the overdense region becomes wider with increase in the tracer depth. A full-angular spread in the overdense region of 22.4 deg.{sub -2.4}{sup +5.4} was obtained from the measured polarization degree.

  5. Hard disk drive based microsecond x-ray chopper for characterization of ionization chambers and photodiodes

    SciTech Connect (OSTI)

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

    2015-03-15

    A fast X-ray chopper capable of producing ms long X-ray pulses with a typical rise time of few μs was realized. It is ideally suited to investigate the temporal response of X-ray detectors with response times of the order of μs to ms, in particular, any kind of ionization chambers and large area photo diodes. The drive mechanism consists of a brushless DC motor and driver electronics from a common hard disk drive, keeping the cost at an absolute minimum. Due to its simple construction and small dimensions, this chopper operates at home lab based X-ray tubes and synchrotron radiation sources as well. The dynamics of the most important detectors used in time resolved X-ray absorption spectroscopy, namely, ionization chambers and Passivated Implanted Planar Silicon photodiodes, were investigated in detail. The results emphasize the applicability of this X-ray chopper.

  6. An analytic model for the response of a CZT detector in diagnostic energy dispersive x-ray spectroscopy

    SciTech Connect (OSTI)

    LeClair, Robert J.; Wang Yinkun; Zhao Peiying; Boileau, Michel; Wang, Lilie; Fleurot, Fabrice [Department of Physics and Astronomy, Laurentian University, 935 Ramsey Lake Road, Sudbury, Ontario P3E 2C6 (Canada) and Biomolecular Sciences Program, Laurentian University, 935 Ramsey Lake Road, Sudbury, Ontario P3E 2C6 (Canada); Department of Physics and Astronomy, Laurentian University, 935 Ramsey Lake Road, Sudbury, Ontario P3E 2C6 (Canada)

    2006-05-15

    A CdZnTe detector (CZTD) can be very useful for measuring diagnostic x-ray spectra. The semiconductor detector does, however, exhibit poor hole transport properties and fluorescence generation upon atomic de-excitations. This article describes an analytic model to characterize these two phenomena that occur when a CZTD is exposed to diagnostic x rays. The analytical detector response functions compare well with those obtained via Monte Carlo calculations. The response functions were applied to 50, 80, and 110 kV x-ray spectra. Two 50 kV spectra were measured; one with no filtration and the other with 1.35 mm Al filtration. The unfiltered spectrum was numerically filtered with 1.35 mm of Al in order to see whether the recovered spectrum resembled the filtered spectrum actually measured. A deviation curve was obtained by subtracting one curve from the other on an energy bin by bin basis. The deviation pattern fluctuated around the zero line when corrections were applied to both spectra. Significant deviations from zero towards the lower energies were observed when the uncorrected spectra were used. Beside visual observations, the exposure obtained using the numerically attenuated unfiltered beam was compared to the exposure calculated with the actual filtered beam. The percent differences were 0.8% when corrections were applied and 25% for no corrections. The model can be used to correct diagnostic x-ray spectra measured with a CdZnTe detector.

  7. Single-Crystal Raman Spectroscopy and X-ray Crystallography at Beamline X26-C of the NSLS

    SciTech Connect (OSTI)

    D Stoner-Ma; J Skinner; D Schneider; M Cowan; R Sweet; A Orville

    2011-12-31

    Three-dimensional structures derived from X-ray diffraction of protein crystals provide a wealth of information. Features and interactions important for the function of macromolecules can be deduced and catalytic mechanisms postulated. Still, many questions can remain, for example regarding metal oxidation states and the interpretation of 'mystery density', i.e. ambiguous or unknown features within the electron density maps, especially at {approx}2 {angstrom} resolutions typical of most macromolecular structures. Beamline X26-C at the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory (BNL), provides researchers with the opportunity to not only determine the atomic structure of their samples but also to explore the electronic and vibrational characteristics of the sample before, during and after X-ray diffraction data collection. When samples are maintained under cryo-conditions, an opportunity to promote and follow photochemical reactions in situ as a function of X-ray exposure is also provided. Plans are in place to further expand the capabilities at beamline X26-C and to develop beamlines at NSLS-II, currently under construction at BNL, which will provide users access to a wide array of complementary spectroscopic methods in addition to high-quality X-ray diffraction data.

  8. Absorption spectroscopy of a laboratory photoionized plasma experiment at Z

    SciTech Connect (OSTI)

    Hall, I. M.; Durmaz, T.; Mancini, R. C.; Bailey, J. E.; Rochau, G. A.; Golovkin, I. E.; MacFarlane, J. J.

    2014-03-15

    The Z facility at the Sandia National Laboratories is the most energetic terrestrial source of X-rays and provides an opportunity to produce photoionized plasmas in a relatively well characterised radiation environment. We use detailed atomic-kinetic and spectral simulations to analyze the absorption spectra of a photoionized neon plasma driven by the x-ray flux from a z-pinch. The broadband x-ray flux both photoionizes and backlights the plasma. In particular, we focus on extracting the charge state distribution of the plasma and the characteristics of the radiation field driving the plasma in order to estimate the ionisation parameter.

  9. NuSTAR study of hard X-ray morphology and spectroscopy of PWN G21.50.9

    SciTech Connect (OSTI)

    Nynka, Melania; Hailey, Charles J.; Gotthelf, Eric V.; Mori, Kaya; Perez, Kerstin [Columbia Astrophysics Laboratory, Columbia University, New York, NY 10027 (United States); Reynolds, Stephen P. [Physics Department, NC State University, Raleigh, NC 27695 (United States); An, Hongjun [Department of Physics, McGill University, Rutherford Physics Building, 3600 University Street, Montreal, Quebec H3A 2T8 (Canada); Baganoff, Frederick K. [Center for Space Research, Massachusetts Institute of Technology, Cambridge, MA 02139-4307 (United States); Boggs, Steven E.; Krivonos, Roman; Zoglauer, Andreas [Space Sciences Laboratory, University of California, Berkeley, CA 94720 (United States); Christensen, Finn E. [DTU Space, National Space Institute, Technical University of Denmark, Elektrovej 327, DK-2800 Lyngby (Denmark); Craig, William W. [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Grefenstette, Brian W.; Harrison, Fiona A.; Madsen, Kristin K. [Cahill Center for Astronomy and Astrophysics, California Institute of Technology, Pasadena, CA 91125 (United States); Stern, Daniel [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109 (United States); Wik, Daniel R.; Zhang, William W. [NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States)

    2014-07-01

    We present NuSTAR high-energy X-ray observations of the pulsar wind nebula (PWN)/supernova remnant G21.50.9. We detect integrated emission from the nebula up to ?40 keV, and resolve individual spatial features over a broad X-ray band for the first time. The morphology seen by NuSTAR agrees well with that seen by XMM-Newton and Chandra below 10 keV. At high energies, NuSTAR clearly detects non-thermal emission up to ?20 keV that extends along the eastern and northern rim of the supernova shell. The broadband images clearly demonstrate that X-ray emission from the North Spur and Eastern Limb results predominantly from non-thermal processes. We detect a break in the spatially integrated X-ray spectrum at ?9 keV that cannot be reproduced by current spectral energy distribution models, implying either a more complex electron injection spectrum or an additional process such as diffusion compared to what has been considered in previous work. We use spatially resolved maps to derive an energy-dependent cooling length scale, L(E)?E{sup m} with m = 0.21 0.01. We find this to be inconsistent with the model for the morphological evolution with energy described by Kennel and Coroniti. This value, along with the observed steepening in power-law index between radio and X-ray, can be quantitatively explained as an energy-loss spectral break in the simple scaling model of Reynolds, assuming particle advection dominates over diffusion. This interpretation requires a substantial departure from spherical magnetohydrodynamic, magnetic-flux-conserving outflow, most plausibly in the form of turbulent magnetic-field amplification.

  10. X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy investigation of Al-related dipole at the HfO{sub 2}/Si interface

    SciTech Connect (OSTI)

    Zhu, L. Q.; Barrett, N.; Jegou, P.

    2009-01-15

    The presence of an ultrathin oxide layer at the high-k/SiO{sub 2} interface may result in an interfacial dipole related to the specific high-k dielectric used for the gate stacks. 1 nm HfO{sub 2}/x nmAl{sub 2}O{sub 3}/SiO{sub 2}/Si stacks with different x values (x=0, 0.4, 0.8, 1.2) have been prepared by atomic layer deposition. Using photoelectron spectroscopy, an Al-related interfacial dipole in the HfO{sub 2}/Al{sub 2}O{sub 3}/SiO{sub 2} gate stack has been identified. X-ray photoelectron spectroscopy analysis shows that the dipole is correlated with the formation of an interfacial Al-silicate. The dipole is located at the Al-silicate interface between Al{sub 2}O{sub 3} and SiO{sub 2}, and its strength increases with the increase in Al{sub 2}O{sub 3} thickness because of Al silicate growth. Such Al-related interfacial dipole should have potential applications in future positive metal-oxide-semiconductor devices.

  11. Spectroscopy

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Spectroscopy Print In spectroscopy experiments, a sample is illuminated with light and the various product particles (electrons, ions, or fluorescent photons) are detected and analyzed.The unifying feature is that some "property" of a material is measured as the x-ray (photon) energy is swept though a range of values. At the most basic level, one measures the absorption, transmission, or reflectivity of a sample as a function of photon energy. Probes that use the vacuum ultraviolet

  12. A Fern Fatale - X-ray Absorption Spectroscopy Imaging an Arsenic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    accumulate large amounts of it. What is more, the plant converts it to the most toxic inorganic form known. How does it do this? First some background; while there is some...

  13. Characterization of the interaction of uranyl ions with humic acids by x-ray absorption spectroscopy

    SciTech Connect (OSTI)

    Reich, T.; Denecke, M.A.; Pompe, S.

    1995-11-01

    Humic substances are present throughout the environment in soil and natural water. They are organic macromolecules with a variable structural formula, molecular weight, and a wide variety of functional groups depending on their origin. In natural waters, humic substances represent the main component of the {open_quotes}dissolved organic carbon{close_quotes} (DOC). The DOC may vary considerably from 1 mg/L at sea water surfaces to 50 mg/L at the surface in dark water swamps. There is strong evidence that all actinides form complexes with humic substances in natural waters. Therefore, humic substances can play an important role in the environmental migration of radionuclides by enhancing their transport. Retardation through humic substance interaction may be also possible due to formation of precipitating agglomerates. For remediation and restoration of contaminated environmental sites and risk assessment of future nuclear waste repositories, it is important to improve the predictive capabilities for radionuclide migration through a better understanding of the interaction of radionuclides with humic substances.

  14. Electronic structure of β-Ga{sub 2}O{sub 3} single crystals investigated by hard X-ray photoelectron spectroscopy

    SciTech Connect (OSTI)

    Li, Guo-Ling; Zhang, Fabi; Guo, Qixin; Cui, Yi-Tao; Oji, Hiroshi; Son, Jin-Young

    2015-07-13

    By combination of hard X-ray photoelectron spectroscopy (HAXPES) and first-principles band structure calculations, the electronic states of β-Ga{sub 2}O{sub 3} were investigated to deepen the understanding of bulk information for this compound. The valence band spectra of HAXPES presented the main contribution from Ga 4sp, which are well represented by photoionization cross section weighted partial density of states. The experimental data complemented with the theoretical study yield a realistic picture of the electronic structure for β-Ga{sub 2}O{sub 3}.

  15. High-Pressure Raman Spectroscopy and X-ray Diffraction Studies of a Terpolymer of Tetrafluoroethylene-Hexafluoropropylene-Vinylidene Fluoride: THV 500

    SciTech Connect (OSTI)

    Emmons, E.D.; Velisavljevic, N.; Schoonover, J.R.; Dattelbaum, D.M.

    2008-04-02

    High-pressure Raman spectroscopy and X-ray diffraction of THV 500, a terpolymer of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride, were performed using diamond anvil cells (DAC). Changes in the interatomic spacing as well as shifts of several of the vibrational bands as a function of pressure were measured up to {approx}10 GPa. The changes in interatomic spacing and shifts of the vibrational bands are compared to those of polytetrafluoroethylene, showing the effects of copolymerization and reduced crystallinity. The high-pressure behavior of polymers is a relatively unexplored field but is becoming increasingly important due to applications where polymers experience extreme conditions.

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

    SciTech Connect (OSTI)

    Sharkov, M. D., E-mail: mischar@mail.ioffe.ru; Boiko, M. E.; Bobyl, A. V.; Ershenko, E. M.; Terukov, E. I. [Russian Academy of Sciences, Ioffe Physical-Technical Institute (Russian Federation); Zubavichus, Y. V. [National Research Centre Kurchatov Institute (Russian Federation)

    2013-12-15

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

  17. X-Ray Diagnostics

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    including film developing and scanning, and image plate scanning. Related images X-ray framing camera being loaded into the TIM in the Trident North Target Area. X-ray framing...

  18. Conduction band offset at GeO{sub 2}/Ge interface determined by internal photoemission and charge-corrected x-ray photoelectron spectroscopies

    SciTech Connect (OSTI)

    Zhang, W. F.; Nishimula, T.; Nagashio, K.; Kita, K.; Toriumi, A.

    2013-03-11

    We report a consistent conduction band offset (CBO) at a GeO{sub 2}/Ge interface determined by internal photoemission spectroscopy (IPE) and charge-corrected X-ray photoelectron spectroscopy (XPS). IPE results showed that the CBO value was larger than 1.5 eV irrespective of metal electrode and substrate type variance, while an accurate determination of valence band offset (VBO) by XPS requires a careful correction of differential charging phenomena. The VBO value was determined to be 3.60 {+-} 0.2 eV by XPS after charge correction, thus yielding a CBO (1.60 {+-} 0.2 eV) in excellent agreement with the IPE results. Such a large CBO (>1.5 eV) confirmed here is promising in terms of using GeO{sub 2} as a potential passivation layer for future Ge-based scaled CMOS devices.

  19. Upgraded high time-resolved x-ray imaging crystal spectroscopy system for J-TEXT ohmic plasmas

    SciTech Connect (OSTI)

    Jin, W.; Chen, Z. Y. Huang, D. W.; Li, Q. L.; Yan, W.; Luo, Y. H.; Huang, Y. H.; Tong, R. H.; Yang, Z. J.; Rao, B.; Ding, Y. H.; Zhuang, G.; Lee, S. G.; Shi, Y. J.

    2014-02-15

    This paper presents the upgraded x-ray imaging crystal spectrometer (XICS) system on Joint Texas Experimental Tokamak (J-TEXT) tokamak and the latest experimental results obtained in last campaign. With 500 Hz frame rate of the new Pilatus detector and 5 cm 10 cm spherically bent crystal, the XICS system can provide core electron temperature (T{sub e}), core ion temperature (T{sub i}), and plasma toroidal rotation (V{sub ?}) with a maximum temporal resolution of 2 ms for J-TEXT pure ohmic plasmas. These parameters with high temporal resolution are very useful in tokamak plasma research, especially for rapidly changed physical processes. The experimental results from the upgraded XICS system are presented.

  20. On the Putative Detection of Z>0 X-Ray Absorption Features in the Spectrum of Mrk 421

    SciTech Connect (OSTI)

    Rasmussen, Andrew P.; Kahn, Steven M.; Paerels, Frits; Herder, Jan Willem den; Kaastra, Jelle; de Vries, Cor; /SRON, Utrecht

    2006-04-28

    In a series of papers, Nicastro et al. have claimed the detection of z > 0 O VII absorption features in the spectrum of Mrk 421 obtained with the Chandra Low Energy Transmission Grating Spectrometer (LETGS). We evaluate those claims in the context of a high quality spectrum of the same source obtained with the Reflection Grating Spectrometer (RGS) on XMM-Newton. The data comprise over 955 ksec of usable exposure time and more than 2.6 x 10{sup 4} counts per 50 m{angstrom} at 21.6 {angstrom}. We concentrate on the spectrally clean region (21.3 < {lambda} < 22.5 {angstrom}) where sharp features due to the astrophysically abundant O VII may reveal an intervening, warm-hot intergalactic medium (WHIM). In spite of the fact that the sensitivity of the RGS data is higher than that of the original LETGS data presented by Nicastro et al., we do not confirm detection of any of the intervening systems claimed to date. Rather, we detect only three unsurprising, astrophysically expected features down to the log (N{sub i}) {approx} 14.6 (3{sigma}) sensitivity level. Each of the two purported WHIM features is rejected with a statistical confidence that exceeds that reported for its initial detection. While we can not rule out the existence of fainter, WHIM related features in these spectra, we suggest that previous discovery claims were premature. A more recent paper by Williams et al. claims to have demonstrated that the RGS data we analyze here do not have the resolution or statistical quality required to confirm or deny the LETGS detections. We show that the Williams et al. reduction of the RGS data was highly flawed, leading to an artificial and spurious degradation of the instrument response. We carefully highlight the differences between our analysis presented here and those published by Williams et al.

  1. X-Ray Diagnostics

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    X-Ray Diagnostics X-Ray Diagnostics Maintenance of existing devices and development of advanced concepts Contact John Oertel (505) 665-3246 Email Hot, dense matter produced by intense laser interaction with a solid target often produces x-rays with energies from 100 eV to those exceeding 100 keV. A suite of diagnostics and methods have been deployed at Trident to diagnose the x-ray emission from laser-matter interaction experiments, or to use the x-rays as a probe of dense matter. These

  2. Controlling X-rays With Light

    SciTech Connect (OSTI)

    Glover, Ernie; Hertlein, Marcus; Southworth, Steve; Allison, Tom; van Tilborg, Jeroen; Kanter, Elliot; Krassig, B.; Varma, H.; Rude, Bruce; Santra, Robin; Belkacem, Ali; Young, Linda

    2010-08-02

    Ultrafast x-ray science is an exciting frontier that promises the visualization of electronic, atomic and molecular dynamics on atomic time and length scales. A largelyunexplored area of ultrafast x-ray science is the use of light to control how x-rays interact with matter. In order to extend control concepts established for long wavelengthprobes to the x-ray regime, the optical control field must drive a coherent electronic response on a timescale comparable to femtosecond core-hole lifetimes. An intense field is required to achieve this rapid response. Here an intense optical control pulse isobserved to efficiently modulate photoelectric absorption for x-rays and to create an ultrafast transparency window. We demonstrate an application of x-ray transparencyrelevant to ultrafast x-ray sources: an all-photonic temporal cross-correlation measurement of a femtosecond x-ray pulse. The ability to control x-ray/matterinteractions with light will create new opportunities at current and next-generation x-ray light sources.

  3. In situ and ex situ spectroelectrochemical and X-ray absorption studies on rechargeable, chemically-modified and other MnO{sub 2} materials

    SciTech Connect (OSTI)

    Conway, B.E.; Qu, D.; McBreen, J. |

    1992-12-31

    A combined series of in situ and ex situ UV spectroelectrochemical and X-ray absorption studies have been made on MnO{sub 2}, chemically-modified by small amounts of Bi(III), and comparatively on other MnO{sub 2} materials such as a blank (Bi-free) and {gamma}-MnO{sub 2}. These procedures are applied in order to follow the oxidation-states of Bi and of Mn during the course of discharge and recharge of MnO{sub 2} as a battery cathode material, and the extents of rechargeability that can be achieved with such materials. Presence of Bi appears to provide a preferred ``heterogeneous`` discharge/recharge pathway involving a soluble Mn(III) intermediate, over the alternative ``electron-proton`` hopping, solid-state mechanism. From XAS results, it is concluded that presence of Bi, although not affecting the O-coordination, does influence the Mn-Mn coordination, determining the way the MnO{sub 2} coordination octahedra are connected.

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

    SciTech Connect (OSTI)

    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.

  5. A high resolution and large solid angle x-ray Raman spectroscopy end-station at the Stanford Synchrotron Radiation Lightsource

    SciTech Connect (OSTI)

    Sokaras, D.; Nordlund, D.; Weng, T.-C.; Velikov, P.; Wenger, D.; Garachtchenko, A.; George, M.; Borzenets, V.; Johnson, B.; Rabedeau, T.; Mori, R. Alonso; Bergmann, U.; Qian, Q.

    2012-04-15

    We present a new x-ray Raman spectroscopy end-station recently developed, installed, and operated at the Stanford Synchrotron Radiation Lightsource. The end-station is located at wiggler beamline 6-2 equipped with two monochromators-Si(111) and Si(311) as well as collimating and focusing optics. It consists of two multi-crystal Johann type spectrometers arranged on intersecting Rowland circles of 1 m diameter. The first one, positioned at the forward scattering angles (low-q), consists of 40 spherically bent and diced Si(110) crystals with 100 mm diameters providing about 1.9% of 4{pi} sr solid angle of detection. When operated in the (440) order in combination with the Si (311) monochromator, an overall energy resolution of 270 meV is obtained at 6462.20 eV. The second spectrometer, consisting of 14 spherically bent Si(110) crystal analyzers (not diced), is positioned at the backward scattering angles (high-q) enabling the study of non-dipole transitions. The solid angle of this spectrometer is about 0.9% of 4{pi} sr, with a combined energy resolution of 600 meV using the Si (311) monochromator. These features exceed the specifications of currently existing relevant instrumentation, opening new opportunities for the routine application of this photon-in/photon-out hard x-ray technique to emerging research in multidisciplinary scientific fields, such as energy-related sciences, material sciences, physical chemistry, etc.

  6. High-resolution elemental mapping of human placental chorionic villi using synchrotron X-ray fluorescence spectroscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Punshon, Tracy; Chen, Si; Finney, Lydia; Howard, Louisa; Jackson, Brian P.; Karagas, Margaret R.; Ornvold, Kim

    2015-07-03

    The placenta is the organ that mediates transport of nutrients and waste materials between mother and fetus. Synchrotron X-ray fluorescence (SXRF) microanalysis is a tool for imaging the distribution and quantity of elements in biological tissue, which can be used to study metal transport across biological membranes. Our aims were to pilot placental biopsy specimen preparation techniques that could be integrated into an ongoing epidemiology birth cohort study without harming rates of sample acquisition. We studied the effects of fixative (formalin or glutaraldehyde) and storage duration (30 days or immediate processing) on metal distribution and abundance and investigated a thaw-fixationmore » protocol for archived specimens stored at -80° C. We measured fixative elemental composition with and without a placental biopsy via inductively coupled plasma mass spectrometry (ICP-MS) to quantify fixative-induced elemental changes. Formalin-fixed specimens showed hemolysis of erythrocytes. The glutaraldehyde-paraformaldehyde solution in HEPES buffer (GTA-HEPES) had superior anatomical preservation, avoided hemolysis, and minimized elemental loss, although some cross-linking of exogenous Zn was evident. Elemental loss from tissue stored in fixative for 1 month showed variable losses (≈ 40 % with GTA-HEPES), suggesting storage duration be controlled for. Lastly, thawing of tissue held at -80 °C in a GTA-HEPES solution provided high-quality visual images and elemental images« less

  7. High-resolution Elemental Mapping of Human Placental Chorionic Villi Using Synchrotron X-ray Fluorescence Spectroscopy

    SciTech Connect (OSTI)

    Punshon, Tracy; Chen, Si; Finney, Lydia; Howard, Louisa; Jackson, Brian P.; Karagas, Margaret R.; Ornvold, Kim

    2015-09-01

    The placenta is the organ that mediates transport of nutrients and waste materials between mother and fetus. Synchrotron X-ray fluorescence (SXRF) microanalysis is a tool for imaging the distribution and quantity of elements in biological tissue, which can be used to study metal transport across biological membranes. Our aims were to pilot placental biopsy specimen preparation techniques that could be integrated into an ongoing epidemiology birth cohort study without harming rates of sample acquisition. We studied the effects of fixative (formalin or glutaraldehyde) and storage duration (30 days or immediate processing) on metal distribution and abundance and investigated a thaw-fixation protocol for archived specimens stored at -80 A degrees C. We measured fixative elemental composition with and without a placental biopsy via inductively coupled plasma mass spectrometry (ICP-MS) to quantify fixative-induced elemental changes. Formalin-fixed specimens showed hemolysis of erythrocytes. The glutaraldehyde-paraformaldehyde solution in HEPES buffer (GTA-HEPES) had superior anatomical preservation, avoided hemolysis, and minimized elemental loss, although some cross-linking of exogenous Zn was evident. Elemental loss from tissue stored in fixative for 1 month showed variable losses (a parts per thousand 40 % with GTA-HEPES), suggesting storage duration be controlled for. Thawing of tissue held at -80 A degrees C in a GTA-HEPES solution provided high-quality visual images and elemental images

  8. The Soft X-ray Research instrument at the Linac Coherent Light...

    Office of Scientific and Technical Information (OSTI)

    The Soft X-ray Research instrument at the Linac Coherent Light Source Georgi L. ... Fremont, CA 94539, USA. Keywords: FEL; X-ray; ultrafast; spectroscopy; materials science. ...

  9. X-Ray Diffraction > Analytical Resources > Research > The Energy Materials

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Center at Cornell Analytical Resources In This Section Differential Electrochemical Mass Spectroscopy (DEMS) Electron Microscopy X-Ray Diffraction X-Ray Diffraction

  10. Time-resolved soft-x-ray spectroscopy of a magnetic octupole transition in nickel-like xenon, cesium, and barium ions

    SciTech Connect (OSTI)

    Trabert, E; Beiersdorfer, P; Brown, G V; Boyce, K; Kelley, R L; Kilbourne, C A; Porter, F S; Szymkowiak, A

    2005-11-11

    A microcalorimeter with event mode capability for time-resolved soft-x-ray spectroscopy, and a high-resolution flat-field EUV spectrometer have been employed at the Livermore EBIT-I electron beam ion trap for observations and wavelength measurements of M1, E2, and M3 decays of long-lived levels in the Ni-like ions Xe{sup 26+}, Cs{sup 27+}, and Ba{sup 28+}. Of particular interest is the lowest excited level, 3d{sup 9}4s {sup 3}D{sub 3}, which can only decay via a magnetic octupole (M3) transition. For this level in Xe an excitation energy of (590.40 {+-} 0.03eV) and a level lifetime of (11.5 {+-} 0.5 ms) have been determined.