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Sample records for absorption x-ray photoelectron

  1. A new endstation at the Swiss Light Source for ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy measurements of liquid solutions.

    PubMed

    Brown, Matthew A; Redondo, Amaia Beloqui; Jordan, Inga; Duyckaerts, Nicolas; Lee, Ming-Tao; Ammann, Markus; Nolting, Frithjof; Kleibert, Armin; Huthwelker, Thomas; Müächler, Jean-Pierre; Birrer, Mario; Honegger, Juri; Wetter, Reto; Wörner, Hans Jakob; van Bokhoven, Jeroen A

    2013-07-01

    A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutions and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented. PMID:23902081

  2. A new endstation at the Swiss Light Source for ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy measurements of liquid solutions

    SciTech Connect

    Brown, Matthew A.; Redondo, Amaia Beloqui; Duyckaerts, Nicolas; Mächler, Jean-Pierre; Jordan, Inga; Wörner, Hans Jakob; Lee, Ming-Tao; Ammann, Markus; Nolting, Frithjof; Kleibert, Armin; Huthwelker, Thomas; Birrer, Mario; Honegger, Juri; Wetter, Reto; Bokhoven, Jeroen A. van

    2013-07-15

    A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutions and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented.

  3. X-ray absorption and X-ray photoelectron spectroscopic study of arsenic mobilization during mackinawite (FeS) oxidation.

    PubMed

    Jeong, Hoon Y; Han, Young-Soo; Hayes, Kim F

    2010-02-01

    In this study we investigated the speciation of the solid-phase As formed by reacting 2 x 10(-4) M As(III) with 1.0 g/L mackinawite and the potential for these sorbed species to be mobilized (released into the aqueous phase) upon exposure to atmospheric oxygen at pH 4.9, 7.1, and 9.1. Before oxygen exposure, X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) analyses indicated that As(III) was removed from the aqueous phase by forming As(0), AsS, and surface precipitates as thioarsenites at pH 4.9 and As(0) and thioarsenite surface precipitates at pH 7.1 and 9.1. When oxygen was introduced, XAS analysis indicated that As(0) and the surface precipitates were quickly transformed, whereas AsS was persistent. During intermediate oxygen exposure times, dissolved As increased at pH 4.9 and 7.1 due to the rapid oxidation of As(0) and the slow precipitation of iron (oxyhydr)oxides, the oxidation products of mackinawite. This indicates that oxidative mobilization is a potential pathway for arsenic contamination of water at acidic to neutral pH. The mobilized As was eventually resorbed by forming edge-sharing and double-corner-sharing surface complexes with iron (oxyhydr)oxides.

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

    NASA Astrophysics Data System (ADS)

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

    2007-11-01

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

  5. Hard X-ray photoelectron and X-ray absorption spectroscopy characterization of oxidized surfaces of iron sulfides

    NASA Astrophysics Data System (ADS)

    Mikhlin, Yuri; Tomashevich, Yevgeny; Vorobyev, Sergey; Saikova, Svetlana; Romanchenko, Alexander; Félix, Roberto

    2016-11-01

    Hard X-ray photoelectron spectroscopy (HAXPES) using an excitation energy range of 2 keV to 6 keV in combination with Fe K- and S K-edge XANES, measured simultaneously in total electron (TEY) and partial fluorescence yield (PFY) modes, have been applied to study near-surface regions of natural polycrystalline pyrite FeS2 and pyrrhotite Fe1-xS before and after etching treatments in an acidic ferric chloride solution. It was found that the following near-surface regions are formed owing to the preferential release of iron from oxidized metal sulfide lattices: (i) a thin, no more than 1-4 nm in depth, outer layer containing polysulfide species, (ii) a layer exhibiting less pronounced stoichiometry deviations and low, if any, concentrations of polysulfide, the composition and dimensions of which vary for pyrite and pyrrhotite and depend on the chemical treatment, and (iii) an extended almost stoichiometric underlayer yielding modified TEY XANES spectra, probably, due to a higher content of defects. We suggest that the extended layered structure should heavily affect the near-surface electronic properties, and processes involving the surface and interfacial charge transfer.

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

    PubMed

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

    2014-08-30

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-07-01

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

  8. Theoretical characterization of X-ray absorption, emission, and photoelectron spectra of nitrogen doped along graphene edges.

    PubMed

    Wang, Xianlong; Hou, Zhufeng; Ikeda, Takashi; Oshima, Masaharu; Kakimoto, Masa-aki; Terakura, Kiyoyuki

    2013-01-24

    K-edge X-ray absorption (XAS), emission (XES), and photoelectron (XPS) spectra of nitrogen doped along graphene edges are systematically investigated by using first-principles methods. In this study we considered pyridinium-like, pyridine-like, cyanide-like, and amine-like nitrogens at armchair and zigzag edges and pyrrole-like nitrogen at armchair edge as well as graphite-like nitrogen at graphene interior site. Our results indicate that nitrogen configuration and its location (armchair or zigzag edge) in nitrogen-doped graphene can be identified via the spectral analysis. Furthermore, some controversial spectral features observed in experiment for N-doped graphene-like materials are unambiguously assigned. The present analysis gives an explanation to the reason why the peak assignment is usually made differently between XPS and XAS.

  9. X-ray Absorption Spectroscopy

    SciTech Connect

    Yano, Junko; Yachandra, Vittal K.

    2009-07-09

    This review gives a brief description of the theory and application of X-ray absorption spectroscopy, both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), especially, pertaining to photosynthesis. The advantages and limitations of the methods are discussed. Recent advances in extended EXAFS and polarized EXAFS using oriented membranes and single crystals are explained. Developments in theory in understanding the XANES spectra are described. The application of X-ray absorption spectroscopy to the study of the Mn4Ca cluster in Photosystem II is presented.

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

    NASA Astrophysics Data System (ADS)

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

    2004-09-01

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

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

    SciTech Connect

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

    2007-05-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  13. X-ray absorption and photoelectron spectroscopic study of the association of As(III) with nanoparticulate FeS and FeS-coated sand.

    PubMed

    Han, Young-Soo; Jeong, Hoon Y; Demond, Avery H; Hayes, Kim F

    2011-11-01

    Iron sulfide (FeS) has been demonstrated to have a high removal capacity for arsenic (As) in reducing environments. However, FeS may be present as a coating, rather than in nanoparticulate form, in both natural and engineered systems. Frequently, the removal capacity of coatings may be different than that of nanoparticulates in batch systems. To assess the differences in removal mechanisms between nanoparticulate FeS and FeS present as a coating, the solid phase products from the reaction of As(III) with FeS-coated sand and with suspensions of nanoparticulate (NP) FeS were determined using x-ray absorption spectroscopy and x-ray photoelectron spectroscopy. In reaction with NP FeS at pH 5, As(III) was reduced to As(II) to form realgar (AsS), while at pH 9, As(III) adsorbed as an As(III) thioarsenite species. In contrast, in the FeS-coated sand system, As(III) formed the solid phase orpiment (As(2)S(3)) at pH 5, but adsorbed as an As(III) arsenite species at pH 9. These different solid reaction products are attributed to differences in FeS concentration and the resultant redox (pe) differences in the FeS-coated sand system versus suspensions of NP FeS. These results point to the importance of accounting for differences in concentration and redox when making inferences for coatings based on batch suspension studies.

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

    NASA Astrophysics Data System (ADS)

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

    2000-11-01

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

  15. X-ray Photoelectron Spectroscopy Database (Version 4.1)

    National Institute of Standards and Technology Data Gateway

    SRD 20 X-ray Photoelectron Spectroscopy Database (Version 4.1) (Web, free access)   The NIST XPS Database gives access to energies of many photoelectron and Auger-electron spectral lines. The database contains over 22,000 line positions, chemical shifts, doublet splittings, and energy separations of photoelectron and Auger-electron lines.

  16. X-ray absorption microscopy of aqueous samples

    NASA Astrophysics Data System (ADS)

    Frazer, Brad; Gilbert, Benjamin; De Stasio, Gelsomina

    2002-03-01

    X-ray photoelectron emission microscopy (X-PEEM) is used for numerous applications in surface microchemical analysis of material science and biological specimens. We have reconfigured the MEPHISTO X-PEEM instrument that is installed at the University of Wisconsin Synchrotron Radiation Center to measure true x-ray transmission spectra by converting transmitted photons to photoelectrons via a thin photocathode layer of gold. We have also developed a method by which to introduce aqueous samples into ultrahigh vacuum. Hence x-ray spectroscopy can be performed on biologically relevant elements (such as K, Ca, etc.) in a physiological environment, i.e., in solution. More important, when coupled with X-PEEM imaging this technique may offer the unique and exciting possibility of studying living cells. We present initial x-ray absorption spectra of solutions of aqueous ionic and chelated Ca, with the aim of distinguishing bound and free ionic calcium in vivo.

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

    SciTech Connect

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

    2009-04-03

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  19. Beyond hard x-ray photoelectron spectroscopy: Simultaneous combination with x-ray diffraction

    SciTech Connect

    Rubio-Zuazo, Juan; Castro, German R.

    2013-05-15

    Hard x-ray photoelectron spectroscopy (HAXPES) is a powerful and novel emerging technique for the nondestructive determination of electronic properties and chemical composition of bulk, buried interfaces and surfaces. It benefits from the exceptionally large escape depth of high kinetic energy photoelectrons, increasing the information depth up to several tens of nanometers. Complementing HAXPES with an atomic structure sensitive technique (such as x-ray diffraction) opens a new research field with major applications for materials science. At SpLine, the Spanish CRG beamline at the European Synchrotron Radiation Facility, we have developed a novel experimental set-up that combines HAXPES and x-ray diffraction (x-ray reflectivity, surface x-ray diffraction, grazing incidence x-ray diffraction, and reciprocal space maps). Both techniques can be operated simultaneously on the same sample and using the same excitation source. The set-up includes a robust 2S + 3D diffractometer hosting a ultrahigh vacuum chamber equipped with a unique photoelectron spectrometer (few eV < electron kinetic energy < 15 keV), x-ray tube (Mg/Ti), 15 keV electron gun, and auxiliary standard surface facilities (molecular beam epitaxy evaporator, ion gun, low energy electron diffraction, sample heating/cooling system, leak valves, load-lock sample transfer, etc.). This end-station offers the unique possibility of performing simultaneous HAXPES + x-ray diffraction studies. In the present work, we describe the experimental set-up together with two experimental examples that emphasize its outstanding capabilities: (i) nondestructive characterization of the Si/Ge and HfO{sub 2}/SiO{sub 2} interfaces on Ge-based CMOS devices, and (ii) strain study on La{sub 0.7}Ca{sub 0.3}MnO{sub 3} ultrathin films grown on SrTiO{sub 3}(001) substrate.

  20. X-ray absorption spectroscopy of metalloproteins.

    PubMed

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

    2014-01-01

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

  1. Feasibility tests of transmission x-ray photoelectron emission microscopy of wet samples

    NASA Astrophysics Data System (ADS)

    De Stasio, Gelsomina; Gilbert, B.; Nelson, T.; Hansen, R.; Wallace, J.; Mercanti, D.; Capozi, M.; Baudat, P. A.; Perfetti, P.; Margaritondo, G.; Tonner, B. P.

    2000-01-01

    We performed feasibility tests of photoelectron emission spectromicroscopy of wet samples in the water window (285-532 eV) soft x-ray spectral region. Water was successfully confined in an ultrahigh vacuum compatible compartment with x-ray transparent sides. This water cell was placed in the MEPHISTO spectromicroscope in a transmission geometry, and complete x-ray absorption spectra of the water window region were acquired. We also show micrographs of test samples, mounted outside of the compartment, and imaged through the water. This technique can be used to study liquid chemistry and, at least to the micron level, the microstructure of wet samples. Possibilities include cells in water or buffer, proteins in solution, oils of tribological interest, liquid crystals, and other samples not presently accessible to the powerful x-ray photoelectron emission spectromicroscopy technique.

  2. Interpretation of nanoparticle X-ray photoelectron intensities

    SciTech Connect

    Werner, Wolfgang S. M. Chudzicki, Maksymillian; Smekal, Werner; Powell, Cedric J.

    2014-06-16

    X-ray photoelectron (XPS) intensities have been simulated for spherical core-shell nanoparticles (NPs) in different geometrical arrangements in order to investigate the validity of commonly made assumptions for the interpretation of XPS NP intensities. The single-sphere approximation is valid for a powder sample when all spatial coordinates of the NP positions are uncorrelated. Correlations along either the depth coordinate or the lateral coordinates lead to features in the angular distribution that provide information on these correlations. The XPS intensity is proportional to the surface-to-volume ratio of nanoparticles but only for NP sizes exceeding the inelastic mean free path of the photoelectrons.

  3. Probing deeper by hard x-ray photoelectron spectroscopy

    SciTech Connect

    Risterucci, P.; Renault, O. Martinez, E.; Delaye, V.; Detlefs, B.; Zegenhagen, J.; Gaumer, C.; Grenet, G.; Tougaard, S.

    2014-02-03

    We report an hard x-ray photoelectron spectroscopy method combining high excitation energy (15 keV) and improved modelling of the core-level energy loss features. It provides depth distribution of deeply buried layers with very high sensitivity. We show that a conventional approach relying on intensities of the core-level peaks is unreliable due to intense plasmon losses. We reliably determine the depth distribution of 1 ML La in a high-κ/metal gate stack capped with 50 nm a-Si. The method extends the sensitivity of photoelectron spectroscopy to depths beyond 50 nm.

  4. Effect of X-ray flux on polytetrafluoroethylene in X-ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Wheeler, D. R.; Pepper, S. V.

    1982-01-01

    The effect of the X-ray flux in X-ray photoelectron spectroscopy (STAT) on the constitution of the polytetrafluoroethylene (PTFE) surface has been examined. The radiation dose rate for our specimen was about 10 to the 7th rad/s. The structure, magnitude and binding energy of the C(1s) and F(1s) features of the XPS spectrum and the mass spectrum of gaseous species evolved during irradiation are observed. The strong time dependence of these signals over a period of several hours indicated that the surface constitution of PTFE is greatly affected by this level of radiation dose. The results are consistent with the development of a heavily cross-linked or branched structure in the PTFE surface region and the evolution of short chain fragments into the gas phase.

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

    SciTech Connect

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

    2006-09-25

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

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

    PubMed

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

    2015-03-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼10(6) photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10(7) laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments. PMID:26798792

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

    DOE PAGESBeta

    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

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

    PubMed

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

    2015-03-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼10(6) photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10(7) laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

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

    SciTech Connect

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

    2015-03-02

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

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

    PubMed Central

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

    2015-01-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments. PMID:26798792

  11. Effects of Galactic absorption on soft X-ray surveys

    NASA Technical Reports Server (NTRS)

    Zamorani, G.; Gioia, I. M.; Maccacaro, T.; Wolter, A.

    1988-01-01

    A bias in the spectral distribution of X-ray sources detected in X-ray surveys is discussed which is due to the combination of the intrinsic characteristics of X-ray telescopes and the effects of low-energy photoelectric absorption within the Galaxy. A statistical method for obtaining information on the average spectrum of X-ray sources detected in well-defined surveys is presented. This method can be applied to surveys performed with X-ray telescopes working at relatively soft X-ray energies, such as Einstein, Exosat, and Rosat.

  12. FORTRAN program for x ray photoelectron spectroscopy data reformatting

    NASA Technical Reports Server (NTRS)

    Abel, Phillip B.

    1989-01-01

    A FORTRAN program has been written for use on an IBM PC/XT or AT or compatible microcomputer (personal computer, PC) that converts a column of ASCII-format numbers into a binary-format file suitable for interactive analysis on a Digital Equipment Corporation (DEC) computer running the VGS-5000 Enhanced Data Processing (EDP) software package. The incompatible floating-point number representations of the two computers were compared, and a subroutine was created to correctly store floating-point numbers on the IBM PC, which can be directly read by the DEC computer. Any file transfer protocol having provision for binary data can be used to transmit the resulting file from the PC to the DEC machine. The data file header required by the EDP programs for an x ray photoelectron spectrum is also written to the file. The user is prompted for the relevant experimental parameters, which are then properly coded into the format used internally by all of the VGS-5000 series EDP packages.

  13. Soft X-Ray Absorption Spectroscopy at an X-ray Free Electron Laser

    NASA Astrophysics Data System (ADS)

    Higley, Daniel; Schlotter, William; Turner, Joshua; Moeller, Stefan; Mitra, Ankush; Tsukamoto, Arata; Marvel, Robert; Haglund, Richard; Durr, Hermann; Stohr, Joachim; Dakovski, Georgi

    2015-03-01

    X-ray free electron lasers, providing coherent, ultrafast, high intensity x-ray pulses, have enabled groundbreaking scattering experiments to probe the atomic structure of materials on femtosecond timescales. Nonetheless, x-ray absorption spectroscopy (XAS), one of the most fundamental and common x-ray techniques practiced at synchrotron light sources, has proven challenging to conduct with satisfactory signal-to-noise levels at soft x-ray energies using free electron laser sources. The ability to routinely collect high quality XAS spectra, especially in a time-resolved manner, will open many new scientific possibilities in the areas of ultrafast demagnetization, phase transitions and chemical dynamics to highlight a few. Here, we report how XAS using total fluorescence yield detection yields high signal-to-noise x-ray absorption spectra at an x-ray free electron laser source. Data were collected over multiple absorption edges on technologically relevant materials. These measurements were recorded on the Soft X-Ray Materials Science instrument at the Linac Coherent Light Source. The results are easily extendable to time-resolved measurements.

  14. X-ray microprobe for micro x-ray fluorescence and absorption spectroscopies at GSECARS

    NASA Astrophysics Data System (ADS)

    Newville, M.; Sutton, S.; Rivers, M.

    2002-12-01

    The hard x-ray microprobe for x-ray fluorescence and absorption spectroscopy at GeoSoilEnviroCARS is presented. Using focused synchrotron radiation from an undulator beamline at the Advanced Photon Source at Argonne National Lab, the x-ray microprobe provides bright, monochromatic x-rays with typical spot sizes down to 1x1 μm for x-ray fluorescence and absorption spectroscopies. Quantitative x-ray fluorescence (XRF) analysis gives precise elemental composition and correlations, while x-ray absorption spectroscopy (XAS) gives the chemical state and local atomic coordination for a selected atomic species. These two techniques can be used in conjunction with one another on a wide range of samples, including minerals, glasses, fluid inclusions, soils, sediments, and plant tissue. This x-ray microprobe is part of the GeoSoilEnviroCARS user facility, available for use in all areas geological, soil, and environmental sciences, and selected examples from these fields will be given.

  15. X-ray Attenuation and Absorption Calculations.

    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.

  16. X-ray and photoelectron spectroscopy of the structure, reactivity, and electronic structure of semiconductor nanocrystals

    SciTech Connect

    Hamad, K.S.

    2000-05-01

    Semiconductor nanocrystals are a system which has been the focus of interest due to their size dependent properties and their possible use in technological applications. Many chemical and physical properties vary systematically with the size of the nanocrystal and thus their study enables the investigation of scaling laws. Due to the increasing surface to volume ratio as size is decreased, the surfaces of nanocrystals are expected to have a large influence on their electronic, thermodynamic, and chemical behavior. In spite of their importance, nanocrystal surfaces are still relatively uncharacterized in terms of their structure, electronic properties, bonding, and reactivity. Investigation of nanocrystal surfaces is currently limited by what techniques to use, and which methods are suitable for nanocrystals is still being determined. This work presents experiments using x-ray and electronic spectroscopies to explore the structure, reactivity, and electronic properties of semiconductor (CdSe, InAs) nanocrystals and how they vary with size. Specifically, x-ray absorption near edge spectroscopy (XANES) in conjunction with multiple scattering simulations affords information about the structural disorder present at the surface of the nanocrystal. X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS) probe the electronic structure in terms of hole screening, and also give information about band lineups when the nanocrystal is placed in electric contact with a substrate. XPS of the core levels of the nanocrystal as a function of photo-oxidation time yields kinetic data on the oxidation reaction occurring at the surface of the nanocrystal.

  17. Resonant X-Ray Scattering and Absorption

    NASA Astrophysics Data System (ADS)

    Collins, S. P.; Bombardi, A.

    This chapter outlines some of the basic ideas behind nonresonant and resonant X-ray scattering, using classical or semiclassical pictures wherever possible; specifically, we highlight symmetry arguments governing the observation of X-ray optical effects, such as X-ray magnetic circular dichroism and resonant "forbidden" diffraction. Without dwelling on the microscopic physics that underlies resonant scattering, we outline some key steps required for calculating its rotation and polarization dependence, based on Cartesian and spherical tensor frameworks. Several examples of resonant scattering, involving electronic anisotropy and magnetism, are given as illustrations. Our goal is not to develop or defend theoretical concepts in X-ray scattering, but to bring together existing ideas in a pragmatic and utilitarian manner.

  18. Corrosion and degradation studies utilizing X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Hixson, Holly Gwyndolen

    1997-08-01

    This dissertation involves studies of corrosion behavior at the surface of various metal samples, as well as the degradation of wool fibers obtained from the Star-Spangled Banner. Molybdenum metal and iron-zinc alloys were examined under corrosive conditions, and the degradation of the wool fibers was studied. The behavior of a polished molybdenum metal surface upon exposure to both aerated and deaerated water and 1.0 M NaCl solution was studied by X-ray Photoelectron Spectroscopy (XPS). Exposure to deaerated water and NaCl failed to produce oxidation of the metal surfaces, but exposing the polished metal surface to aerated water produced significant oxidation. Metal surfaces cleaned by argon-ion etching were found to be inert to oxidation by aerated water. The etching process also appears to passivate the metal surface. The behavior of molybdenum metal in 0.5 M Hsb2SOsb4 treated at various potentials has been studied using core and valence band XPS. The study indicates that Mosp{IV} and Mosp{VI} (including possibly Mosp{V} in some cases) were formed as the potential of the system was increased within the active range of molybdenum. The corrosive behavior of iron-zinc alloys that have been electroplated on plain steel in both aerated and deaerated quadruply-distilled water has been studied using XPS. Several different iron-zinc alloys were electroplated for comparative purposes: an iron-rich alloy, a zinc-rich alloy, and an alloy of similar iron and zinc composition. Treatment in aerated water produces oxidation for the iron-rich and similar composition alloys, but the oxide is reduced for the zinc-rich alloy. Degradation of the fibers in the original Star-Spangled Banner has been monitored using XPS and Scanning Electron Microscopy (SEM). Comparison of white and red wool fibers and linen fibers from the flag with new, mechanically-abraded, and chemically-treated white, red, and linen fibers, respectively, was performed in an attempt to determine the fibers' levels

  19. Synchrotron x-ray fluorescence and extended x-ray absorption fine structure analysis

    SciTech Connect

    Chen, J.R.; Gordon, B.M.; Hanson, A.L.; Jones, K.W.; Kraner, H.W.; Chao, E.C.T.; Minkin, J.A.

    1984-01-01

    The advent of dedicated synchrotron radiation sources has led to a significant increase in activity in many areas of science dealing with the interaction of x-rays with matter. Synchrotron radiation provides intense, linearly polarized, naturally collimated, continuously tunable photon beams, which are used to determine not only the elemental composition of a complex, polyatomic, dilute material but also the chemical form of the elements with improved accuracy. Examples of the application of synchrotron radiation include experiments in synchrotron x-ray fluorescence (SXRF) analysis and extended x-ray absorption fine structure (EXAFS) analysis. New synchrotron radiation x-ray microprobes for elemental analysis in the parts per billion range are under construction at several laboratories. 76 references, 24 figures.

  20. Absorption and phase X-ray imaging using reflected beam

    NASA Astrophysics Data System (ADS)

    Jakubek, Jan

    2011-05-01

    The X-ray structure imaging of the soft thin biological samples is particularly difficult as they are often attached to the solid carrier, which has much higher absorption of X-rays. The highly absorbing carrier forces the use of higher energies of X-rays decreasing the achievable contrast of the sample structure. The proposed method uses a flat sample carrier (metallic, glass or even plastic) acting as a mirror. The carrier with the sample is irradiated at grazing angle and the X-ray beam is reflected from the interface between the sample and carrier. That way the beam penetrates through the sample only without entering into the carrier. The energy of the X-ray beam can be low (e.g. nanofocus X-ray tube with Cr, Fe or Cu cathode) providing good contrast for soft sample imaging. The beam path in the sample is prolonged giving more chance for absorption in very thin samples. The reflectivity of X-ray depends on the beam properties and on the refractive index of the sample (for a given carrier material). Then, it is possible to make imaging of the refractive index distribution across the sample. Sufficient spatial resolution and good sensitivity can be achieved using nanofocus X-ray tube together with a highly sensitive pixelated detector Timepix. Several experimental results obtained with such a system verifying the principles described above are presented.

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

    SciTech Connect

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

    2006-09-25

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

  2. X-ray photoelectron spectroscopy peak assignment for perfluoropolyether oils

    NASA Technical Reports Server (NTRS)

    Mori, Shigeyuki; Morales, Wilfredo

    1990-01-01

    Perfluoroalkylpolyether (PFPE) oils are increasingly being used as vacuum pump oils and as lubricants for magnetic recording media and instrumentation for satellites. In this paper, the relative binding energies of three PFPE oils are determined. When sample oils are continuously irradiated during X-ray spectroscopy (XPS) measurements, the relative peak intensity of the spectra is altered significantly, indicating that gaseous products form from the oils during XPS measurements. Thus, attention should be paid to chemical changes when XPE is used to characterize fluorinated carbons such as PFPE oils.

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

    SciTech Connect

    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

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

    NASA Astrophysics Data System (ADS)

    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 HfO2 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 × 10-6 for 445 nm illumination.

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

    SciTech Connect

    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.

  6. Polytetrafluoroethylene transfer film studied with X-ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Wheeler, D. R.

    1980-01-01

    Polytetrafluoroethylene (PTFE) was rubbed against nickel in ultrahigh vacuum at loads up to 3.9 N and speeds up to 94 mm/sec. The transfer film formed on the nickel was analyzed using X-ray phototectron spectroscopy. The film was indistinguishable from bulk PTFE except for the possible presence of a small amount of NiF2. The transfer film was found to be about 1 molecule (0.5 nm) thick under all conditions; but at speeds above 10 mm/sec, there was evidence of bulk transfer in the form of fragments as well. The thickness measurements required a choice among conflicting published values of the inelastic mean free path for electrons in polymers. The values chosen gave internally consistent results.

  7. Capturing interfacial photoelectrochemical dynamics with picosecond time-resolved X-ray photoelectron spectroscopy.

    PubMed

    Neppl, Stefan; Shavorskiy, Andrey; Zegkinoglou, Ioannis; Fraund, Matthew; Slaughter, Daniel S; Troy, Tyler; Ziemkiewicz, Michael P; Ahmed, Musahid; Gul, Sheraz; Rude, Bruce; Zhang, Jin Z; Tremsin, Anton S; Glans, Per-Anders; Liu, Yi-Sheng; Wu, Cheng Hao; Guo, Jinghua; Salmeron, Miquel; Bluhm, Hendrik; Gessner, Oliver

    2014-01-01

    Time-resolved core-level spectroscopy using laser pulses to initiate and short X-ray pulses to trace photoinduced processes has the unique potential to provide electronic state- and atomic site-specific insight into fundamental electron dynamics in complex systems. Time-domain studies using transient X-ray absorption and emission techniques have proven extremely valuable to investigate electronic and structural dynamics in isolated and solvated molecules. Here, we describe the implementation of a picosecond time-resolved X-ray photoelectron spectroscopy (TRXPS) technique at the Advanced Light Source (ALS) and its application to monitor photoinduced electron dynamics at the technologically pertinent interface formed by N3 dye molecules anchored to nanoporous ZnO. Indications for a dynamical chemical shift of the Ru3d photoemission line originating from the N3 metal centre are observed ∼30 ps after resonant HOMO-LUMO excitation with a visible laser pump pulse. The transient changes in the TRXPS spectra are accompanied by a characteristic surface photovoltage (SPV) response of the ZnO substrate on a pico- to nanosecond time scale. The interplay between the two phenomena is discussed in the context of possible electronic relaxation and recombination pathways that lead to the neutralisation of the transiently oxidised dye after ultrafast electron injection. A detailed account of the experimental technique is given including an analysis of the chemical modification of the nano-structured ZnO substrate during extended periods of solution-based dye sensitisation and its relevance for studies using surface-sensitive spectroscopy techniques.

  8. X-Ray Weak Broad-Line Quasars: Absorption or Intrinsic X-Ray Weakness

    NASA Technical Reports Server (NTRS)

    Risaliti, Guido; Mushotzky, Richard F. (Technical Monitor)

    2004-01-01

    XMM observations of X-ray weak quasars have been performed during 2003. The data for all but the last observation are now available (there has been a delay of several months on the initial schedule, due to high background flares which contaminated the observations: as a consequence, most of them had to be rescheduled). We have reduced and analyzed these data, and obtained interesting preliminary scientific results. Out of the eight sources, 4 are confirmed to be extrimely X-ray weak, in agreement with the results of previous Chandra observations. 3 sources are confirmed to be highly variable both in flux (by factors 20-50) and in spectral properties (dramatic changes in spectral index). For both these groups of objects, an article is in preparation. Preliminary results have been presented at an international workshop on AGN surveys in December 2003, in Cozumel (Mexico). In order to further understand the nature of these X-ray weak quasars, we submitted proposals for spectroscopy at optical and infrared telescopes. We obtained time at the TNG 4 meter telescope for near-IR observations, and at the Hobby-Eberly Telescope for optical high-resolution spectroscopy. These observations will be performed in early 2004, and will complement the XMM data, in order to understand whether the X-ray weakness of these sources is an intrinsic property or is due to absorption by circumnuclear material.

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

    SciTech Connect

    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

    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.

  10. High ionisation absorption in low mass X-ray binaries

    NASA Astrophysics Data System (ADS)

    Ponti, G.; Bianchi, S.; Muñoz-Darias, T.; De, K.; Fender, R.; Merloni, A.

    2016-05-01

    The advent of the new generation of X-ray telescopes yielded a significant step forward in our understanding of ionised absorption generated in the accretion discs of X-ray binaries. It has become evident that these relatively weak and narrow absorption features, sporadically present in the X-ray spectra of some systems, are actually the signature of equatorial outflows, which might carry away more matter than that being accreted. Therefore, they play a major role in the accretion phenomenon. These outflows (or ionised atmospheres) are ubiquitous during the softer states but absent during the power-law dominated, hard states, suggesting a strong link with the state of the inner accretion disc, presence of the radio-jet and the properties of the central source. Here, we discuss the current understanding of this field.

  11. Ultrafast absorption of intense x rays by nitrogen molecules

    SciTech Connect

    Buth, Christian; Liu Jicai; Chen, Mau Hsiung; Cryan, James P.; Fang Li; Hoener, Matthias; Berrah, Nora; Glownia, James M.; Coffee, Ryan N.

    2012-06-07

    We devise a theoretical description for the response of nitrogen molecules (N{sub 2}) to ultrashort and intense x rays from the free electron laser Linac Coherent Light Source (LCLS). We set out from a rate-equation description for the x-ray absorption by a nitrogen atom. The equations are formulated using all one-x-ray-photon absorption cross sections and the Auger and radiative decay widths of multiply-ionized nitrogen atoms. Cross sections are obtained with a one-electron theory and decay widths are determined from ab initio computations using the Dirac-Hartree-Slater (DHS) method. We also calculate all binding and transition energies of nitrogen atoms in all charge states with the DHS method as the difference of two self-consistent field (SCF) calculations ({Delta}SCF method). To describe the interaction with N{sub 2}, a detailed investigation of intense x-ray-induced ionization and molecular fragmentation are carried out. As a figure of merit, we calculate ion yields and the average charge state measured in recent experiments at the LCLS. We use a series of phenomenological models of increasing sophistication to unravel the mechanisms of the interaction of x rays with N{sub 2}: a single atom, a symmetric-sharing model, and a fragmentation-matrix model are developed. The role of the formation and decay of single and double core holes, the metastable states of N{sub 2}{sup 2+}, and molecular fragmentation are explained.

  12. Biological X-ray absorption spectroscopy and metalloproteomics.

    PubMed

    Ascone, Isabella; Strange, Richard

    2009-05-01

    In the past seven years the size of the known protein sequence universe has been rapidly expanding. At present, more then five million entries are included in the UniProtKB/TrEMBL protein database. In this context, a retrospective evaluation of recent X-ray absorption studies is undertaken to assess its potential role in metalloproteomics. Metalloproteomics is the structural and functional characterization of metal-binding proteins. This is a new area of active research which has particular relevance to biology and for which X-ray absorption spectroscopy is ideally suited. In the last three years, biological X-ray absorption spectroscopy (BioXAS) has been included among the techniques used in post-genomics initiatives for metalloprotein characterization. The emphasis of this review is on the progress in BioXAS that has emerged from recent meetings in 2007-2008. Developments required to enable BioXAS studies to better contribute to metalloproteomics throughput are also discussed. Overall, this paper suggests that X-ray absorption spectroscopy could have a higher impact on metalloproteomics, contributing significantly to the understanding of metal site structures and of reaction mechanisms for metalloproteins. PMID:19395808

  13. Determining the Uncertainty of X-Ray Absorption Measurements

    PubMed Central

    Wojcik, Gary S.

    2004-01-01

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

  14. Secondary ion mass spectrometry and X-ray photoelectron spectroscopy of derivitized coal surfaces

    SciTech Connect

    Martin, R.R.; Mc Intyre, N.S.; Mac Phee, J.A.; Aye, K.T.

    1987-04-01

    Secondary Ion Mass Spectrometry (SIMS) and X-ray Photoelectron Spectroscopy (XPS) have been used to study the low temperature oxidation of coal. /sup 18/O has been used to trace the oxygen distribution on the coal surface. Several chemical derivations have been observed on the oxidized coal surface and the reactivity of specific regions have been monitored.

  15. Soft-x-ray transmission photoelectron spectromicroscopy with the MEPHISTO system

    NASA Astrophysics Data System (ADS)

    De Stasio, Gelsomina; Gilbert, B.; Perfetti, Luca; Fauchoux, O.; Valiquer, A.; Nelson, T.; Capozi, M.; Baudat, P. A.; Cerrina, F.; Chen, Z.; Perfetti, P.; Tonner, B. P.; Margaritondo, G.

    1998-09-01

    We complemented with data taken in transmission mode the recently described tests of the novel spectromicroscope MEPHISTO (Microscope à Emission de Photoélectrons par Illumination Synchrotronique de type Onduleur). Transmitted x rays were converted by a photocathode into photoelectrons, which were subsequently electron-optically processed by the spectromicroscope producing submicron-resolution images. Test images demonstrated excellent contrast.

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

    SciTech Connect

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

    2012-08-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

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

    SciTech Connect

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

    2010-07-20

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

  19. Photoelectron diffraction from laser-aligned molecules with X-ray free-electron laser pulses

    PubMed Central

    Nakajima, Kyo; Teramoto, Takahiro; Akagi, Hiroshi; Fujikawa, Takashi; Majima, Takuya; Minemoto, Shinichirou; Ogawa, Kanade; Sakai, Hirofumi; Togashi, Tadashi; Tono, Kensuke; Tsuru, Shota; Wada, Ken; Yabashi, Makina; Yagishita, Akira

    2015-01-01

    We report on the measurement of deep inner-shell 2p X-ray photoelectron diffraction (XPD) patterns from laser-aligned I2 molecules using X-ray free-electron laser (XFEL) pulses. The XPD patterns of the I2 molecules, aligned parallel to the polarization vector of the XFEL, were well matched with our theoretical calculations. Further, we propose a criterion for applying our molecular-structure-determination methodology to the experimental XPD data. In turn, we have demonstrated that this approach is a significant step toward the time-resolved imaging of molecular structures. PMID:26369428

  20. X-ray absorption spectroscopy of liquid surface

    NASA Astrophysics Data System (ADS)

    Watanabe, Iwao; Tanida, Hajime; Kawauchi, Sigehiro; Harada, Makoto; Nomura, Masaharu

    1997-09-01

    An apparatus has been constructed for x-ray absorption spectroscopy of elements at air/aqueous solution interface. Its surface sensitivity is gained from glancing incidence of synchrotron radiation under total reflection condition. The absorption is detected by total conversion He ion-yield method. This apparatus was operated at the beam line 7C of Photon Factory, where the incident photon beam comes from a sagittal focus double-crystal monochromator via a 70-cm-long bent mirror. The mirror focuses the beam vertically and changes the beam direction downward by 1 mrad to irradiate solution surface. The essential requirement of this technique, ripple-free liquid surface at accurate position, was attained by introducing a trough on a floating boat, continuous surface level monitoring, and an automatic Z-stage control. The x-ray absorption edge jump demonstrated that surface concentration of bromide ion follows the Langmuir type adsorption for tetraalkylammonuim bromide solution. By comparing the jump values for surface-active and -inactive bromide salt solutions, the detecting depth of the present technique was determined to be 8.8 nm. An extended x-ray absorption fine structure analysis of bromide ion segregated to the surface by stearyltrimethylammonium cation indicated that its solvation structure is different from that of bulk.

  1. X-ray absorption and high redshift quasars

    NASA Technical Reports Server (NTRS)

    Elvis, Martin

    1996-01-01

    The low energy cut-offs toward radio-loud quasars with z greater than 2, red quasars, and broad absorption line quasars are discussed. The X-ray absorption seems to be common among different types of red shift quasar. The Rosat position sensitive proportional counter (PSPC) spectra of z = 3 quasars and of a red quasar are presented. Broad absorption lines show outflow velocities of up to 0.1 c to 0.2 c. The advantages and the disadvantages of high red shift observations are underlined.

  2. X-ray absorption spectroscopy of chicken sulfite oxidase crystals

    SciTech Connect

    George, G.N.; Pickering, I.J.; Kisker, C.

    1999-05-17

    Sulfite oxidase catalyzes the physiologically vital oxidation of sulfite to sulfate. Recently, the crystal structure of chicken sulfite oxidase has been reported at 1.9 {angstrom} resolution. In contrast to the information available from previous X-ray absorption spectroscopic studies, the active site indicated by crystallography was a mono-oxo species. Because of this the possibility that the crystals did in fact contain a reduced molybdenum species was considered in the crystallographic work. The authors report herein an X-ray absorption spectroscopic study of polycrystalline sulfite oxidase prepared in the same manner as the previous single-crystal samples, and compare this with data for frozen solutions of oxidized and reduced enzyme.

  3. Auger electron and X-ray photoelectron spectroscopic study of the biocorrosion of copper by alginic acid polysaccharide

    NASA Astrophysics Data System (ADS)

    Jolley, John G.; Geesey, Gill G.; Hankins, Michael R.; Wright, Randy B.; Wichlacz, Paul L.

    1989-08-01

    Thin films (3.4 nm) of copper on germanium substrates were exposed to 2% alginic acid polysaccharide aqueous solution. Pre- and post-exposure characterization were done by Auger electron spectroscopy and X-ray photoelectron spectroscopy. Ancillary graphite furnace atomic absorption spectroscopy was used to monitor the removal process of the copper thin film from the germanium substrate. Results indicate that some of the copper was oxidized by the alginic acid solution. Some of the copper was removed from the Cu/Ge interface and incorporated into the polymer matrix. Thus, biocorrosion of copper was exhibited by the alginic acid polysaccharide.

  4. Optical and x-ray photoelectron spectroscopy studies of α-Al2O3

    NASA Astrophysics Data System (ADS)

    Prakash, Ram; Kumar, Sandeep; Kumar, Vinay; Choudhary, R. J.; Phase, D. M.

    2016-05-01

    α-Al2O3 powder sample was synthesized at 550 °C via solution combustion synthesis (SCS) method using urea as an organic fuel. The sample was characterized by X-ray diffraction (XRD), Optical spectroscopy and X-ray photoelectron spectroscopy (XPS) without any further thermal treatment. XRD study reveals that the powder crystallized directly in the hexagons α-Al2O3 phase. A band gap of 5.7 eV was estimated using diffuse reflectance spectra. For surface investigation X-ray photo electron spectroscopy (XPS) was carried out. The XPS survey scan study of α-Al2O3 powder reveals that the sample is free from impurity. The core levels of Al-2s and O-1s are also reported.

  5. A lab-based ambient pressure x-ray photoelectron spectrometer with exchangeable analysis chambers

    SciTech Connect

    Newberg, John T. Arble, Chris; Goodwin, Chris; Khalifa, Yehia; Broderick, Alicia; Åhlund, John

    2015-08-15

    Ambient pressure X-ray photoelectron spectroscopy (APXPS) is a powerful spectroscopy tool that is inherently surface sensitive, elemental, and chemical specific, with the ability to probe sample surfaces under Torr level pressures. Herein, we describe the design of a new lab-based APXPS system with the ability to swap small volume analysis chambers. Ag 3d(5/2) analyses of a silver foil were carried out at room temperature to determine the optimal sample-to-aperture distance, x-ray photoelectron spectroscopy analysis spot size, relative peak intensities, and peak full width at half maximum of three different electrostatic lens modes: acceleration, transmission, and angular. Ag 3d(5/2) peak areas, differential pumping pressures, and pump performance were assessed under varying N{sub 2}(g) analysis chamber pressures up to 20 Torr. The commissioning of this instrument allows for the investigation of molecular level interfacial processes under ambient vapor conditions in energy and environmental research.

  6. X-ray photoelectron spectroscopy of γ-ray-irradiated single-stranded DNA

    NASA Astrophysics Data System (ADS)

    Lee, Eunmo; Hong, W.; Han, J. H.; Choi, D. M.; Lee, Cheol Eui; Kim, H. D.; Kim, J.

    2015-07-01

    The effects of γ-ray irradiation on herring sperm single-stranded DNA have been studied by using X-ray photoelectron spectroscopy (XPS) in the view of the bonding configurations and the structural modifications. The significant changes in the hydrogen, carbon, nitrogen, and phosphorous bonding energies, as revealed by the XPS analysis, indicate that electron transfers result in the creation of radicals and in DNA strand breaks.

  7. Simple photoelectron x-ray beam position monitor for synchrotron radiation

    SciTech Connect

    Heald, S.M.

    1985-01-01

    A UHV compatible x-ray beam position monitor is described. The monitor operates by detecting the photoelectrons emitted by two parallel tungsten wires. A key feature of the monitor is the simplicity of its design and construction which allows it to fit on a 2 3/4 in. conflat flange. When combined with a simple log-ratio current amplifier the monitor gives an output linear in the beam position with a sensitivity better than 0.02 mm.

  8. X-ray photoelectron spectroscopy of copper(II), copper(I), and mixed valence systems.

    PubMed

    Rupp, H; Weser, U

    1976-01-01

    X-ray photoelectron spectroscopy using copper(II), copper(I) and the mixed valence Cu(II)/Cu(I) compounds was employed as a means of studying electron transfer reactions in copper proteins. The X-ray photoelectron spectra of copper(II) compounds display characteristic satellites of both variable size and resolution. Some of these satellites could be assigned to specific ligand interactions. Unlike electron paramagnetic resonance spectroscopy, the X-ray photoelectron spectroscopic measurements of copper(I) compounds allowed the unequivocal assignment of this oxidation state. No satellites at all could be detected in the Cu(I) spectra. Furthermore, established mixed valence Cu(II)/Cu(I) complexes including Cu2SO3-CuSO3-2H2O and Cu4Cl5 (ethylenediamine)2 proved essentially a mixture of distinct portions of Cu(I) and Cu(II). This indicates that both oxidation states of copper survive in such complexes. In contrast, all Cu X-ray photoelectron signals of the more tentatively described mixed valence complexes Na2Cu3S3 and the mineral covellite, CuI4CuII2(S2)2S2, could be attributed exclusively to Cu(I). In view of the known binding of copper with sulfur in many copper proteins, it was of utmost importance to study the copper-sulfur interactions. We have demonstrated the absence of Cu(II) in CuS. This indicates strong metal-induced polarization of sulfur resulting in electron transfer to copper to yield Cu(I). PMID:953045

  9. Modeling Broadband X-Ray Absorption of Massive Star Winds

    NASA Technical Reports Server (NTRS)

    Leutenegger, Maurice A.; Cohen,David H.; Zsargo, Janos; Martell, Erin M.; MacArthur, James P.; Owocki, Stanley P.; Gagne, Marc; Hillier, D. John

    2010-01-01

    We present a method for computing the net transition of X-rays emitted by shock-heated plasma distributed throughout a partially optically thick stellar wind from a massive star. We find the transmission by an exact integration of the formal solution, assuming the emitting plasma and absorbing plasma are mixed at a constant mass ratio above some minimum radius, below which there is assumed to be no emission. This model is more realistic than either the slab absorption associated with a corona at the base of the wind or the exospheric approximation that assumes all observed X-rays are emitted without attenuation from above the radius of optical depth unity. Our model is implemented in XSPEC as a pre-calculated table that can be coupled to a user-defined table of the wavelength dependent wind opacity. We provide a default wind opacity model that is more representative of real wind opacities than the commonly used neutral ISM tabulation. Preliminary modeling of Chandra grating data indicates that the X-ray hardness trend of OB stars with spectral subtype cars largely be understood as a wind absorption effect.

  10. X-ray absorption studies of battery materials

    SciTech Connect

    McBreen, J.

    1996-10-01

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

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

    SciTech Connect

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

    2014-11-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    SciTech Connect

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

    2009-12-11

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

  14. X-RAY ABSORPTION OF HIGH-REDSHIFT QUASARS

    SciTech Connect

    Eitan, Assaf; Behar, Ehud E-mail: behar@physics.technion.ac.il

    2013-09-01

    The soft X-ray photoelectric absorption of high-z quasars has been known for two decades, but has no unambiguous astrophysical context. We construct the largest sample to date of 58 high-redshift quasars (z > 0.45) selected from the XMM-Newton archive based on a high photon count criterion (>1800). We measure the optical depth {tau} at 0.5 keV and find that 43% of the quasars show significant absorption. We aim to find which physical parameters of the quasars, e.g., redshift, radio luminosity, radio loudness, or X-ray luminosity, drive their observed absorption. We compare the absorption behavior with redshift with the pattern expected if the diffuse intergalactic medium (IGM) is responsible for the observed absorption. We also compare the absorption with a comparison sample of gamma-ray burst (GRB) X-ray afterglows. Although the z > 2 quasar opacity is consistent with diffuse IGM absorption, many intermediate-z (0.45 < z < 2) quasars are not sufficiently absorbed for this scenario, and are appreciably less absorbed than GRBs. Only 10/37 quasars at z < 2 are absorbed, and only 5/30 radio-quiet quasars are absorbed. We find a weak correlation between {tau} and z, and an even weaker correlation between {tau} and radio luminosity. These findings lead to the conclusion that although a diffuse IGM origin for the quasar absorption is unlikely, the optical depth does seem to increase with redshift, roughly as (1 + z){sup 2.2{+-}0.6}, tending to {tau} Almost-Equal-To 0.4 at high redshifts, similar to the high-z GRBs. This result can be explained by an ionized and clumpy IGM at z < 2, and a cold, diffuse IGM at higher redshift. If, conversely, the absorption occurs at the quasar, and owing to the steep L{sub x} {proportional_to}(1 + z){sup 7.1{+-}0.5} correlation in the present sample, the host column density scales as N{sub H}{proportional_to}L{sub x}{sup 0.7{+-}0.1}.

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

    SciTech Connect

    Masuda, Takuya; Yoshikawa, Hideki; Kobata, Masaaki; Kobayashi, Keisuke; Noguchi, Hidenori; Kawasaki, Tadahiro; Uosaki, Kohei

    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. An X-ray photoelectron spectroscopic study of the B-N-Ti system

    SciTech Connect

    Seal, S.; Barr, T.L.; Sobczak, N.; Benko, E.; Morgiel, J.

    1997-03-01

    Composite nitrides (such as BN, TiN) are widely used in various industrial applications because of their extreme wear and corrosion resistance, thermal and electrical properties. In order to obtain composite materials with these optimal properties, it is important to elucidate whether any chemical reactions occur at nitride/metal interfaces, e.g., those involving BN-Ti/TiN. Materials of interest include the deposition by PVD of Ti and TiN on BN substrates. Some of these systems were then subjected to varying degrees of physical and thermal alteration. Detailed X-ray photoelectron spectroscopy (XPS) has therefore been rendered of these interfaces using cross-sectional display and sputter etching. Resulting structural and morphological features have been investigated with transmission electron microscopy (TEM) and X-ray diffraction (XRD). Diffusion of the nitridation, oxynitride formation and interfacial growth are of general interest.

  17. Surface state analysis of wet ground silicon nitride powders by x-ray photoelectron spectroscopy

    SciTech Connect

    Kameshima, Yoshikazu; Yasumori, Atsuo; Okada, Kiyoshi

    1995-09-01

    Three kinds of silicon nitride powders, i.e. as-prepared direct-nitridation powder, HF-treated direct-nitridation powder, and as-prepared imide decomposition powder, were wet ground by ball milling in water and the surface state change due to the grinding was examined by X-ray photoelectron spectroscopy (XPS) and X-ray Auger electron spectroscopy (XAES). The thickness of the oxidized surface layer of the powder was calculated from the peak area ratio and the chemical composition was evaluated from the Auger parameter (AP). Surface oxidized phase amount gradually increased with longer milling time and the thickness increased almost three times after 7 days milling, compared to as those of the unground samples. Chemical composition of the oxidized phase formed by the grinding was pure silica irrespective to the samples, although those of the oxidized phase in the unground samples differed among the samples.

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

    SciTech Connect

    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.

  19. Comparison of hard and soft x-ray photoelectron spectra of silicon

    NASA Astrophysics Data System (ADS)

    Offi, F.; Werner, W. S. M.; Sacchi, M.; Torelli, P.; Cautero, M.; Cautero, G.; Fondacaro, A.; Huotari, S.; Monaco, G.; Paolicelli, G.; Smekal, W.; Stefani, G.; Panaccione, G.

    2007-08-01

    A detailed comparison of the surface sensitivity of x-ray photoemission spectroscopy for hard and soft x rays is presented and discussed. Electron scattering parameters and their energy dependence are given for Si and two Si spectra are analyzed: a MgKα (hν=1253.6eV) excited spectrum of the Si2p and 2s lines and a hard x-ray excited spectrum (hν=5925eV) of the Si1s line. The differential inelastic scattering characteristics for Si are extracted from reflection electron energy loss spectra taken at energies of 1500 and 4000eV . Using these scattering characteristics and electron mean free paths from the literature, simulated spectra are compared with experiment. The experimental spectra are deconvoluted to give the true intrinsic line shape corresponding to the theoretical collision statistics when interference effects between intrinsic and extrinsic scattering are neglected. The magnitude of interference effects cannot be assessed by our analysis. Within the (unknown) uncertainty introduced by neglecting interference effects, it is possible to determine the relative intensity of intrinsic and extrinsic excitations. In this way, it is found that in the case of the soft x-ray excited photoelectron spectrum of the shallower electronic shells ( 2p and 2s ), intrinsic plasmon creation is rather weak, and the apparent asymmetric line shape of the spectrum might be interpreted as the fact that electron-hole pair creation dominates the intrinsic loss spectrum, while an alternative explanation in terms of surface core level shifted components is also proposed. For the deeper core electronic shell, probed with hard x rays, the opposite situation is observed: while intrinsic electron-hole pair creation was not observed, a strong contribution of intrinsic plasmon losses of about 30% was seen.

  20. X-Ray Absorption of High- Redshift Quasars

    NASA Astrophysics Data System (ADS)

    Behar, Ehud; Eitan, Assaf

    2012-09-01

    Soft X-ray absorption of high-z quasars has been known for more than a decade, but its astrophysical context remains a mystery. In order to better understand this absorption, we have constructed the largest to date high-S/N sample of high-z quasars (z > 0.5) from the XMM-Newton archive. We find that generally, z<2 and radio quiet objects provide only upper limits for the 0.5 keV optical depth (tau). Thus, we use censored statistics methods to seek correlations between tau and other quasar parameters. We find a dramatic increase of tau with z [(1+z)^{2.5}], although the correlation is rather weak. The correlation of tau with radio luminosity (or loudness) is even weaker. We also compare the absorption behavior with redshift with a large sample of GRBs, and with the pattern expected if the diffuse intergalactic medium (IGM) is responsible for the observed absorption. We find that although the z > 2 quasar opacity is consistent with a diffuse IGM effect and with the high-z GRB opacities, absorption of intermediate z (0.5 < z < 2) quasars is too low for this scenario, which leads to the conclusion that a simple IGM origin for this absorption is unlikely.

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

    SciTech Connect

    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.

  2. Oxidation of stepped Pt(111) studied by x-ray photoelectron spectroscopy and density functional theory

    SciTech Connect

    Bandlow, Jochen; Kaghazchi, Payam; Jacob, Timo; Papp, C.; Traenkenschuh, B.; Streber, R.; Lorenz, M. P. A.; Fuhrmann, T.; Steinrueck, H.-P.; Denecke, R.

    2011-05-01

    In this comparative density functional theory and x-ray photoelectron spectroscopy study on the interaction of oxygen with stepped Pt(111) surfaces, we show that both the initial adsorption and oxidation occur at the steps rather than terraces. An equivalent behavior was observed for the oxide formation at higher chemical potentials, where, after the formation of a one-dimensional PtO{sub 2}-type oxide at the steps, similar oxide chains form on the (111) terraces, indicating the initial stages of bulk oxide formation.

  3. Composition of RF-sputtered refractory compounds determined by X-ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Wheeler, D. R.; Brainard, W. A.

    1978-01-01

    RF-sputtered coatings of CrB2, MoSi2, Mo2C, TiC, and MoS2 were examined by X-ray photoelectron spectroscopy (XPS). Data on stoichiometry, impurity content, and chemical bonding were obtained. The influences of sputtering target history, deposition time, RF power level, and substrate bias were studied. Significant deviations from stoichiometry and high oxide levels were related to target outgassing. The effect of substrate bias depended on the particular coating material studied.

  4. Short-range order in amorphous SiO{sub x} by x ray photoelectron spectroscopy

    SciTech Connect

    Novikov, Yu. N.; Gritsenko, V. A.

    2011-07-01

    The Si 2p x ray photoelectron spectra of SiO{sub x} with a different composition of 0 {<=} x {<=} 2 have been studied experimentally and theoretically. The SiO{sub x} films were prepared by low-pressure chemical vapor deposition from SiH{sub 4} and N{sub 2}O source at 750 deg. C. Neither random bonding nor random mixture models can adequately describe the structure of these compounds. The interpretation of the experimental results is discussed according to a large scale potential fluctuation due to the spatial variation of chemical composition in SiO{sub x}.

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

    SciTech Connect

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

    2010-02-15

    A new hard x-ray beamline, 10B KIST-PAL beamline (BL10B), has been designed and constructed at the Pohang Light Source (PLS) in Korea. The beamline, operated by Pohang Accelerator Laboratory-Korean Institute of Science and Technology consortium, is dedicated to x-ray scattering (XRS) and x-ray absorption fine structure (XAFS) experiments. X rays with photon energies from 4.0 to 16.0 keV are delivered to the experimental station passing a collimating mirror, a fixed-exit double-crystal Si(111) monochromator, and a toroidal mirror. Basic experimental equipments for XAFS measurement, a high resolution diffractometry, an image plate detector system, and a hot stage have been prepared for the station. From our initial commissioning and performance testing of the beamline, it is observed that BL10B beamline can perform XRS and XAFS measurements successfully.

  6. Depth-resolved soft x-ray photoelectron emission microscopy in nanostructures via standing-wave excited photoemission

    SciTech Connect

    Kronast, F.; Ovsyannikov, R.; Kaiser, A.; Wiemann, C.; Yang, S.-H.; Locatelli, A.; Burgler, D.E.; Schreiber, R.; Salmassi, F.; Fischer, P.; Durr, H.A.; Schneider, C.M.; Eberhardt, W.; Fadley, C.S.

    2008-11-24

    We present an extension of conventional laterally resolved soft x-ray photoelectron emission microscopy. A depth resolution along the surface normal down to a few {angstrom} can be achieved by setting up standing x-ray wave fields in a multilayer substrate. The sample is an Ag/Co/Au trilayer, whose first layer has a wedge profile, grown on a Si/MoSi2 multilayer mirror. Tuning the incident x-ray to the mirror Bragg angle we set up standing x-ray wave fields. We demonstrate the resulting depth resolution by imaging the standing wave fields as they move through the trilayer wedge structure.

  7. The GALAXIES beamline at the SOLEIL synchrotron: inelastic X-ray scattering and photoelectron spectroscopy in the hard X-ray range.

    PubMed

    Rueff, J P; Ablett, J M; Céolin, D; Prieur, D; Moreno, Th; Balédent, V; Lassalle-Kaiser, B; Rault, J E; Simon, M; Shukla, A

    2015-01-01

    The GALAXIES beamline at the SOLEIL synchrotron is dedicated to inelastic X-ray scattering (IXS) and photoelectron spectroscopy (HAXPES) in the 2.3-12 keV hard X-ray range. These two techniques offer powerful complementary methods of characterization of materials with bulk sensitivity, chemical and orbital selectivity, resonant enhancement and high resolving power. After a description of the beamline components and endstations, the beamline capabilities are demonstrated through a selection of recent works both in the solid and gas phases and using either IXS or HAXPES approaches. Prospects for studies on liquids are discussed.

  8. The GALAXIES beamline at the SOLEIL synchrotron: inelastic X-ray scattering and photoelectron spectroscopy in the hard X-ray range.

    PubMed

    Rueff, J P; Ablett, J M; Céolin, D; Prieur, D; Moreno, Th; Balédent, V; Lassalle-Kaiser, B; Rault, J E; Simon, M; Shukla, A

    2015-01-01

    The GALAXIES beamline at the SOLEIL synchrotron is dedicated to inelastic X-ray scattering (IXS) and photoelectron spectroscopy (HAXPES) in the 2.3-12 keV hard X-ray range. These two techniques offer powerful complementary methods of characterization of materials with bulk sensitivity, chemical and orbital selectivity, resonant enhancement and high resolving power. After a description of the beamline components and endstations, the beamline capabilities are demonstrated through a selection of recent works both in the solid and gas phases and using either IXS or HAXPES approaches. Prospects for studies on liquids are discussed. PMID:25537606

  9. Boron Doped diamond films as electron donors in photovoltaics: An X-ray absorption and hard X-ray photoemission study

    SciTech Connect

    Kapilashrami, M.; Zegkinoglou, I.; Conti, G.; Nemšák, S.; Conlon, C. S.; Fadley, C. S.; Törndahl, T.; Fjällström, V.; Lischner, J.; Louie, Steven G.; Hamers, R. J.; Zhang, L.; Guo, J.-H.; Himpsel, F. J.

    2014-10-14

    Highly boron-doped diamond films are investigated for their potential as transparent electron donors in solar cells. Specifically, the valence band offset between a diamond film (as electron donor) and Cu(In,Ga)Se₂ (CIGS) as light absorber is determined by a combination of soft X-ray absorption spectroscopy and hard X-ray photoelectron spectroscopy, which is more depth-penetrating than standard soft X-ray photoelectron spectroscopy. In addition, a theoretical analysis of the valence band is performed, based on GW quasiparticle band calculations. The valence band offset is found to be small: VBO=VBM{sub CIGS} – VBM{sub diamond}=0.3 eV±0.1 eV at the CIGS/Diamond interface and 0.0 eV±0.1 eV from CIGS to bulk diamond. These results provide a promising starting point for optimizing the band offset by choosing absorber materials with a slightly lower valence band maximum.

  10. Boron Doped diamond films as electron donors in photovoltaics: An X-ray absorption and hard X-ray photoemission study

    NASA Astrophysics Data System (ADS)

    Kapilashrami, M.; Conti, G.; Zegkinoglou, I.; Nemšák, S.; Conlon, C. S.; Törndahl, T.; Fjällström, V.; Lischner, J.; Louie, Steven G.; Hamers, R. J.; Zhang, L.; Guo, J.-H.; Fadley, C. S.; Himpsel, F. J.

    2014-10-01

    Highly boron-doped diamond films are investigated for their potential as transparent electron donors in solar cells. Specifically, the valence band offset between a diamond film (as electron donor) and Cu(In,Ga)Se2 (CIGS) as light absorber is determined by a combination of soft X-ray absorption spectroscopy and hard X-ray photoelectron spectroscopy, which is more depth-penetrating than standard soft X-ray photoelectron spectroscopy. In addition, a theoretical analysis of the valence band is performed, based on GW quasiparticle band calculations. The valence band offset is found to be small: VBO = VBMCIGS - VBMdiamond = 0.3 eV ± 0.1 eV at the CIGS/Diamond interface and 0.0 eV ± 0.1 eV from CIGS to bulk diamond. These results provide a promising starting point for optimizing the band offset by choosing absorber materials with a slightly lower valence band maximum.

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

    SciTech Connect

    Tobin, J G

    2011-03-17

    The subjects of discussion included: VUV photoelectron spectroscopy, X-ray photoelectron spectroscopy, Synchrotron-radiation-based photoelectron spectroscopy, Soft x-ray absorption spectroscopy, Soft x-ray emission spectroscopy, Inverse photoelectron spectroscopy, Bremstrahlung Isochromat Spectroscopy, Low energy IPES, Resonant inverse photoelectron spectroscopy.

  12. X-ray photoelectron spectroscopy of graphitic carbon nanomaterials doped with heteroatoms

    PubMed Central

    Pichler, Thomas; Ayala, Paola

    2015-01-01

    Summary X-ray photoelectron spectroscopy (XPS) is one of the best tools for studying the chemical modification of surfaces, and in particular the distribution and bonding of heteroatom dopants in carbon nanomaterials such as graphene and carbon nanotubes. Although these materials have superb intrinsic properties, these often need to be modified in a controlled way for specific applications. Towards this aim, the most studied dopants are neighbors to carbon in the periodic table, nitrogen and boron, with phosphorus starting to emerge as an interesting new alternative. Hundreds of studies have used XPS for analyzing the concentration and bonding of dopants in various materials. Although the majority of works has concentrated on nitrogen, important work is still ongoing to identify its precise atomic bonding configurations. In general, care should be taken in the preparation of a suitable sample, consideration of the intrinsic photoemission response of the material in question, and the appropriate spectral analysis. If this is not the case, incorrect conclusions can easily be drawn, especially in the assignment of measured binding energies into specific atomic configurations. Starting from the characteristics of pristine materials, this review provides a practical guide for interpreting X-ray photoelectron spectra of doped graphitic carbon nanomaterials, and a reference for their binding energies that are vital for compositional analysis via XPS. PMID:25671162

  13. X-ray photoelectron spectroscopy characterization of the {omega} phase in water quenched Ti-5553 alloy

    SciTech Connect

    Qin, Dongyang; Lu, Yafeng; Zhang, Kong; Liu, Qian; Zhou, Lian

    2012-11-15

    X-ray photoelectron spectroscopy was used to investigate the {omega} phase in water quenched Ti-5553 alloy with a nominal composition of Ti-5Al-5V-5Mo-3Cr (wt.%), and the {omega} and the {beta} phase were distinguished by deconvoluting the XPS spectra of Al2p, V2p and Cr2p core level regions. In addition, it is found that the binding energy of core level electron of alloying elements shifts comparing with that of pure metals, and the fact was interpreted by charge redistribution model. X-ray photoelectron spectroscopy technique could be used to characterize the nano-scale {omega} phase in {beta} alloys. - Highlights: Black-Right-Pointing-Pointer We characterize the {omega} phase in Ti-5553 alloy by XPS. Black-Right-Pointing-Pointer Binding energy of Al2p, V2p and Cr2p electron are different in the {omega} and {beta} phase. Black-Right-Pointing-Pointer Structural difference leads to the binding energy gap.

  14. X-ray photoelectron spectroscopy of graphitic carbon nanomaterials doped with heteroatoms.

    PubMed

    Susi, Toma; Pichler, Thomas; Ayala, Paola

    2015-01-01

    X-ray photoelectron spectroscopy (XPS) is one of the best tools for studying the chemical modification of surfaces, and in particular the distribution and bonding of heteroatom dopants in carbon nanomaterials such as graphene and carbon nanotubes. Although these materials have superb intrinsic properties, these often need to be modified in a controlled way for specific applications. Towards this aim, the most studied dopants are neighbors to carbon in the periodic table, nitrogen and boron, with phosphorus starting to emerge as an interesting new alternative. Hundreds of studies have used XPS for analyzing the concentration and bonding of dopants in various materials. Although the majority of works has concentrated on nitrogen, important work is still ongoing to identify its precise atomic bonding configurations. In general, care should be taken in the preparation of a suitable sample, consideration of the intrinsic photoemission response of the material in question, and the appropriate spectral analysis. If this is not the case, incorrect conclusions can easily be drawn, especially in the assignment of measured binding energies into specific atomic configurations. Starting from the characteristics of pristine materials, this review provides a practical guide for interpreting X-ray photoelectron spectra of doped graphitic carbon nanomaterials, and a reference for their binding energies that are vital for compositional analysis via XPS.

  15. Ab initio X-Ray Absorption Fine Structure Cumulants

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  16. Metalloprotein active site structure determination: synergy between X-ray absorption spectroscopy and X-ray crystallography.

    PubMed

    Cotelesage, Julien J H; Pushie, M Jake; Grochulski, Pawel; Pickering, Ingrid J; George, Graham N

    2012-10-01

    Structures of metalloprotein active sites derived from X-ray crystallography frequently contain chemical anomalies such as unexpected atomic geometries or elongated bond-lengths. Such anomalies are expected from the known errors inherent in macromolecular crystallography (ca. 0.1-0.2Å) and from the lack of appropriate restraints for metal sites which are often without precedent in the small molecule structure literature. Here we review the potential of X-ray absorption spectroscopy to provide information and perspective which could aid in improving the accuracy of metalloprotein crystal structure solutions. We also review the potential problem areas in analysis of the extended X-ray absorption fine structure (EXAFS) and discuss the use of density functional theory as another possible source of geometrical restraints for crystal structure analysis of metalloprotein active sites.

  17. X-Ray Absorption Spectroscopy of Strontium(II) Coordination.

    PubMed

    Sahai; Carroll; Roberts; O'Day

    2000-02-15

    Sorption of dissolved strontium on kaolinite, amorphous silica, and goethite was studied as a function of pH, aqueous strontium concentration, the presence or absence of atmospheric CO(2) or dissolved phosphate, and aging over a 57-day period. Selected sorption samples ([Sr(aq)](i) approximately 0.5-1x10(-3) m) were examined with synchrotron X-ray absorption spectroscopy (XAS) at low (13-23 K) and room temperatures to determine the local molecular coordination around strontium. Quantitative analyses of the extended X-ray absorption fine structure (EXAFS) of kaolinite, amorphous silica, and most goethite sorption samples showed a single first shell of 9-10 (+/-1) oxygen atoms around strontium at an average Sr-O bond-distance of 2.61 (+/-0.02) Å, indicating hydrated surface complexes. The EXAFS spectra were unchanged after reaction for up to 57 days. Likewise, in kaolinite sorption samples prepared in 100% nitrogen atmosphere, the presence of dissolved phosphate (0.5x10(-3) m) in addition to strontium did not change the local coordination around strontium. In two goethite sorption samples reacted in air at pH approximately 8.5, the EXAFS spectra (collected at low and room temperature) clearly showed that the local structure around strontium is that of strontianite (SrCO(3)(s)). We also noted an increase in strontium uptake on goethite in the presence of atmospheric CO(2) in batch experiments, relative to CO(2)-free experiments. These observations suggest that sorption of carbonate may nucleate the precipitation of SrCO(3) in the pH range in which carbonate sorption on goethite is near a maximum. At higher pH, carbonate surface sorption decreases as dissolved CO(2) decreases. For goethite sorption samples above pH 8.6, hydrated surface complexes, rather than a precipitate, were observed in the EXAFS spectra. Copyright 2000 Academic Press.

  18. Characterization of SiC fibers by soft x-ray photoelectron and photoabsorption spectroscopies and scanning Auger microscopy

    SciTech Connect

    Ma, Qing; McDowell, M.W.; Rosenberg, R.A.

    1996-08-01

    Synchrotron radiation soft x-ray photoelectron and photoabsorption spectroscopy was used to characterize commercially obtained SiC fibers produced by CVD on a W core and followed by a C passivating layer. Depth profiling of the fiber through the C/SiC interface was done by making Si 2p and C 1s core level PES and PAS, as well as scanning Auger microscopy, measurements following Ar{sup +} sputtering. No significant changes in either photoemission or absorption or Auger line shapes were observed versus depth, indicating no significant interfacial reaction. The line shapes of the carbonaceous coatings are predominantely graphite-like and those of the CVD SiC coatings are microcrystalline, with disorder present to some extent in both cases.

  19. Weak hard X-ray emission from broad absorption line quasars: evidence for intrinsic X-ray weakness

    SciTech Connect

    Luo, B.; Brandt, W. N.; Scott, A. E.; Alexander, D. M.; Gandhi, P.; Stern, D.; Teng, S. H.; Arévalo, P.; Bauer, F. E.; Boggs, S. E.; Craig, W. W.; Christensen, F. E.; Comastri, A.; Farrah, D.; Hailey, C. J.; Harrison, F. A.; Koss, M.; Ogle, P.; Puccetti, S.; Saez, C.; and others

    2014-10-10

    We report NuSTAR observations of a sample of six X-ray weak broad absorption line (BAL) quasars. These targets, at z = 0.148-1.223, are among the optically brightest and most luminous BAL quasars known at z < 1.3. However, their rest-frame ≈2 keV luminosities are 14 to >330 times weaker than expected for typical quasars. Our results from a pilot NuSTAR study of two low-redshift BAL quasars, a Chandra stacking analysis of a sample of high-redshift BAL quasars, and a NuSTAR spectral analysis of the local BAL quasar Mrk 231 have already suggested the existence of intrinsically X-ray weak BAL quasars, i.e., quasars not emitting X-rays at the level expected from their optical/UV emission. The aim of the current program is to extend the search for such extraordinary objects. Three of the six new targets are weakly detected by NuSTAR with ≲ 45 counts in the 3-24 keV band, and the other three are not detected. The hard X-ray (8-24 keV) weakness observed by NuSTAR requires Compton-thick absorption if these objects have nominal underlying X-ray emission. However, a soft stacked effective photon index (Γ{sub eff} ≈ 1.8) for this sample disfavors Compton-thick absorption in general. The uniform hard X-ray weakness observed by NuSTAR for this and the pilot samples selected with <10 keV weakness also suggests that the X-ray weakness is intrinsic in at least some of the targets. We conclude that the NuSTAR observations have likely discovered a significant population (≳ 33%) of intrinsically X-ray weak objects among the BAL quasars with significantly weak <10 keV emission. We suggest that intrinsically X-ray weak quasars might be preferentially observed as BAL quasars.

  20. High energy X-ray phase and dark-field imaging using a random absorption mask

    NASA Astrophysics Data System (ADS)

    Wang, Hongchang; Kashyap, Yogesh; Cai, Biao; Sawhney, Kawal

    2016-07-01

    High energy X-ray imaging has unique advantage over conventional X-ray imaging, since it enables higher penetration into materials with significantly reduced radiation damage. However, the absorption contrast in high energy region is considerably low due to the reduced X-ray absorption cross section for most materials. Even though the X-ray phase and dark-field imaging techniques can provide substantially increased contrast and complementary information, fabricating dedicated optics for high energies still remain a challenge. To address this issue, we present an alternative X-ray imaging approach to produce transmission, phase and scattering signals at high X-ray energies by using a random absorption mask. Importantly, in addition to the synchrotron radiation source, this approach has been demonstrated for practical imaging application with a laboratory-based microfocus X-ray source. This new imaging method could be potentially useful for studying thick samples or heavy materials for advanced research in materials science.

  1. Quantitative interpretation of molecular dynamics simulations for X-ray photoelectron spectroscopy of aqueous solutions

    NASA Astrophysics Data System (ADS)

    Olivieri, Giorgia; Parry, Krista M.; Powell, Cedric J.; Tobias, Douglas J.; Brown, Matthew A.

    2016-04-01

    Over the past decade, energy-dependent ambient pressure X-ray photoelectron spectroscopy (XPS) has emerged as a powerful analytical probe of the ion spatial distributions at the vapor (vacuum)-aqueous electrolyte interface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt to provide a complete description of the liquid interface. There is, however, no systematic protocol that permits a straightforward comparison of the two sets of results. XPS is an integrated technique that averages signals from multiple layers in a solution even at the lowest photoelectron kinetic energies routinely employed, whereas MD simulations provide a microscopic layer-by-layer description of the solution composition near the interface. Here, we use the National Institute of Standards and Technology database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to quantitatively interpret atom-density profiles from MD simulations for XPS signal intensities using sodium and potassium iodide solutions as examples. We show that electron inelastic mean free paths calculated from a semi-empirical formula depend strongly on solution composition, varying by up to 30% between pure water and concentrated NaI. The XPS signal thus arises from different information depths in different solutions for a fixed photoelectron kinetic energy. XPS signal intensities are calculated using SESSA as a function of photoelectron kinetic energy (probe depth) and compared with a widely employed ad hoc method. SESSA simulations illustrate the importance of accounting for elastic-scattering events at low photoelectron kinetic energies (<300 eV) where the ad hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquid interfaces are discussed.

  2. Quantitative interpretation of molecular dynamics simulations for X-ray photoelectron spectroscopy of aqueous solutions.

    PubMed

    Olivieri, Giorgia; Parry, Krista M; Powell, Cedric J; Tobias, Douglas J; Brown, Matthew A

    2016-04-21

    Over the past decade, energy-dependent ambient pressure X-ray photoelectron spectroscopy(XPS) has emerged as a powerful analytical probe of the ion spatial distributions at the vapor (vacuum)-aqueous electrolyteinterface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt to provide a complete description of the liquidinterface. There is, however, no systematic protocol that permits a straightforward comparison of the two sets of results. XPS is an integrated technique that averages signals from multiple layers in a solution even at the lowest photoelectron kinetic energies routinely employed, whereas MD simulations provide a microscopic layer-by-layer description of the solution composition near the interface. Here, we use the National Institute of Standards and Technology database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to quantitatively interpret atom-density profiles from MD simulations for XPS signal intensities using sodium and potassium iodide solutions as examples. We show that electron inelastic mean free paths calculated from a semi-empirical formula depend strongly on solution composition, varying by up to 30% between pure water and concentrated NaI. The XPS signal thus arises from different information depths in different solutions for a fixed photoelectron kinetic energy. XPS signal intensities are calculated using SESSA as a function of photoelectron kinetic energy (probe depth) and compared with a widely employed ad hoc method. SESSA simulations illustrate the importance of accounting for elastic-scattering events at low photoelectron kinetic energies (<300 eV) where the ad hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquidinterfaces are discussed. PMID:27389231

  3. Electronic Structures of Uranium Compounds Studied by Soft X-ray Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Fujimori, Shin-ichi; Takeda, Yukiharu; Okane, Tetsuo; Saitoh, Yuji; Fujimori, Atsushi; Yamagami, Hiroshi; Haga, Yoshinori; Yamamoto, Etsuji; Ōnuki, Yoshichika

    2016-06-01

    The electronic structures of uranium-based compounds have been studied by photoelectron spectroscopy with soft X-ray synchrotron radiation. Angle-resolved photoelectron spectroscopy with soft X-rays has made it possible to directly observe their bulk band structures and Fermi surfaces. It has been shown that the band structures and Fermi surfaces of itinerant compounds such as UB2, UN, and UFeGa5 are quantitatively described by a band-structure calculation treating all U 5f electrons as itinerant. Furthermore, the overall electronic structures of heavy-fermion compounds such as UPd2Al3, UNi2Al3, and URu2Si2 are also explained by a band-structure calculation, although some disagreements exist, which might originate from the electron correlation effect. This suggests that the itinerant description of U 5f states is an appropriate starting point for the description of their electronic structures. The situation is similar for ferromagnetic superconductors such as UGe2, URhGe, UCoGe, and UIr, although the complications from their low-symmetry crystal structures make it more difficult to describe their detailed electronic structures. The local electronic structures of the uranium site have been probed by core-level photoelectron spectroscopy with soft X-rays. The comparisons of core-level spectra of heavy-fermion compounds with typical itinerant and localized compounds suggest that the local electronic structures of most itinerant and heavy-fermion compounds are close to the U 5f3 configuration except for UPd2Al3 and UPt3. The core-level spectrum of UPd2Al3 has similarities to those of both itinerant and localized compounds, suggesting that it is located at the boundary between the itinerant and localized states. Moreover, the spectrum of UPt3 is very close to that of the localized compound UPd3, suggesting that it is nearly localized, although there are narrow quasi-particle bands in the vicinity of EF.

  4. A Comprehensive X-Ray Absorption Model for Atomic Oxygen

    NASA Technical Reports Server (NTRS)

    Gorczyca, T. W.; Bautista, M. A.; Hasoglu, M. F.; Garcia, J.; Gatuzz, E.; Kaastra, J. S.; Kallman, T. R.; Manson, S. T.; Mendoza, C.; Raassen, A. J. J.; de Vries, C. P.; Zatsarinny, O.

    2013-01-01

    An analytical formula is developed to accurately represent the photoabsorption cross section of atomic Oxygen for all energies of interest in X-ray spectral modeling. In the vicinity of the K edge, a Rydberg series expression is used to fit R-matrix results, including important orbital relaxation effects, that accurately predict the absorption oscillator strengths below threshold and merge consistently and continuously to the above-threshold cross section. Further, minor adjustments are made to the threshold energies in order to reliably align the atomic Rydberg resonances after consideration of both experimental and observed line positions. At energies far below or above the K-edge region, the formulation is based on both outer- and inner-shell direct photoionization, including significant shake-up and shake-off processes that result in photoionization-excitation and double-photoionization contributions to the total cross section. The ultimate purpose for developing a definitive model for oxygen absorption is to resolve standing discrepancies between the astronomically observed and laboratory-measured line positions, and between the inferred atomic and molecular oxygen abundances in the interstellar medium from XSTAR and SPEX spectral models.

  5. A comprehensive X-ray absorption model for atomic oxygen

    SciTech Connect

    Gorczyca, T. W.; Bautista, M. A.; Mendoza, C.; Hasoglu, M. F.; García, J.; Gatuzz, E.; Kaastra, J. S.; Raassen, A. J. J.; De Vries, C. P.; Kallman, T. R.; Manson, S. T.; Zatsarinny, O.

    2013-12-10

    An analytical formula is developed to accurately represent the photoabsorption cross section of O I for all energies of interest in X-ray spectral modeling. In the vicinity of the K edge, a Rydberg series expression is used to fit R-matrix results, including important orbital relaxation effects, that accurately predict the absorption oscillator strengths below threshold and merge consistently and continuously to the above-threshold cross section. Further, minor adjustments are made to the threshold energies in order to reliably align the atomic Rydberg resonances after consideration of both experimental and observed line positions. At energies far below or above the K-edge region, the formulation is based on both outer- and inner-shell direct photoionization, including significant shake-up and shake-off processes that result in photoionization-excitation and double-photoionization contributions to the total cross section. The ultimate purpose for developing a definitive model for oxygen absorption is to resolve standing discrepancies between the astronomically observed and laboratory-measured line positions, and between the inferred atomic and molecular oxygen abundances in the interstellar medium from XSTAR and SPEX spectral models.

  6. Infrared and x-ray photoelectron spectra of ruthenium oxide films and ruthenium hydroxide

    SciTech Connect

    Belova, I.D.; Shifrina, R.R.; Roginskaya, Yu.E.; Popov, A.V.; Varlamova, T.V.

    1988-03-01

    The IR and x-ray photoelectron spectra of ruthenium hydroxide and of ruthenium oxide films produced by ruthenium chloride hydroxide decomposition at 300, 400, 500, and 600 degrees C were examined in order to obtain information concerning the effect of hydration on the structure and electronic properties of the surface of ruthenium oxide electrodes. It was shown that Ru hydroxide and Ru oxide films contain both water molecules and hydroxyl groups; the latter are retained up to higher temperatures (600 degrees C) in the Ru oxide films than in Ru hydroxide. It was found that water makes the materials studied amorphous, and it also was found that hydration influences their electronic structure (valence band and the electronic core levels of Ru and O).

  7. X-ray photoelectron spectroscopy study of radiofrequency-sputtered refractory compound steel interfaces

    NASA Technical Reports Server (NTRS)

    Wheeler, D. R.; Brainard, W. A.

    1978-01-01

    Radiofrequency sputtering was used to deposit Mo2C, Mo2B5, and MoSi2 coatings on 440C steel substrates. Both sputter etched and preoxidized substrates were used, and the films were deposited with and without a substrate bias of -300 V. The composition of the coatings was measured as a function of depth by X-ray photoelectron spectroscopy combined with argon ion etching. In the interfacial region there was evidence that bias produced a graded interface in Mo2B5 but not in Mo2C. Oxides of iron and of all film constituents except carbon were presented in all cases but the iron oxide concentration was higher and the layer thicker on the preoxidized substrates. The film and iron oxides were mixed in the MoSi2 and Mo2C films but layered in the Mo2B5 film. The presence of mixed oxides correlates with enhanced film adhesion.

  8. X-ray photoelectron spectroscopic analysis of rice kernels and flours: Measurement of surface chemical composition.

    PubMed

    Nawaz, Malik A; Gaiani, Claire; Fukai, Shu; Bhandari, Bhesh

    2016-12-01

    The objectives of this study were to evaluate the ability of X-ray photoelectron spectroscopy (XPS) to differentiate rice macromolecules and to calculate the surface composition of rice kernels and flours. The uncooked kernels and flours surface composition of the two selected rice varieties, Thadokkham-11 (TDK11) and Doongara (DG) demonstrated an over-expression of lipids and proteins and an under-expression of starch compared to the bulk composition. The results of the study showed that XPS was able to differentiate rice polysaccharides (mainly starch), proteins and lipids in uncooked rice kernels and flours. Nevertheless, it was unable to distinguish components in cooked rice samples possibly due to complex interactions between gelatinized starch, denatured proteins and lipids. High resolution imaging methods (Scanning Electron Microscopy and Confocal Laser Scanning Microscopy) were employed to obtain complementary information about the properties and location of starch, proteins and lipids in rice kernels and flours. PMID:27374542

  9. Surface properties of SmB6 from x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Heming, N.; Treske, U.; Knupfer, M.; Büchner, B.; Inosov, D. S.; Shitsevalova, N. Y.; Filipov, V. B.; Krause, S.; Koitzsch, A.

    2014-11-01

    We have investigated the properties of cleaved SmB6 single crystals by x-ray photoelectron spectroscopy. At low temperatures and freshly cleaved samples a surface core level shift is observed which vanishes when the temperature is increased. A Sm valence between 2.5 and 2.6 is derived from the relative intensities of the Sm2 + and Sm3 + multiplets. The B/Sm intensity ratio obtained from the core levels is always larger than the stoichiometric value. Possible reasons for this deviation are discussed. The B 1s signal shows an unexpected complexity: An anomalous low energy component appears with increasing temperature and is assigned to the formation of a suboxide at the surface. While several interesting intrinsic and extrinsic properties of the SmB6 surface are elucidated in this manuscript, no clear indication of a trivial mechanism for the prominent surface conductivity is found.

  10. Determination of InN/Diamond Heterojunction Band Offset by X-ray Photoelectron Spectroscopy

    PubMed Central

    2011-01-01

    Diamond is not only a free standing highly transparent window but also a promising carrier confinement layer for InN based devices, yet little is known of the band offsets in InN/diamond system. X-ray photoelectron spectroscopy was used to measure the energy discontinuity in the valence band offset (VBO) of InN/diamond heterostructure. The value of VBO was determined to be 0.39 ± 0.08 eV and a type-I heterojunction with a conduction band offset (CBO) of 4.42 ± 0.08 eV was obtained. The accurate determination of VBO and CBO is important for the application of III-N alloys based electronic devices. PMID:27502672

  11. An x ray photoelectron spectroscopy study of Au(x)In(y) alloys

    NASA Technical Reports Server (NTRS)

    Jayne, Douglas T.; Fatemi, Navid S.; Weizer, Victor G.

    1990-01-01

    Four gold-indium alloys were studied by x ray photoelectron spectroscopy. The binding energies and intensity ratios of the Au 4f7/2 and In 3d5/2 core levels were determined for the bulk alloy compositions of Au(10 percent In), Au3In, AuIn, and AuIn2. These values were determined for the native oxides on the materials, for the surfaces prepared by ion bombardment to remove the oxide and for surfaces scraped in-situ with a ceramic tool to expose the bulk composition. These results furnish calibration values that allow determination of the composition of thin films of this alloy system. In addition the binding energies add to the data base for understanding the effect of alloying on core level binding energies. As an illustration, these results are used to determine the composition of a series of alloy films formed by incongruent evaporation of an alloy charge.

  12. X-ray photoelectron spectroscopy study of chemically-etched Nd-Ce-Cu-O surfaces

    NASA Technical Reports Server (NTRS)

    Vasquez, R. P.; Gupta, A.; Kussmaul, A.

    1991-01-01

    Acetic acid, Br2, and HCl solutions are investigated for removing insulating species from Nd(1.85)Ce(0.15)CuO(4-delta) (NCCO) thin film surfaces. X-ray photoelectron spectroscopy (XPS) shows that the HCl etch is most effective, yielding O 1s spectra comparable to those obtained from samples cleaned in vacuum and a clear Fermi edge in the valence band region. Reduction and oxidation reversibly induces and eliminates, respectively, Fermi level states for undoped samples, but has no clearly observable effect on the XPS spectra for doped samples. Reactivity to air is much less for NCCO compared to hole superconductors, which is attributed to the lack of reactive alkaline earth elements in NCCO.

  13. Uses of Auger and x ray photoelectron spectroscopy in the study of adhesion and friction

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa

    1990-01-01

    Three studies are described characterizing the possible contributions of surface science to tribology. These include surface contamination formed by the interaction of a surface with the environment, contaminants obtained with diffusion of compounds, and surface chemical changes resulting from selective thermal evaporation. Surface analytical tools such as Auger electron spectroscopy (AES) and x ray photoelectron spectroscopy (XPS) incorporated directly into adhesion and friction systems are primarily used to define the nature of tribological surfaces before and after tribological experimentation and to characterize the mechanism of solid-to-solid interaction. Emphasis is on fundamental studies involving the role of surfaces in controlling the adhesion and friction properties of materials emerging as a result of the surface analyses. The materials which were studied include metals and ceramics such as elemental metals, amorphous alloys (metallic glasses), and silicon-based ceramics.

  14. X-ray photoelectron and mass spectroscopic study of electron irradiation and thermal stability of polytetrafluoroethylene

    NASA Technical Reports Server (NTRS)

    Wheeler, Donald R.; Pepper, Stephen V.

    1990-01-01

    Polytetrafluoroethylene (PTFE) was subjected to 3 keV electron bombardment and then heated in vacuum to 300 C. The behavior of the material as a function of radiation dose and temperature was studied by X-ray photoelectron spectroscopy (XPS) of the surface and mass spectroscopy of the species evolved. A quantitative comparison of the radiation dose rate with that in other reported studies showed that, for a given total dose, the damage observed by XPS is greater for higher dose rates. Lightly damaged material heated to 300 C evolved saturated fluorocarbon species, whereas unsaturated fluorocarbon species evolved from heavily damaged material. After heating the heavily damaged material, those features in the XPS that were associated with damage diminished, giving the appearance that the radiation damage annealed. The apparent annealing of the radiation damage was found to be due to the covering of the network by saturated fragments that easily diffused through the decomposed material to the surface region upon heating.

  15. Highly Angle-Resolved X-Ray Photoelectron Diffraction from Solid Surfaces

    NASA Astrophysics Data System (ADS)

    Tamura, K.; Shiraki, S.; Ishii, H.; Owari, M.; Nihei, Y.

    We have carried out the highly angle-resolved X-ray photoelectron diffraction (XPED) measurements by using the input-lens system for restriction of the detection angle. In the input-lens system, high angular resolution and high throughput are accomplished by placing an aperture not on the image plane but on the diffraction plane of electron optics. The aperture sizes (ϕ 4 mm, ϕ 2 mm, ϕ 0.5 mm, ϕ 0.25 mm) correspond to the angular resolutions (± 0.6°, ± 0.3°, ± 0.08°, ± 0.04°) respectively. Highly angle-resolved Ge3d XPED patterns from Ge(111) obtained by the angle-resolving system contain fine structure such as Kikuchi patterns. The fine structure was reproduced by multiple scattering cluster calculations.

  16. [Surface and interface analysis of PTCDA/ITO using X-ray photoelectron spectroscopy (XPS)].

    PubMed

    Ou, Gu-ping; Song, Zhen; Gui, Wen-ming; Zhang, Fu-jia

    2006-04-01

    X-ray photoelectron spectroscopy (XPS) of surface and interface of PTCDA/ITO in PTCDA/p-Si organic-on-inorganic photoelectric detector was investigated. From C1s fine spectrum we found that the binding energy of C atoms in perylene rings was 284.6 eV; and the binding energy of C atoms in acid radical was 288.7 eV; moreover, some C atoms were oxidized by O atoms from ITO. The binding energy of O atoms in C=O bonds and C-O-C bonds was 531.5 and 533.4 eV, respectively. At the interface, the peak of high binding energy in C1s spectrum disappeared, and the main peak shifted toward lower binding energy.

  17. Measurement of barrier height of Pd on diamond (100) surface by X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, F. N.; Liu, J. W.; Zhang, J. W.; Wang, X. L.; Wang, W.; Liu, Z. C.; Wang, H. X.

    2016-05-01

    Barrier height (VBH) values for Pd/hydrogen-terminated diamond (H-diamond) and Pd/oxygen-terminated diamond (O-diamond) have been investigated by X-ray photoelectron spectroscopy technique. H-diamond and O-diamond have been formed on the same diamond (100) layer grown by microwave plasma-enhanced chemical vapor deposition on which Pd layers have been evaporated. The VBH values for Pd/H-diamond and Pd/O-diamond are determined to be -0.27 eV and 1.73 eV, respectively. It indicates that Pd is a suitable metal for ohmic and Schottky contacts on H-diamond and O-diamond, respectively. The experimental ΦBH values are in good agreement with the theoretical calculation results.

  18. A laser-based instrument for the study of ultrafast chemical dynamics by soft x-ray-probe photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Nugent-Glandorf, Lora; Scheer, Michael; Samuels, David A.; Bierbaum, Veronica; Leone, Stephen R.

    2002-04-01

    A laser-based instrument is described for the study of femtosecond dissociation dynamics of gas phase molecules via time-resolved vacuum ultraviolet and soft x-ray photoelectron spectroscopy. Visible or UV pump pulses are generated with nonlinear crystal techniques on a Ti:sapphire laser output, while soft x-ray probe pulses are created via high-order harmonic generation of the same laser in rare gases. Here we describe the optical layout of the pump-probe system, the means for separation of the high-order harmonics in the soft x-ray probe beam, including a description of the two grating setup used to compress the high-harmonic pulses and the magnetic bottle photoelectron spectrometer used for data collection. The feasibility of using the generated high-harmonic pulses for an array of gaseous phase photoelectron spectroscopy experiments is established. These include measurements of valence shell and core-level photoelectron transitions in atoms and molecules, the tunability of the soft x-ray harmonic through Rydberg resonances, and the energy bandwidths of the harmonics. Cross correlations between the visible/UV and soft x-ray pulses, by above threshold ionization, are used to establish the pulse timing, pulse duration, and spatial overlap for ultrafast studies. The observed real time photodissociation of Br2 serves as a demonstration of the pump-probe ultrafast technique and the applicability to ultrafast time-resolved chemical dynamics.

  19. Thomson Thick X-Ray Absorption in a Broad Absorption Line Quasar, PG 0946+301.

    PubMed

    Mathur; Green; Arav; Brotherton; Crenshaw; deKool; Elvis; Goodrich; Hamann; Hines; Kashyap; Korista; Peterson; Shields; Shlosman; van Breugel W; Voit

    2000-04-20

    We present a deep ASCA observation of a broad absorption line quasar (BALQSO) PG 0946+301. The source was clearly detected in one of the gas imaging spectrometers, but not in any other detector. If BALQSOs have intrinsic X-ray spectra similar to normal radio-quiet quasars, our observations imply that there is Thomson thick X-ray absorption (NH greater, similar1024 cm-2) toward PG 0946+301. This is the largest column density estimated so far toward a BALQSO. The absorber must be at least partially ionized and may be responsible for attenuation in the optical and UV. If the Thomson optical depth toward BALQSOs is close to 1, as inferred here, then spectroscopy in hard X-rays with large telescopes like XMM would be feasible.

  20. X-ray photoelectron spectroscopy and luminescent properties of Y2O3:Bi3+ phosphor

    NASA Astrophysics Data System (ADS)

    Jafer, R. M.; Coetsee, E.; Yousif, A.; Kroon, R. E.; Ntwaeaborwa, O. M.; Swart, H. C.

    2015-03-01

    X-ray photoelectron spectroscopy (XPS) results provided proof for the blue and green emission of Bi3+ in the Y2O3:Bi3+ phosphor. The Y2O3:Bi3+ phosphor was successfully prepared by the combustion process during the investigation of down-conversion materials for Si solar cell application. The X-ray diffraction (XRD) patterns indicated that a single-phase cubic crystal structure with the Ia3 space group was formed. X-ray photoelectron spectroscopy (XPS) showed that the Bi3+ ion replaces the Y3+ ion in two different coordination sites in the Y2O3 crystal structure. The O 1s peak shows five peaks, two which correlate with the O2- ion in Y2O3 in the two different sites, two which correlate with O2- in Bi2O3 in the two different sites and the remaining peak relates to hydroxide. The Y 3d spectrum shows two peaks for the Y3+ ion in the Y2O3 structure in two different sites and the Bi 4f spectrum shows the Bi3+ ion in the two different sites in Bi2O3. The photoluminescence (PL) results showed three broad emission bands in the blue and green regions under ultraviolet excitation, which were also present for panchromatic cathodoluminescence (CL) results. These three peaks have maxima at ∼3.4, 3.0 and 2.5 eV. The PL emission ∼3.0 eV (blue emission) showed two excitation bands centered at ∼3.7 and 3.4 eV while the PL emission at ∼2.5 eV (green emission) showed a broad excitation band from ∼4 to 3.4 eV. The panchromatic CL images were obtained for selected wavelengths at (2.99 ± 0.08) eV (for blue emission) and (2.34 ± 0.06) eV (for green emission). These luminescence results correlate with the XPS results that show that there are two different Bi3+ sites in the host lattice.

  1. Near Edge X-ray Absorption Spectroscopy of Polymers

    NASA Astrophysics Data System (ADS)

    Dhez, Olivier; Ade, Harald; Urquhart, Stephen

    2001-03-01

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

  2. X-Ray Continua of Broad Absorption Line Quasars

    NASA Technical Reports Server (NTRS)

    Mathur, S.

    1999-01-01

    The targets for this program, PG1416-129 and LBQS 2212-1759 were known to be Broad Absorption Line Quasars (BALQSOs). BALQSOs are highly absorbed in soft X-rays. Good high energy response of Rossi-XTE made them ideal targets for observation. We observed LBQS 2212-1759 with PCA. We have now analyzed the data and found that the source was not detected. Since our target was expected to be faint, reliable estimate of background was very important. With the release of new FTOOLS (version 4.1) we were able to do so. We also analyzed a well known bright object and verified our results with the published data. This gave us confidence in the non-detection of our target LBQS 2212-1759. We are currently investigating the implications of this non-detection. Due to some scheduling problems, our second target PG1416-129 was not observed in A01. It was observed on 06/26/98. This target was detected with RXTE. We are now working on the spectral analysis with XSPEC.

  3. Reactive ZnO/Ti/ZnO interfaces studied by hard x-ray photoelectron spectroscopy

    SciTech Connect

    Knut, Ronny Lindblad, Rebecka; Rensmo, Håkan; Karis, Olof; Grachev, Sergey; Faou, Jean-Yvon; Søndergård, Elin

    2014-01-28

    The chemistry and intermixing at buried interfaces in sputter deposited ZnO/Ti/ZnO thin layers were studied by hard x-ray photoelectron spectroscopy. The long mean free path of the photoelectrons allowed for detailed studies of the oxidation state, band bending effects, and intrinsic doping of the buried interfaces. Oxidation of the Ti layer was observed when ZnO was deposited on top. When Ti is deposited onto ZnO, Zn Auger peaks acquire a metallic character indicating a strong reduction of ZnO at the interface. Annealing of the stack at 200 °C results in further reduction of ZnO and oxidation of Ti. Above 300 °C, oxygen transport from the bulk of the ZnO layer takes place, leading to re-oxidation of ZnO at the interface and further oxidation of Ti layer. Heating above 500 °C leads to an intermixing of the layers and the formation of a Zn{sub x}TiO{sub y} compound.

  4. X-ray absorption in matter. Reengineering XCOM

    NASA Astrophysics Data System (ADS)

    Gerward, L.; Guilbert, N.; Bjørn Jensen, K.; Levring, H.

    2001-01-01

    A Windows version of XCOM, the well-known program for calculating X-ray and gamma-ray attenuation coefficients and interaction cross sections, has been developed. The new program, called WinXCom, has an improved user interface.

  5. Enhancement of X-ray dose absorption for medical applications

    NASA Astrophysics Data System (ADS)

    Lim, Sara; Nahar, S.; Pradhan, A.; Barth, R.

    2013-05-01

    A promising technique for cancer treatment is radiation therapy with high-Z (HZ) nanomoities acting as radio-sensitizers attached to tumor cells and irradiated with X-rays. But the efficacy of radiosenstization is highly energy dependent. We study the physical effects in using platinum (Pt) as the radio-sensitizing agent, coupled with commonly employed broadband x-ray sources with mean energies around 100 keV, as opposed to MeV energies produced by clinical linear accelerators (LINAC) used in radiation therapy. Numerical calculations, in vitro, and in vivo studies of F98 rat glioma (brain cancer) demonstrate that irradiation from a medium energy X-ray (MEX) 160 kV source is far more effective than from a high energy x-ray (HEX) 6 MV LINAC. We define a parameter to quantify photoionization by an x-ray source, which thereby provides a measure of subsequent Auger decays. The platinum (Z = 78) results are also relevant to ongoing studies on x-ray interaction with gold (Z = 79) nanoparticles, widely studied as an HZ contrast agent. The present study should be of additional interest for a combined radiation plus chemotherapy treatment since Pt compounds such cis-Pt and carbo-Pt are commonly used in chemotherapy.

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

    SciTech Connect

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

    2010-06-15

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

  7. X-ray photoelectron spectra structure and chemical bond nature in NpO2

    NASA Astrophysics Data System (ADS)

    Teterin, Yu. A.; Teterin, A. Yu.; Ivanov, K. E.; Ryzhkov, M. V.; Maslakov, K. I.; Kalmykov, St. N.; Petrov, V. G.; Enina, D. A.

    2014-01-01

    Quantitative analysis was done of the x-ray photoelectron spectra structure in the binding energy (BE) range of 0 to ˜35 eV for neptunium dioxide (NpO2) valence electrons. The BEs and structure of the core electronic shells (˜35-1250 eV) as well as the relativistic discrete variation calculation results for the finite fragment of the NpO2 lattice and the data of other authors were taken into account. The experimental data show that the many-body effects and the multiplet splitting contribute to the spectral structure much less than the effects of formation of the outer (0-˜15 eV) and the inner (˜15-˜35 eV) valence molecular orbitals (OVMO and IVMO, respectively). The filled Np 5f electronic states were shown to form in the NpO2 valence band. The Np 6p electrons participate in formation of both the IVMO and the OVMO (bands). The filled Np 6p3/2 and the O 2s electronic shells were found to take the maximum part in the IVMO formation. The MO composition and the sequence order in the BE range 0-˜35 eV in NpO2 were established. The experimental and theoretical data allowed a quantitative MO scheme for NpO2, which is fundamental for both understanding the chemical bond nature in neptunium dioxide and the interpretation of other x-ray spectra of NpO2.

  8. X-ray Photoelectron Spectroscopy Study of Argon-Plasma-Treated Fluoropolymers

    NASA Technical Reports Server (NTRS)

    Golub, Morton A.; Lopata, Eugene S.; Finney, Lorie S.

    1994-01-01

    Films of poly(tetrafluoroethylene) (PTFE) and of a tetrafluoroethylene-perfluoroalkyl vinyl ether (approximately 49:1) copolymer (PFA) were exposed to a radio-frequency argon plasma and then examined by X-ray photoelectron spectroscopy (XPS). The use of fluoropolymer films nearly free of surface hydrocarbon contamination as well as the use of a monochromatized X-ray source for XPS removed two factors contributing to conflicting reports on the effect of exposure time on the fluorine-to-carbon (F/C) and oxygen-to-carbon (O/C) ratios for several Ar-plasma-treated fluoropolymers. Contrary to literature indications, a common pattern was found for PTFE and PFA: a moderate decrease in F/C ratio (from 1.99 to 1.40, and from 1.97 to 1.57, respectively), together with a moderate increase in O/C ratio (from negligible to about 0.10, and from 0.012 to about O.10, respectively) at very short exposures, after which the F/C ratios remained essentially constant on prolonged exposures, while the O/C ratios for PTFE and PFA leveled off at 0.11 and 0.15, respectively. The XPS C(sub 1s), spectra for these polymers exposed to the Ar plasma for 20 min were similar and presented, besides a prominent peak at 292.0 eV (CF2,) and a minor peak at 294.0 or 294.1 eV (CF3), a composite band of four curve-resolved peaks (approximately 285-290 eV) representing various CH, CC, CO, CN, and CF functionalities.

  9. First-principles core-level X-ray photoelectron spectroscopy calculation on arsenic defects in silicon crystal

    SciTech Connect

    Kishi, Hiroki; Miyazawa, Miki; Matsushima, Naoki; Yamauchi, Jun

    2014-02-21

    We investigate the X-ray photoelectron spectroscopy (XPS) binding energies of As 3d in Si for various defects in neutral and charged states by first-principles calculation. It is found that the complexes of a substitutional As and a vacancy in charged and neutral states explain the experimentally observed unknown peak very well.

  10. X-ray photoelectron spectroscopic evidence for bacteria-enhanced dissolution of hornblende

    NASA Astrophysics Data System (ADS)

    Kalinowski, B. E.; Liermann, L. J.; Brantley, S. L.; Barnes, A.; Pantano, C. G.

    2000-04-01

    An Arthrobacter species capable of extracting Fe from hornblende was isolated from a soil from the Adirondacks, NY (USA). This bacteria isolate, used in batch experiments with hornblende, accelerated the release of Fe from hornblende without measurably affecting Al release. The isolate produces both low molecular weight organic acids (LMWOA) and a catecholate siderophore. Polished hornblende (glass and crystal) discs were analyzed with X-ray photoelectron spectroscopy (XPS) before and after incubation with growing Arthrobacter sp. to investigate whether the bacteria caused a distinguishable chemical signature on the upper 100 Å of mineral surface. After removal of the arthrobacter grown on hornblende crystal or glass substrates using lysozyme, XPS revealed surface depletion of Fe for samples grown for several days in buffered (crystal) and unbuffered (crystal and glass) media. Fe/Si ratios of hornblende surfaces dissolved under biotic conditions are significantly lower than Fe/Si ratios on surfaces dissolved under abiotic conditions for similar amounts of time. Enhanced Fe release and the formation of Fe-depleted surfaces is inferred to be caused by catechol complexation at the mineral surface. Because natural siderophore was not isolated in sufficient quantities to run bacteria-free leaching experiments, parallel investigations were run with a commercially available siderophore (desferrioxamine B). Desferrioxamine B was observed to enhance release of Fe, Si, and Al from hornblende both with and without added bacteria. Formation of desferrioxamine-Fe surface complexes were probed by studying the multiple splitting and shift in intensities of the N 1s line analyzed by XPS on siderophore ± Fe on gold surfaces and siderophore + hornblende crystal surfaces. Based upon the observed formation of an hydroxamate (desferrioxamine) surface complex on hornblende, we infer that catecholate siderophores, such as those produced by the arthrobacter, also complex on the

  11. Enhancement of X-ray dose absorption for medical applications

    NASA Astrophysics Data System (ADS)

    Lim, Sara; Montenegro, Maximiliano; Nahar, Sultana; Pradhan, Anil; Barth, Rolf; Nakkula, Robin; Bell, Erica; Yu, Yan

    2012-06-01

    Interaction of high-Z (HZ) elements with X-rays occurs efficiently at specific resonant energies. Cross sections for photoionization rapidly decrease after the K-edge; higher energy X-rays are mostly Compton-scattered. These features restrict the energy range for the use of HZ moities for radiosensitization in cancer therapy. Conventional X-ray sources such as linear accelerators (LINAC) used in radiotherapy emit a broad spectrum up to MeV energies. We explore the dichotomy between X-ray radiotherapy in two ranges: (i) E < 100 keV including HZ sensitization, and (ii) E > 100 keV where sensitization is inefficient. We perform Monte Carlo numerical simulations of tumor tissue embedded with platinum compounds and gold nanoparticles and compute radiation dose enhancement factors (DEF) upon irradiation with 100 kV, 170 kV and 6 MV sources. Our results demonstrate that the DEF peak below 100 keV and fall sharply above 200 keV to very small values. Therefore most of the X-ray output from LINACs up to the MeV range is utilized very inefficiently. We also describe experimental studies for implementation of option (i) using Pt and Au reagents and selected cancer cell lines. Resultant radiation exposure to patients could be greatly reduced, yet still result in increased tumoricidal ability.

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

    SciTech Connect

    Tan, G.O.

    1993-06-01

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

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

    SciTech Connect

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

    2007-11-27

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

  14. Surface composition analysis of HF vapour cleaned silicon by X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Ermolieff, A.; Martin, F.; Amouroux, A.; Marthon, S.; Westendorp, J. F. M.

    1991-06-01

    X-ray photoelectron spectroscopy (XPS) measurements on silicon surfaces treated by HF gaseous cleaning are described. Various cleaning recipes, which essentially differ by the amount of water present during the reaction were studied; the composition of the silicon surface was measured in terms of monolayer coverage of oxygen, fluorine and carbon. These gaseous cleaned surfaces are compared with those of commonly deglazed silicon samples by using an aqueous HF bath. The F(1s), O(1s), Si(2p), C(1s) photoelectron lines were monitored, and concentrations determined as usual by integration of the lines after removal of the non-linear backgroune. The F(1s), C(1s) and Si(2p) lines were decomposed into several components corresponding to different chemical bonds. The results show that the amount of fluorine is directly correlated with the amount of oxygen: the higher the oxygen level on the sample, the more important is the fluorine content till 0.7 ML, essentially in a O sbnd Si sbnd F bonding state. For more aggresive etching leaving less than one monolayer of oxygen, the Si sbnd F bond becomes predominant. The ratio of the SiF to OSiF concentrations is a significant signature of the deoxidation state of the surface. Hydrophobicity of the water appears in the range of 25% Si sbnd F bonds. With very aggresive etching processes, 67% Si sbnd F bonds and 33% O sbnd Si sbnd F bonds are reached and the total amount of fluoride drops below 0.3 ML. For comparison, only Si sbnd F bonds are observed after a wet etching in a dilute HF bath without a rinse with a much lower fluorine concentration. The balance between Si sbnd F and O sbnd Si sbnd F remains stable and seems to be representative of the surface states provided by the etching process.

  15. X-ray photoelectron spectroscopy as a probe of rhodium-ligand interaction in ionic liquids

    NASA Astrophysics Data System (ADS)

    Men, Shuang; Lovelock, Kevin R. J.; Licence, Peter

    2016-02-01

    We use X-ray photoelectron spectroscopy (XPS) to identify the interaction between the rhodium atom and phosphine ligands in six 1-octyl-3-methylimidazolium-based ionic liquids ([C8C1Im][X]). The formation of a mono-phosphine rhodium complex based upon addition of triphenylphosphine (PPh3) is confirmed by XPS in all ionic liquids studied herein. Due to the electron donation effect of the ligand, the rhodium atom becomes more negatively charged and thus exhibits a lower measured binding energy. The influence of the anion basicity on the formation of different types of rhodium complexes is also investigated. By introducing a biphosphine ligand, a chelated diphosphine rhodium complex is formed in ionic liquids with more basic anions and verified by both XPS and Infrared Spectroscopy (IR). The measured Rh 3d binding energies are correlated to the reaction selectivity of a hydroformylation reaction which inspires a method to design a metal catalyst to control the chemical reaction towards desired products in the future.

  16. Interpretation of x-ray photoelectron spectra of elastic amorphous carbon nitride thin films

    SciTech Connect

    Holloway, B.C.; Kraft, O.; Shuh, D.K.; Kelly, M.A.; Nix, W.D.; Pianetta, P.; Hagstroem, S.

    1999-05-01

    We report the synthesis and characterization of amorphous carbon nitride (CN{sub x}) thin films using a direct current magnetron reactive sputter system. Nanoindentation of the CN{sub x} films and amorphous carbon films deposited under similar conditions shows the CN{sub x} films are extremely elastic, that the addition of nitrogen fundamentally changes the mechanical properties of the films, and that traditional methods of calculating the hardness and Young{close_quote}s modulus may not be valid. X-ray photoelectron spectroscopy (XPS) of the N(1s) and C(1s) core levels show multiple bonding arrangements. In a new interpretation of the XPS data, the two predominant N(1s) spectral features have been identified, based on comparison to reference data in the literature, as those belonging to nitrogen in a four-bond arrangement and nitrogen in a three-bond arrangement, independent of hybridization. The formation of a fourth bond allows nitrogen to substitute for C atoms in a carbon-based graphitic system without the formation of dangling bonds or unfilled states. The relationship between nitrogen incorporation in a carbon-based ring structure and measured film properties is rationalized based on previously published models. {copyright} {ital 1999 American Institute of Physics.}

  17. Challenges for lithium species identification in complementary Auger and X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Hoffmann, M.; Zier, M.; Oswald, S.; Eckert, J.

    2015-08-01

    The combination of high spatial resolution and near-surface chemical information makes Auger electron spectroscopy (AES) a powerful tool for comprehensive surface analysis. The recent interest in lithium metal as an active material in lithium sulphur or lithium air batteries increases the demand for a thorough knowledge of the reactions happening at the electrode interface. Applying AES to the complex surfaces of batteries, however, requires a detailed understanding of the interactions occurring with the highly reactive materials during investigation, especially when using metallic lithium with its passivation layers formed even under glove box atmosphere. The article is focused on the influence of electron beam damage and residual gas under ultra-high vacuum conditions on the observations made. Immediate irradiation effects are shown to highly depend on electron dose leading to misinterpretation the surface composition and a non-sufficient stability of the sample. The results are further supported by coupled X-ray photoelectron spectroscopy (XPS) measurements that help to understand the beam induced phenomena. An improved output of the spectroscopic measurement could be achieved employing AES mappings. This allows an improved insight into the local distribution of different lithium compounds in the material surface and can also be applied to other battery active materials.

  18. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    SciTech Connect

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2015-12-01

    A detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented in this work for select MXenes—a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Thus we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, single bondO, single bondOH and single bondF, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. Moreover, from XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

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

    SciTech Connect

    Delmelle, Renaud; Borgschulte, Andreas; Probst, Benjamin; Alberto, Roger; Züttel, 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.

  20. Internal Photoemission and X-Ray Photoelectron Spectroscopic Studies of Sulfur-Passivated GaAs

    NASA Astrophysics Data System (ADS)

    Sato, Kenji; Ikoma, Hideaki

    1993-02-01

    Internal photoemission and X-ray photoelectron spectroscopic (XPS) measurements were performed to investigate the effect of sulfur passivation on the GaAs surface and the degradation of the GaAs surface exposed to air ambient after the passivation. The reverse bias dependence of the Schottky barrier height was very small in the as-sulfur-treated sample and was mainly explained by the image force lowering effect. However, it increased as this sample was exposed to air, indicating an increase in the interface state density. The XPS studies showed that both the Ga and As oxides were hardly observed in the sulfur-passivated samples. This indicates that sulfur passivation strongly suppresses oxidation of GaAs. However, a small amount of elemental arsenic was observed with a trace of the As suboxides (such as AsO) after exposure to air and it increased as the exposure time was increased. These results were probably correlated with the increase in the bias dependence of the Schottky barrier height in samples exposed to air after the passivation. Thermal oxidation of GaAs was found to be retarded by sulfur passivation until oxidation time was about 10 min at 300°C. A possible model of suppression of oxidation by sulfur passivation was also discussed.

  1. [Characterization of biochar by X-ray photoelectron spectroscopy and 13C nuclear magnetic resonance].

    PubMed

    Xu, Dong-yu; Jin, Jie; Yan, Yu; Han, Lan-fang; Kang, Ming-jie; Wang, Zi-ying; Zhao, Ye; Sun, Ke

    2014-12-01

    The wood (willow branch) and grass (rice straw) materials were pyrolyzed at different temperatures (300, 450 and 600 °C) to obtain the biochars used in the present study. The biochars were characterized using elementary analysis, X-ray photoelectron spectroscopy (XPS) and solid state 13C cross-polarization and magic angle spinning nuclear magnetic resonance spectroscopy (13C NMR) to illuminate the structure and composition of the biochars which were derived from the different thermal temperatures and biomass. The results showed that the H/C, O/C and (O+N)/C ratios of the biochars decreased with the increase in the pyrolysis temperatures. The surface polarity and ash content of the grass-derived biochars were higher than those of the wood-derived biochars. The minerals of the wood-derived biochars were mainly covered by the organic matter; in contrast, parts of the mineral surfaces of the grass-derived biochars were not covered by organic matter? The 13C NMR of the low temperature-derived biochars revealed a large contribution of aromatic carbon, aliphatic carbon, carboxyl and carbonyl carbon, while the high temperature-derived biochars contained a large amount of aromatic carbon. Moreover, the wood-derived biochars produced at low heat treatment temperatures contained more lignin residues than grass-derived ones, probably due to the existence of high lignin content in the feedstock soures of wood-derived biochars. The results of the study would be useful for environmental application of biochars.

  2. X-ray photoelectron spectroscopic investigation of nanocrystalline calcium silicate hydrates synthesised by reactive milling

    SciTech Connect

    Black, Leon . E-mail: l.black@shu.ac.uk; Garbev, Krassimir; Beuchle, Guenter; Stemmermann, Peter; Schild, Dieter

    2006-06-15

    X-ray photoelectron spectroscopy (XPS) has been used to analyse a series of mechanochemically synthesised, nanocrystalline calcium silicate hydrates (C-S-H). The samples, with Ca/Si ratios of 0.2 to 1.5, showed structural features of C-S-H(I). XPS analysis revealed changes in the extent of silicate polymerisation. Si 2p, Ca 2p and O 1s spectra showed that, unlike for the crystalline calcium silicate hydrate phases studied previously, there was no evidence of silicate sheets (Q{sup 3}) at low Ca/Si ratios. Si 2p and O 1s spectra indicated silicate depolymerisation, expressed by decreasing silicate chain length, with increasing C/S. In all spectra, peak narrowing was observed with increasing Ca/Si, indicating increased structural ordering. The rapid changes of the slope of FWHM of Si 2p, {delta} {sub Ca-Si} and {delta} {sub NBO-BO} as function of C/S ratio indicated a possible miscibility gap in the C-S-H-solid solution series between C/S 5/6 and 1. The modified Auger parameter ({alpha}') of nanocrystalline C-S-H decreased with increasing silicate polymerisation, a trend already observed studying crystalline C-S-H. Absolute values of {alpha}' were shifted about - 0.7 eV with respect to crystalline phases of equal C/S ratio, due to reduced crystallinity.

  3. Thickness determination of molecularly thin lubricant films by angle-dependent X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Pang, Chongjun; Bai, Mingwu

    2007-03-01

    An angle-dependent X-ray photoelectron spectroscopy (XPS) method used to measure the thickness of molecularly thin lubricants was developed. The method was built based on an island model of patched overlayer on a flat substrate by using the photoemission signal solely from the lubricant film. Typical molecularly thin Zdol films on the CHx overcoat of unused commercial magnetic disks were measured to verify the metrology. The lubricant thickness determined by the metrology was equal to the recent result by thermostatic high vacuum atomic force microscopy. The measured deduction in the thickness of the molecularly thin lubricant films, successively irradiated by the monochromatic source operated at 14 kV/250 W, was as low as 1 Ǻ during the first irradiation hour. XPS spectra showed that no hydrocarbons, water or oxygen were adsorbed over the Zdol outer surfaces in the tested XPS conditions. The inelastic mean free path (IMFP) of C 1s in Zdol or in CHx was found to be independent of take off angle (TOA) when TOA < 40°. The IMFP of C 1s in Zdol was ˜63.5 Ǻ and the lubricant island thickness was ˜35 Ǻ.

  4. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    DOE PAGESBeta

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2015-12-01

    A detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented in this work for select MXenes—a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Thus we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, single bondO, single bondOHmore » and single bondF, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. Moreover, from XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.« less

  5. Effect of Space Radiation Processing on Lunar Soil Surface Chemistry: X-Ray Photoelectron Spectroscopy Studies

    NASA Technical Reports Server (NTRS)

    Dukes, C.; Loeffler, M.J.; Baragiola, R.; Christoffersen, R.; Keller, J.

    2009-01-01

    Current understanding of the chemistry and microstructure of the surfaces of lunar soil grains is dominated by a reference frame derived mainly from electron microscopy observations [e.g. 1,2]. These studies have shown that the outermost 10-100 nm of grain surfaces in mature lunar soil finest fractions have been modified by the combined effects of solar wind exposure, surface deposition of vapors and accretion of impact melt products [1,2]. These processes produce surface-correlated nanophase Feo, host grain amorphization, formation of surface patinas and other complex changes [1,2]. What is less well understood is how these changes are reflected directly at the surface, defined as the outermost 1-5 atomic monolayers, a region not easily chemically characterized by TEM. We are currently employing X-ray Photoelectron Spectroscopy (XPS) to study the surface chemistry of lunar soil samples that have been previously studied by TEM. This work includes modification of the grain surfaces by in situ irradiation with ions at solar wind energies to better understand how irradiated surfaces in lunar grains change their chemistry once exposed to ambient conditions on earth.

  6. Ultrafast x-ray photoelectron spectroscopy in the microsecond time domain

    SciTech Connect

    Höfert, O.; Gleichweit, C.; Steinrück, H.-P.; Papp, C.

    2013-09-15

    We introduce a new approach for ultrafast in situ high-resolution X-ray photoelectron spectroscopy (XPS) to study surface processes and reaction kinetics on the microsecond timescale. The main idea is to follow the intensity at a fixed binding energy using a commercial 7 channeltron electron analyzer with a modified signal processing setup. This concept allows for flexible switching between measuring conventional XP spectra and ultrafast XPS. The experimental modifications are described in detail. As an example, we present measurements for the adsorption and desorption of CO on Pt(111), performed at the synchrotron radiation facility BESSY II, with a time resolution of 500 μs. Due to the ultrafast measurements, we are able to follow adsorption and desorption in situ at pressures of 2 × 10{sup −6} mbar and temperatures up to 500 K. The data are consistently analyzed using a simple model in line with data obtained with conventional fast XPS at temperatures below 460 K. Technically, our new approach allows measurement on even shorter timescales, down to 20 μs.

  7. X-ray photoelectron spectroscopy surface analysis of aluminum ion stress in barley roots. [Hordeum vulgare

    SciTech Connect

    Millard, M.M.; Foy, C.D.; Coradetti, C.A.; Reinsel, M.D. )

    1990-06-01

    X-ray photoelectron spectroscopy (XPS) has been used to analyze root surface changes when Dayton barley (Hordeum vulgare) (Al tolerant) and Kearney barley (Al sensitive) seedlings were grown in nutrient solution in the presence and absence of 37.0 micromolar Al. The electron spectra from root surfaces contained strong lines in order of decreasing intensity from organic forms of carbon, oxygen, and nitrogen and weak lines due to inorganic elements in the form of anions and cations on the surface. The surface composition of root tips from Kearney was C, 65.6%; 0, 26.8%; N, 4.4% and tips from Dayton was C, 72.7%; O, 23.6%; N, 1.9%, grown in the absence of aluminum. Electron lines characteristic of nitrate, potassium, chloride, phosphate were also present in the spectra from those roots. Dayton roots grown in the presence of 37.0 micromolar aluminum contained 2.1% aluminum while Kearney contained 1.3% aluminum. The ratio of aluminum to phosphate was close to 1.0. Dayton roots usually contained twice as much aluminum phosphate in the surface region as Kearney. Dayton may be less susceptible to Al toxic effects by accumulation of aluminum phosphate on the root surface which then acts as a barrier to the transport of aluminum into the interior of the roots.

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

    DOE PAGESBeta

    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

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

    SciTech Connect

    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.

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

    PubMed

    Newberg, John T; Bluhm, Hendrik

    2015-09-28

    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 × 10(3) 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. PMID:26299301

  11. Chemistry of carbon polymer composite electrode - An X-ray photoelectron spectroscopy study

    NASA Astrophysics Data System (ADS)

    Andersen, Shuang Ma; Dhiman, Rajnish; Skou, Eivind

    2015-01-01

    Surface chemistry of the electrodes in a proton exchange membrane fuel cell is of great importance for the cell performance. Many groups have reported that electrode preparation condition has a direct influence on the resulting electrode properties. In this work, the oxidation state of electrode components and the composites (catalyst ionomer mixtures) in various electrode structures were systematically studied with X-ray photoelectron spectroscopy (XPS). Based on the spectra, when catalyst is physically mixed with Nafion ionomer, the resulting electrode surface chemistry is a combination of the two components. When the electrode is prepared with a lamination procedure, the ratio between fluorocarbon and graphitic carbon is decreased. Moreover, ether type oxide content is decreased although carbon oxide is slightly increased. This indicates structure change of the catalyst layer due to an interaction between the ionomer and the catalyst and possible polymer structural change during electrode fabrication. The surface of micro porous layer was found to be much more influenced by the lamination, especially when it is in contact with catalysts in the interphase. Higher amount of platinum oxide was observed in the electrode structures (catalyst ionomer mixture) compared to the catalyst powder. This also indicates a certain interaction between the functional groups in the polymer and platinum surface.

  12. Study of the oxidation of gold-tin preforms using x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Taylor, J. Ashley; Merchant, Sailesh M.; Perry, D. L.

    1995-11-01

    This study uses x-ray photoelectron spectroscopy (XPS) to investigate the nature of the oxide formed on clean Au-Sn binary alloys (ζ and δ phases) and on preforms with the eutectic composition (29 at % Sn) at low O2 pressures (<10-3 Torr) and at high O2 pressures (up to one atmosphere) at temperatures ranging from room temperature to 200 °C. Sn Auger parameters and XPS angular-resolved data were obtained in addition to the core binding energies to identify the oxide layer. The oxidation of the Au-Sn alloys is basically similar to the oxidation of metallic Sn. The Auger parameter indicates that with low-pressure oxidation a layered oxide structure is formed consisting of SnO and a slightly tin-rich oxide at the interface. Probably a thin skin of Sn(IV) oxide exists on the outer surface of the low-pressure oxide. High-temperature and low-pressure promotes the growth of SnO. As the pressure is increased the Sn(IV) oxide grows more noticeably and with high-pressure oxidation the Sn(IV) oxide grows thicker than the Sn(II) oxide at the interface. The Sn(II) oxide at the interface appears similar to the Sn(II) oxide structure formed at low pressure. The Auger parameter indicates that the Sn(IV) oxide possesses a structure different than that of Cassiterite.

  13. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

    PubMed Central

    Lu, Yi-Chun; Crumlin, Ethan J.; Veith, Gabriel M.; Harding, Jonathon R.; Mutoro, Eva; Baggetto, Loïc; Dudney, Nancy J.; Liu, Zhi; Shao-Horn, Yang

    2012-01-01

    The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, lithium intercalated into LixV2O5 while molecular oxygen was reduced to form lithium peroxide on LixV2O5 in the presence of oxygen upon discharge. Interestingly, the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of conventional Li-O2 cells with aprotic electrolytes (~1000 mV). Our study provides the first evidence of reversible lithium peroxide formation and decomposition in situ on an oxide surface using a solid-state cell, and new insights into the reaction mechanism of Li-O2 chemistry. PMID:23056907

  14. A versatile instrument for ambient pressure x-ray photoelectron spectroscopy: The Lund cell approach

    NASA Astrophysics Data System (ADS)

    Knudsen, Jan; Andersen, Jesper N.; Schnadt, Joachim

    2016-04-01

    During the past one and a half decades ambient pressure x-ray photoelectron spectroscopy (APXPS) has grown to become a mature technique for the real-time investigation of both solid and liquid surfaces in the presence of a gas or vapour phase. APXPS has been or is being implemented at most major synchrotron radiation facilities and in quite a large number of home laboratories. While most APXPS instruments operate using a standard vacuum chamber as the sample environment, more recently new instruments have been developed which focus on the possibility of custom-designed sample environments with exchangeable ambient pressure cells (AP cells). A particular kind of AP cell solution has been driven by the development of the APXPS instrument for the SPECIES beamline of the MAX IV Laboratory: the solution makes use of a moveable AP cell which for APXPS measurements is docked to the electron energy analyser inside the ultrahigh vacuum instrument. Only the inner volume of the AP cell is filled with gas, while the surrounding vacuum chamber remains under vacuum conditions. The design enables the direct connection of UHV experiments to APXPS experiments, and the swift exchange of AP cells allows different custom-designed sample environments. Moreover, the AP cell design allows the gas-filled inner volume to remain small, which is highly beneficial for experiments in which fast gas exchange is required. Here we report on the design of several AP cells and use a number of cases to exemplify the utility of our approach.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    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 H2 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 CO2 hydrogenation and the hydrogenation of a water reduction catalyst for photocatalytic H2 production, but it opens the possibility of the new in situ characterisation of energy materials and catalysts.

  16. CHARACTERIZING SURFACE LAYERS IN NITINOL USING X-RAY PHOTOELECTRON SPECTROSCOPY

    SciTech Connect

    Christopfel, R.; Mehta, A.

    2008-01-01

    Nitinol is a shape memory alloy whose properties allow for large reversible deformations and a return to its original geometry. This nickel-titanium (NiTi) alloy has become a material used widely in the biomedical fi eld as a stent to open up collapsed arteries. Both ambient and biological conditions cause surface oxidation in these devices which in turn change its biocompatibility. The thickness of oxidized layers can cause fractures in the material if too large and can allow for penetration if too thin. Depending on the type and abundance of the chemical species on or near the surface, highly toxic metal ions can leak into the body causing cell damage or even cell death. Thus, biocompatibility of such devices is crucial. By using highly surface sensitive x-ray photoelectron spectroscopy to probe the surface of these structures, it is possible to decipher both layer composition and layer thickness. Two samples, both of which were mechanically polished, were investigated. Of the two samples, one was then exposed to a phosphate buffered saline (PBS) solution to mimic the chemical properties of blood, while the other remained unexposed. Although both samples were found to have oxide layers of appropriate thickness (on the order of a few nm), it was found that the sample exposed to the saline solution had a slightly thicker oxide layer and more signifi cantly, a phosphate layer very near the surface suggesting toxic metal components are well contained within the sample. These are considerable indications of a biocompatible device.

  17. Light-induced atom desorption from glass surfaces characterized by X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Kumagai, Ryo; Hatakeyama, Atsushi

    2016-07-01

    We analyzed the surfaces of vitreous silica (quartz) and borosilicate glass (Pyrex) substrates exposed to rubidium (Rb) vapor by X-ray photoelectron spectroscopy (XPS) to understand the surface conditions of alkali metal vapor cells. XPS spectra indicated that Rb atoms adopted different bonding states in quartz and Pyrex. Furthermore, Rb atoms in quartz remained in the near-surface region, while they diffused into the bulk in Pyrex. For these characterized surfaces, we measured light-induced atom desorption (LIAD) of Rb atoms. Clear differences in time evolution, photon energy dependence, and substrate temperature dependence were found; the decay of LIAD by continuous ultraviolet irradiation for quartz was faster than that for Pyrex, a monotonic increase in LIAD with increasing photon energy from 1.8 to 4.3 eV was more prominent for quartz, and LIAD from quartz was more efficient at higher temperatures in the range from 300 to 580 K, while that from Pyrex was almost independent of temperature.

  18. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    NASA Astrophysics Data System (ADS)

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2016-01-01

    In this work, a detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented for select MXenes-a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Herein we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, sbnd O, sbnd OH and sbnd F, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. From XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

  19. Characterization of plasma fluorinated zirconia for dental applications by X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Wolter, S. D.; Piascik, J. R.; Stoner, B. R.

    2011-09-01

    This paper discusses fluorination of biomedical-grade yttria-stabilized zirconia (YSZ) by sulfur hexafluoride plasma treatment and characterization of near-surface chemistry products by X-ray photoelectron spectroscopy (XPS). Deconvolution of the Zr 3d and Y 3d XPS core level spectra revealed formation of both ZrF4 and YF3. In addition, seven-coordinate ZrO2F5 and/or ZrO3F4 phases were deconvolved, retaining similar atomic coordination as the parent oxide and believed to have formed by substitutional displacement of oxygen by fluorine. No additional components attributed to yttria oxyfluoride were deconvolved. Argon ion sputter depth profiling determined the overlayer to be ∼4.0 nm in thickness, and angle resolved XPS showed no angle dependence on component percentages likely due to fluorination extending into the grain boundaries of the polycrystalline substrates. Importantly, the conversion layer did not induce any apparent change in zirconia crystallinity by inspection of Zr-O 3d5/2,3/2 peak positions and full-width-at-half-maximum values, important for retaining its desirable mechanical properties.

  20. Self-detection of x-ray Fresnel transmissivity using photoelectron-induced gas ionization

    NASA Astrophysics Data System (ADS)

    Stoupin, Stanislav

    2016-01-01

    Electric response of an x-ray mirror enclosed in a gas flow ionization chamber was studied under the conditions of total external reflection for hard x-rays. It is shown that the electric response of the system as a function of the incidence angle is defined by x-ray Fresnel transmissivity and photon-electron attenuation properties of the mirror material. A simple interpretation of quantum yield of the system is presented. The approach could serve as a basis for non-invasive in situ diagnostics of hard x-ray optics, easy access to complementary x-ray transmissivity data in x-ray reflectivity experiments, and might also pave the way to advanced schemes for angle and energy resolving x-ray detectors.

  1. Discovery of an X-ray Violently Variable Broad Absorption Line Quasar

    NASA Technical Reports Server (NTRS)

    Ghosh, Kajal K.; Gutierrez, Carlos M.; Punsly, Brian; Chevallier, Loic; Goncalves, Anabela C.

    2006-01-01

    In this letter, we report on a quasar that is violently variable in the X-rays, XVV. It is also a broad absorption line quasar (BALQSO) that exhibits both high ionization and low ionization UV absorption lines (LoBALQSO). It is very luminous in the X-rays (approximately 10(exp 46) ergs s(sup -l) over the entire X-ray band). Surprisingly, this does not over ionize the LoBAL outflow. The X-rays vary by a factor of two within minutes in the quasar rest frame, which is shorter than 1/30 of the light travel time across a scale length equal to the black hole radius. We concluded that the X-rays are produced in a relativistic jet beamed toward earth in which variations in the Doppler enhancement produce the XVV behavior.

  2. X-Ray Absorption Characterization of Diesel Exhaust Particulates

    SciTech Connect

    Nelson, A J; Ferreira, J L; Reynolds, J G; Roos, J W

    1999-11-18

    We have characterized particulates from a 1993 11.1 Detroit Diesel Series 60 engine with electronic unit injectors operated using fuels with and without methylcyclopentadienyl manganese tricarbonyl (MMT) and overbased calcium sulfonate added. X-ray photoabsorption (XAS) spectroscopy was used to characterize the diesel particulates. Results reveal a mixture of primarily Mn-phosphate with some Mn-oxide, and Ca-sulfate on the surface of the filtered particulates from the diesel engine.

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

    SciTech Connect

    Booth, C.H.; Bridges, F.

    2003-06-04

    Extended x-ray absorption fine-structure (EXAFS) data collected in the fluorescence mode are susceptible to an apparent amplitude reduction due to the self-absorption of the fluorescing photon by the sample before it reaches a detector. Previous treatments have made the simplifying assumption that the effect of the EXAFS on the correction term is negligible, and that the samples are in the thick limit. We present a nearly exact treatment that can be applied for any sample thickness or concentration, and retains the EXAFS oscillations in the correction term.

  4. ASCITOVG - FORTRAN PROGRAM FOR X-RAY PHOTOELECTRON SPECTROSCOPY DATA REFORMATTING

    NASA Technical Reports Server (NTRS)

    Able, P. B.

    1994-01-01

    It is often desirable to use a central, more powerful computer to analyze data captured on a local machine. ASCITOVG is a program for use on an IBM PC series computer which creates binary format files from columns of ASCII-format numbers. The resultant files are suitable for interactive analysis on a DEC PDP-11/73 under the Micro-RSX operating system running the VGS-5000 Enhanced Data Processing (EDP) software package. EDP performs data analysis interactively with a color graphics display, speeding up the analysis considerably when compared with batch job processing. Its interactive analysis capabilities also allow the researcher to watch for spurious data that might go undetected when some form of automatic spectrum processing is used. The incompatibility in floating-point number representations of an IBM PC and a DEC computer were resolved by a FORTRAN subroutine that correctly converts single-precision, floating-point numbers on the PC so that they can be directly read by DEC computers, such as a VAX. The subroutine also can convert binary DEC files (single-precision, floating-point numbers) to IBM PC format. This may prove a more efficient method of moving data from, for instance, a VAX-cluster down to a local IBM PC for further examination, manipulation, or display. The input data file used by ASCITOVG is simply a text file in the form of a column of ASCII numbers, with each value followed by a carriage return. These can be the output of a data collection routine or can even be keyed in through the use of a program editor. The data file header required by the EDP programs for an x-ray photoelectron spectrum is also written to the file. The spectrum parameters, entered by the user when the program is run, are coded into the header format used internally by all of the VGS-5000 series EDP packages. Any file transfer protocol having provision for binary data can be used to transmit the resulting file from the PC to the DEC machine. Each EDP data file has at least

  5. WEAK HARD X-RAY EMISSION FROM TWO BROAD ABSORPTION LINE QUASARS OBSERVED WITH NuSTAR: COMPTON-THICK ABSORPTION OR INTRINSIC X-RAY WEAKNESS?

    SciTech Connect

    Luo, B.; Brandt, W. N.; Alexander, D. M.; Hickox, R.; Harrison, F. A.; Fuerst, F.; Grefenstette, B. W.; Madsen, K. K.; Stern, D.; Bauer, F. E.; Boggs, S. E.; Craig, W. W.; Christensen, F. E.; Comastri, A.; Fabian, A. C.; Farrah, D.; Fiore, F.; Hailey, C. J.; Matt, G.; Ogle, P.; and others

    2013-08-01

    We present Nuclear Spectroscopic Telescope Array (NuSTAR) hard X-ray observations of two X-ray weak broad absorption line (BAL) quasars, PG 1004+130 (radio loud) and PG 1700+518 (radio quiet). Many BAL quasars appear X-ray weak, probably due to absorption by the shielding gas between the nucleus and the accretion-disk wind. The two targets are among the optically brightest BAL quasars, yet they are known to be significantly X-ray weak at rest-frame 2-10 keV (16-120 times fainter than typical quasars). We would expect to obtain Almost-Equal-To 400-600 hard X-ray ({approx}> 10 keV) photons with NuSTAR, provided that these photons are not significantly absorbed (N{sub H} {approx}< 10{sup 24} cm{sup -2}). However, both BAL quasars are only detected in the softer NuSTAR bands (e.g., 4-20 keV) but not in its harder bands (e.g., 20-30 keV), suggesting that either the shielding gas is highly Compton-thick or the two targets are intrinsically X-ray weak. We constrain the column densities for both to be N{sub H} Almost-Equal-To 7 Multiplication-Sign 10{sup 24} cm{sup -2} if the weak hard X-ray emission is caused by obscuration from the shielding gas. We discuss a few possibilities for how PG 1004+130 could have Compton-thick shielding gas without strong Fe K{alpha} line emission; dilution from jet-linked X-ray emission is one likely explanation. We also discuss the intrinsic X-ray weakness scenario based on a coronal-quenching model relevant to the shielding gas and disk wind of BAL quasars. Motivated by our NuSTAR results, we perform a Chandra stacking analysis with the Large Bright Quasar Survey BAL quasar sample and place statistical constraints upon the fraction of intrinsically X-ray weak BAL quasars; this fraction is likely 17%-40%.

  6. Weak Hard X-Ray Emission from Two Broad Absorption Line Quasars Observed with NuStar: Compton-Thick Absorption or Intrinsic X-Ray Weakness?

    NASA Technical Reports Server (NTRS)

    Luo, B.; Brandt, W. N.; Alexander, D. M.; Harrison, F. A.; Stern, D.; Bauer, F. E.; Boggs, S. E.; Christensen, F. E.; Comastri, A.; Craig, W. W..; Fabian, A. C.; Farrah, D.; Fiore, F.; Fuerst, F.; Grefenstette, B. W.; Hailey, C. J.; Hickox, R.; Madsen, K. K.; Matt, G.; Ogle, P.; Risaliti, G.; Saez, C.; Teng, S. H.; Walton, D. J.; Zhang, W. W.

    2013-01-01

    We present Nuclear Spectroscopic Telescope Array (NuSTAR) hard X-ray observations of two X-ray weak broad absorption line (BAL) quasars, PG 1004+130 (radio loud) and PG 1700+518 (radio quiet). Many BAL quasars appear X-ray weak, probably due to absorption by the shielding gas between the nucleus and the accretion-disk wind. The two targets are among the optically brightest BAL quasars, yet they are known to be significantly X-ray weak at rest-frame 2-10 keV (16-120 times fainter than typical quasars). We would expect to obtain approx. or equal to 400-600 hard X-ray (is greater than or equal to 10 keV) photons with NuSTAR, provided that these photons are not significantly absorbed N(sub H) is less than or equal to 10(exp24) cm(exp-2). However, both BAL quasars are only detected in the softer NuSTAR bands (e.g., 4-20 keV) but not in its harder bands (e.g., 20-30 keV), suggesting that either the shielding gas is highly Compton-thick or the two targets are intrinsically X-ray weak. We constrain the column densities for both to be N(sub H) 7 × 10(exp 24) cm(exp-2) if the weak hard X-ray emission is caused by obscuration from the shielding gas. We discuss a few possibilities for how PG 1004+130 could have Compton-thick shielding gas without strong Fe Ka line emission; dilution from jet-linked X-ray emission is one likely explanation. We also discuss the intrinsic X-ray weakness scenario based on a coronal-quenching model relevant to the shielding gas and disk wind of BAL quasars. Motivated by our NuSTAR results, we perform a Chandra stacking analysis with the Large Bright Quasar Survey BAL quasar sample and place statistical constraints upon the fraction of intrinsically X-ray weak BAL quasars; this fraction is likely 17%-40%.

  7. X-Ray Attenuation and Absorption for Materials of Dosimetric Interest

    National Institute of Standards and Technology Data Gateway

    SRD 126 X-Ray Attenuation and Absorption for Materials of Dosimetric Interest (Web, free access)   Tables and graphs of the photon mass attenuation coefficient and the mass energy-absorption coefficient are presented for all of the elements Z = 1 to 92, and for 48 compounds and mixtures of radiological interest. The tables cover energies of the photon (x-ray, gamma ray, bremsstrahlung) from 1 keV to 20 MeV.

  8. Properties of Liquid Silicon Observed by Time-Resolved X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, S. L.; Heimann, P. A.; Lindenberg, A. M.; Jeschke, H. O.; Garcia, M. E.; Chang, Z.; Lee, R. W.; Rehr, J. J.; Falcone, R. W.

    2003-10-01

    Time-resolved x-ray spectroscopy at the Si L edges is used to probe the electronic structure of an amorphous Si foil as it melts following absorption of an ultrafast laser pulse. Picosecond temporal resolution allows observation of the transient liquid phase before vaporization and before the liquid breaks up into droplets. The melting causes changes in the spectrum that match predictions of molecular dynamics and ab initio x-ray absorption codes.

  9. Diamond solid state ionization chambers for x-ray absorption spectroscopy applications

    SciTech Connect

    De Sio, A.; Bocci, A.; Pace, E.; Castellano, C.; Cinque, G.; Tartoni, N.; D'Acapito, F.

    2008-08-25

    The photoresponse of a diamond detector has been compared with a standard ionization chamber in x-ray absorption spectroscopy applications. A photoconductive device based on a nitrogen-doped single crystal diamond has been tested by synchrotron radiation. Time stability and linearity have been studied by x rays at 10 keV to assess its performances. Finally, extended x-ray absorption fine structure at the Fe K-edge was carried on a standard iron target using both the diamond device and the IC. Spectroscopical results have been compared including references to literature.

  10. Absorption of the x ray background by the large magellanic cloud

    NASA Technical Reports Server (NTRS)

    Hamilton, Thomas T.

    1991-01-01

    Soft x ray flux of extragalactic origin should be partially absorbed during passage through the Large Magellanic Cloud. Past attempts to measure this absorption have been frustrated by the LMC's intrinsic x ray emission. New calibration techniques were developed to enable precise (within 5 pct.) measurement of the flux and spectrum of diffuse x rays detected by the Einstein Observatory IPC. These techniques were used to measure the absorption of extragalactic flux by neutral gas in the LMC, and to determine that at least 50 pct. of the observed flux in the 0.16 to 2 keV band is of extragalactic origin.

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

    SciTech Connect

    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.

  12. X-Ray Photoelectron Spectroscopic Analysis of the Oxide of GaAs

    NASA Astrophysics Data System (ADS)

    Ishikawa, Toshifumi; Ikoma, Hideaki

    1992-12-01

    Oxides of GaAs grown using various oxidation processes were analyzed with X-ray photoelectron spectroscopy (XPS). Oxides investigated were the native (naturally grown or exposed to air), the chemical (grown in boiling deionized water) and the thermal (at 350°C and 500°C in dry oxygen) ones. With the use of a spectral deconvolution technique, all types of suboxides of both As and Ga including elemental arsenic were observed in addition to well-known As2O3 and Ga2O3. Elemental arsenic is considered to be one of the oxidized forms of GaAs. As2O5 was observed in the thermal oxides. In the chemical oxide and the native oxide grown in short exposure to air, elemental arsenic is the main component of oxide, while As2O3 is the dominant species in more highly oxidized films such as the thermal oxide. XPS data suggest that oxidation of As bonded in GaAs proceeds as GaAs→elemental As (As0)→As2O (As1+)→AsO (As2+)→As2O3 (As3+)→As2O5 (As5+). Oxidation of Ga bonded in GaAs advances as GaAs→Ga2O (Ga1+)→GaO (Ga2+)→Ga2O3 (Ga3+). Angle-resolved XPS measurements and semiquantitative analyses of these data were performed and an effective thickness of each oxide was also derived with simplified assumptions. The native and the chemical oxides were nearly stoichiometric. However, the thermal oxide was substantially Ga-rich due to desorption and evaporation of As2O3 from the surface during oxidation.

  13. [Characterization of biochar by X-ray photoelectron spectroscopy and 13C nuclear magnetic resonance].

    PubMed

    Xu, Dong-yu; Jin, Jie; Yan, Yu; Han, Lan-fang; Kang, Ming-jie; Wang, Zi-ying; Zhao, Ye; Sun, Ke

    2014-12-01

    The wood (willow branch) and grass (rice straw) materials were pyrolyzed at different temperatures (300, 450 and 600 °C) to obtain the biochars used in the present study. The biochars were characterized using elementary analysis, X-ray photoelectron spectroscopy (XPS) and solid state 13C cross-polarization and magic angle spinning nuclear magnetic resonance spectroscopy (13C NMR) to illuminate the structure and composition of the biochars which were derived from the different thermal temperatures and biomass. The results showed that the H/C, O/C and (O+N)/C ratios of the biochars decreased with the increase in the pyrolysis temperatures. The surface polarity and ash content of the grass-derived biochars were higher than those of the wood-derived biochars. The minerals of the wood-derived biochars were mainly covered by the organic matter; in contrast, parts of the mineral surfaces of the grass-derived biochars were not covered by organic matter? The 13C NMR of the low temperature-derived biochars revealed a large contribution of aromatic carbon, aliphatic carbon, carboxyl and carbonyl carbon, while the high temperature-derived biochars contained a large amount of aromatic carbon. Moreover, the wood-derived biochars produced at low heat treatment temperatures contained more lignin residues than grass-derived ones, probably due to the existence of high lignin content in the feedstock soures of wood-derived biochars. The results of the study would be useful for environmental application of biochars. PMID:25881450

  14. Repair and Utilization of the Kratos XSAM 800 X-Ray Photoelectron Spectrometer (XPS)

    NASA Technical Reports Server (NTRS)

    Hampton, Michael D.

    2002-01-01

    The objectives for this summer faculty fellowship were first to repair the Kratos XSAM 800 X-ray Photoelectron Spectrometer (XPS) and then to utilize the instrument to participate in ongoing research projects at KSC and in the researcher's own laboratory at UCF. The first 6 weeks were used in repairing the instrument. Working both alone and with the Kratos service engineer, a number of hardware problems, largely associated with the sample stage control system, were corrected. Defective parts were identified and fixed in the computer driver boards, the stage power supply, and the driver interface. The power supply was completely replaced. After four weeks of work, the instrument was functional. This occurred on a Wednesday. The following Friday the instrument had to be completely shut down because the power to the O & C Building was to be turned off. The instrument was properly secured. On Monday, the instrument was powered up and the original problems returned. After another 2 weeks of work, a software problem was identified. This problem caused the computer to use a defective port for the sample stage control. It was circumvented by rewriting the startup routine. The final 3 weeks of the fellowship were spent using the XPS to analyze samples being studied in the Langley materials project (Martha Williams) and a catalyst project (Dr. Orlando Melendez). During this time, several sample analysis requests from other groups at KSC also came in and those samples were run as well. The summer faculty fellowship also allowed many contacts to be made. After meeting with the sensors group, two projects were identified for collaboration and white papers are being prepared. One project aims to develop small, very sensitive hydrogen detectors and the other to develop a broad area, easily monitored, zero power consumption hydrogen detector. In addition to the work mentioned above, the XPS was utilized in a study underway in Dr. Hampton's laboratory at UCF.

  15. X-ray photoelectron spectroscopy (XPS) investigation of the surface film on magnesium powders.

    PubMed

    Burke, Paul J; Bayindir, Zeynel; Kipouros, Georges J

    2012-05-01

    Magnesium (Mg) and its alloys are attractive for use in automotive and aerospace applications because of their low density and good mechanical properties. However, difficulty in forming magnesium and the limited number of available commercial alloys limit their use. Powder metallurgy may be a suitable solution for forming near-net-shape parts. However, sintering pure magnesium presents difficulties due to surface film that forms on the magnesium powder particles. The present work investigates the composition of the surface film that forms on the surface of pure magnesium powders exposed to atmospheric conditions and on pure magnesium powders after compaction under uniaxial pressing at a pressure of 500 MPa and sintering under argon at 600 °C for 40 minutes. Initially, focused ion beam microscopy was utilized to determine the thickness of the surface layer of the magnesium powder and found it to be ~10 nm. The X-ray photoelectron analysis of the green magnesium sample prior to sintering confirmed the presence of MgO, MgCO(3)·3H(2)O, and Mg(OH)(2) in the surface layer of the powder with a core of pure magnesium. The outer portion of the surface layer was found to contain MgCO(3)·3H(2)O and Mg(OH)(2), while the inner portion of the layer is primarily MgO. After sintering, the MgCO(3)·3H(2)O was found to be almost completely absent, and the amount of Mg(OH)(2) was also decreased significantly. This is postulated to occur by decomposition of the compounds to MgO and gases during the high temperature of sintering. An increase in the MgO content after sintering supports this theory.

  16. Observation and simulation of hard x ray photoelectron diffraction to determine polarity of polycrystalline zinc oxide films with rotation domains

    SciTech Connect

    Williams, Jesse R.; Adachi, Yutaka; Ohashi, Naoki; Pis, Igor; Kobata, Masaaki; Winkelmann, Aimo; Matsushita, Tomohiro; Kobayashi, Keisuke

    2012-02-01

    X ray photoelectron diffraction (XPD) patterns of polar zinc oxide (ZnO) surfaces were investigated experimentally using hard x rays and monochromatized Cr K{alpha} radiation and theoretically using a cluster model approach and a dynamical Bloch wave approach. We focused on photoelectrons emitted from the Zn 2p{sub 3/2} and O 1s orbitals in the analysis. The obtained XPD patterns for the (0001) and (0001) surfaces of a ZnO single crystal were distinct for a given emitter and polarity. Polarity determination of c-axis-textured polycrystalline ZnO thin films was also achieved with the concept of XPD, even though the in-plane orientation of the columnar ZnO grains was random.

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

    SciTech Connect

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

    2004-06-04

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

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

    SciTech Connect

    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.

  19. Soft X-ray induced damage in PVA-based membranes in water environment monitored by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Tzvetkov, George; Späth, Andreas; Fink, Rainer H.

    2014-10-01

    The effect of synchrotron X-ray flux in a soft X-ray scanning-transmission microspectroscope (STXM) instrument on the chemical structure of air-filled poly(vinyl alcohol) (PVA) based microbubbles and their stabilizing shell has been examined. Prolonged soft X-ray illumination of the particles in aqueous suspension leads to the breaking of the microbubbles' protective polymer shell and substantial chemical changes. The latter were clarified via a micro-spot C K-edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy with further respect to the absorbed X-ray doses. Our results revealed a continuous degradation of the PVA network associated with formation of carbonyl- and carboxyl-containing species as well as an increased content of unsaturated bonds. The observed effects must be taken into account in studies of micro- and nanostructured polymer materials utilizing X-rays.

  20. High energy X-ray phase and dark-field imaging using a random absorption mask.

    PubMed

    Wang, Hongchang; Kashyap, Yogesh; Cai, Biao; Sawhney, Kawal

    2016-01-01

    High energy X-ray imaging has unique advantage over conventional X-ray imaging, since it enables higher penetration into materials with significantly reduced radiation damage. However, the absorption contrast in high energy region is considerably low due to the reduced X-ray absorption cross section for most materials. Even though the X-ray phase and dark-field imaging techniques can provide substantially increased contrast and complementary information, fabricating dedicated optics for high energies still remain a challenge. To address this issue, we present an alternative X-ray imaging approach to produce transmission, phase and scattering signals at high X-ray energies by using a random absorption mask. Importantly, in addition to the synchrotron radiation source, this approach has been demonstrated for practical imaging application with a laboratory-based microfocus X-ray source. This new imaging method could be potentially useful for studying thick samples or heavy materials for advanced research in materials science. PMID:27466217

  1. High energy X-ray phase and dark-field imaging using a random absorption mask

    PubMed Central

    Wang, Hongchang; Kashyap, Yogesh; Cai, Biao; Sawhney, Kawal

    2016-01-01

    High energy X-ray imaging has unique advantage over conventional X-ray imaging, since it enables higher penetration into materials with significantly reduced radiation damage. However, the absorption contrast in high energy region is considerably low due to the reduced X-ray absorption cross section for most materials. Even though the X-ray phase and dark-field imaging techniques can provide substantially increased contrast and complementary information, fabricating dedicated optics for high energies still remain a challenge. To address this issue, we present an alternative X-ray imaging approach to produce transmission, phase and scattering signals at high X-ray energies by using a random absorption mask. Importantly, in addition to the synchrotron radiation source, this approach has been demonstrated for practical imaging application with a laboratory-based microfocus X-ray source. This new imaging method could be potentially useful for studying thick samples or heavy materials for advanced research in materials science. PMID:27466217

  2. ON NEUTRAL ABSORPTION AND SPECTRAL EVOLUTION IN X-RAY BINARIES

    SciTech Connect

    Miller, J. M.; Cackett, E. M.; Reis, R. C.

    2009-12-10

    Current X-ray observatories make it possible to follow the evolution of transient and variable X-ray binaries across a broad range in luminosity and source behavior. In such studies, it can be unclear whether evolution in the low-energy portion of the spectrum should be attributed to evolution in the source, or instead to evolution in neutral photoelectric absorption. Dispersive spectrometers make it possible to address this problem. We have analyzed a small but diverse set of X-ray binaries observed with the Chandra High Energy Transmission Grating Spectrometer across a range in luminosity and different spectral states. The column density in individual photoelectric absorption edges remains constant with luminosity, both within and across source spectral states. This finding suggests that absorption in the interstellar medium strongly dominates the neutral column density observed in spectra of X-ray binaries. Consequently, evolution in the low-energy spectrum of X-ray binaries should properly be attributed to evolution in the source spectrum. We discuss our results in the context of X-ray binary spectroscopy with current and future X-ray missions.

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

    NASA Astrophysics Data System (ADS)

    Corrales, Lia

    2016-06-01

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

  4. Modelling of the X-ray broad absorption features in Narrow-Line Seyfert 1s

    NASA Astrophysics Data System (ADS)

    Porquet, Delphine; Mouchet, Martine; Dumont Anne-Marie

    2000-09-01

    We investigate the origin of the broad absorption features detected near 1-1.4 keV in several Narrow-Line Seyfert 1 galaxies, by modelling the absorbing medium with various physical parameters, using the ionization code PEGAS. The observed properties of the X-ray absorption features can be reproduced by taking into account the peculiar soft X-ray excess which is well fitted by a blackbody plus an underlying power law. We equally stress that the emission coming from the absorbing medium (related to the covering factor) has a strong influence on the resulting X-ray spectrum, in particular on the apparent position and depth of the absorption features. A non-solar iron abundance may be required to explain the observed deep absorption. We also investigate the influence of an additional collisional ionization process ("hybrid case") on the predicted absorption features.

  5. X-Ray Photoelectron Spectroscopy and the Role of Relaxation Energy in Understanding Chemical Shifts

    ERIC Educational Resources Information Center

    Ellison, Frank O.; White, Michael G.

    1976-01-01

    Discusses the measurement of electrons ejected from a system which is being irradiated with X-rays or ultraviolet photons, and a theoretical model for calculating core-electron ionization energies. (MLH)

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

    SciTech Connect

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

    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 liquid 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.

  7. Using “Tender” X-ray Ambient Pressure X-Ray Photoelectron Spectroscopy as A Direct Probe of Solid-Liquid Interface

    PubMed Central

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

    2015-01-01

    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 liquid 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. PMID:25950241

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

    DOE PAGESBeta

    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

  9. Refraction and absorption of x rays by laser-dressed atoms.

    SciTech Connect

    Buth, C.; Santra, R.; Young, L.

    2010-06-01

    X-ray refraction and absorption by neon atoms under the influence of an 800 nm laser with an intensity of 10{sup 13} W/cm{sup 2} is investigated. For this purpose, we use an ab initio theory suitable for optical strong-field problems. Its results are interpreted in terms of a three-level model. On the Ne 1s {yields} 3p resonance, we find electromagnetically induced transparency (EIT) for x rays. Our work opens novel perspectives for ultrafast x-ray pulse shaping.

  10. High-Energy X-ray Absorption Diagnostics as an Experimental Combustion Technique

    NASA Astrophysics Data System (ADS)

    Dunnmon, Jared; Sobhani, Sadaf; Hinshaw, Waldo; Fahrig, Rebecca; Ihme, Matthias

    2015-11-01

    X-ray diagnostics such as X-ray Computed Tomography (XCT) have recently been utilized for measurement of scalar concentration fields in gas-phase flow phenomena. In this study, we apply high-energy X-ray absorption techniques to visualize a laboratory-scale flame via fluoroscopic measurements by using krypton as a radiodense tracer media. Advantages of X-ray absorption diagnostics in a combustion context, including application to optically inaccessible environments and lack of ambient photon interference, are demonstrated. Analysis methods and metrics for extracting physical insights from these data are presented. The accuracy of the diagnostic is assessed via comparison to known results from canonical flame configurations, and the potential for further applications is discussed. Support from the NDSEG fellowship, Bosch, and NASA are gratefully acknolwedged.

  11. Note: Application of a pixel-array area detector to simultaneous single crystal x-ray diffraction and x-ray absorption spectroscopy measurements

    SciTech Connect

    Sun, Cheng-Jun Brewe, Dale L.; Heald, Steve M.; Zhang, Bangmin; Chen, Jing-Sheng; Chow, G. M.; Venkatesan, T.

    2014-04-15

    X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) are two main x-ray techniques in synchrotron radiation facilities. In this Note, we present an experimental setup capable of performing simultaneous XRD and XAS measurements by the application of a pixel-array area detector. For XRD, the momentum transfer in specular diffraction was measured by scanning the X-ray energy with fixed incoming and outgoing x-ray angles. By selecting a small fixed region of the detector to collect the XRD signal, the rest of the area was available for collecting the x-ray fluorescence for XAS measurements. The simultaneous measurement of XRD and X-ray absorption near edge structure for Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film was demonstrated as a proof of principle for future time-resolved pump-probe measurements. A static sample makes it easy to maintain an accurate overlap of the X-ray spot and laser pump beam.

  12. Femtosecond X-ray magnetic circular dichroism absorption spectroscopy at an X-ray free electron laser.

    PubMed

    Higley, Daniel J; Hirsch, Konstantin; Dakovski, Georgi L; Jal, Emmanuelle; Yuan, Edwin; Liu, Tianmin; Lutman, Alberto A; MacArthur, James P; Arenholz, Elke; Chen, Zhao; Coslovich, Giacomo; Denes, Peter; Granitzka, Patrick W; Hart, Philip; Hoffmann, Matthias C; Joseph, John; Le Guyader, Loïc; Mitra, Ankush; Moeller, Stefan; Ohldag, Hendrik; Seaberg, Matthew; Shafer, Padraic; Stöhr, Joachim; Tsukamoto, Arata; Nuhn, Heinz-Dieter; Reid, Alex H; Dürr, Hermann A; Schlotter, William F

    2016-03-01

    X-ray magnetic circular dichroism spectroscopy using an X-ray free electron laser is demonstrated with spectra over the Fe L(3,2)-edges. The high brightness of the X-ray free electron laser combined with high accuracy detection of incident and transmitted X-rays enables ultrafast X-ray magnetic circular dichroism studies of unprecedented sensitivity. This new capability is applied to a study of all-optical magnetic switching dynamics of Fe and Gd magnetic sublattices in a GdFeCo thin film above its magnetization compensation temperature. PMID:27036761

  13. Oxygen binding by Helix pomatia alpha-haemocyanin studied by X-ray-absorption spectroscopy.

    PubMed Central

    Torensma, R; Phillips, J C

    1983-01-01

    The X-ray absorption spectra of haemocyanin from Helix pomatia were obtained by using X-rays from synchrotron radiation. Cu K-edges were recorded at four conditions, namely fully oxygenated, 85% oxygenated, 12% oxygenated and fully deoxygenated. The percentage oxygenation calculated from the edge-shift of the partially oxygenated samples did not agree with the percentage oxygenation as determined by u.v. measurements. Two intermediates in the oxygenation process are presented to explain the observed dissimilarities. PMID:6847624

  14. Ultraintense X-Ray Induced Ionization, Dissociation, and Frustrated Absorption in Molecular Nitrogen

    SciTech Connect

    Hoener, M.; Fang, L.; Murphy, B.; Berrah, N.; Kornilov, O.; Gessner, O.; Pratt, S. T.; Kanter, E. P.; Guehr, M.; Bucksbaum, P. H.; Cryan, J.; Glownia, M.; McFarland, B.; Petrovic, V.; Blaga, C.; DiMauro, L.; Bostedt, C.; Bozek, J. D.; Coffee, R.; Messerschmidt, M.

    2010-06-25

    Sequential multiple photoionization of the prototypical molecule N{sub 2} is studied with femtosecond time resolution using the Linac Coherent Light Source (LCLS). A detailed picture of intense x-ray induced ionization and dissociation dynamics is revealed, including a molecular mechanism of frustrated absorption that suppresses the formation of high charge states at short pulse durations. The inverse scaling of the average target charge state with x-ray peak brightness has possible implications for single-pulse imaging applications.

  15. Ultraintense x-ray induced ionization, dissociation and frustrated absorption in molecular nitrogen.

    SciTech Connect

    Hoener, M.; Fang, L.; Kornilov, O.; Gessner, O.; Pratt, S. T.; Guhr, M.; Kanter, E. P.; Blaga, C.; Bostedt, C.; Bozek, J. D.; Bucksbaum, P. H.; Buth, C.; Chen, M.; Coffee, R.; Cryan, J.; DiMauro, L.; Glownia, M.; Hosler, E.; Kukk, E.; Leone, S. R.; McFarland, B.; Messerschmidt, M.; Murphy, B.; Petrovic, V.; Rolles, D.; Berrah, N.; Chemical Sciences and Engineering Division; Western Michigan Univ.; LBNL; Ohio State Univ.; Louisiana State Univ.; LLNL; Univ. of Turku; Univ. of California at Berkeley; Max Planck Advanced Study Group, CFEL; LCLS

    2010-06-23

    Sequential multiple photoionization of the prototypical molecule N2 is studied with femtosecond time resolution using the Linac Coherent Light Source (LCLS). A detailed picture of intense x-ray induced ionization and dissociation dynamics is revealed, including a molecular mechanism of frustrated absorption that suppresses the formation of high charge states at short pulse durations. The inverse scaling of the average target charge state with x-ray peak brightness has possible implications for single-pulse imaging applications.

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

    NASA Astrophysics Data System (ADS)

    Grunwaldt, J.-D.; Hagelstein, M.; Rothe, J.

    2016-05-01

    This preface of the proceedings volume of the 16th International Conference on X- ray Absorption Fine Structure (XAFS16) gives a glance on the five days of cutting-edge X-ray science which were held in Karlsruhe, Germany, August 23 - 28, 2015. In addition, several satellite meetings took place in Hamburg, Berlin and Stuttgart, a Sino-German workshop, three data analysis tutorials as well as special symposia on industrial catalysis and XFELs were held at the conference venue.

  17. XMM-Newton Spectroscopy of the X-ray Detected Broad Absorption Line QSO CSO 755

    NASA Technical Reports Server (NTRS)

    Brandt, Niel

    2005-01-01

    We present the results from XMM-Newton observations of the highly optically polarized broad absorption line quasar (BALQSO) CSO 755. By analyzing its X-ray spectrum with a total of approximately 3000 photons we find that this source has an X-ray continuum of "typical" radio-quiet quasars, with a photon index of Gamma=1.83, and a rather flat (X-ray bright) intrinsic optical-to-X-ray spectral slope of alpha_ox=- 1.51. The source shows evidence for intrinsic absorption, and fitting the spectrum with a neutral-absorption model gives a column density of N_H approximately 1.2x10^22 cm^{-2}; this is among the lowest X-ray columns measured for BALQSOs. We do not detect, with high significance, any other absorption features in the X-ray spectrum. Upper limits we place on the rest-frame equivalent width of a neutral (ionized) Fe K-alpha line, less than =180 eV (less than =120 eV), and on the Compton-reflection component parameter, R less than =0.2, suggest that most of the X-rays from the source are directly observed rather than being scattered or reflected; this is also supported by the relatively flat intrinsic alpha ox we measure. The possibility that most of the X-ray flux is scattered due to the high level of UV-optical polarization is ruled out. Considering data for 46 BALQSOs from the literature, including CSO 755, we have found that the UV-optical continuum polarization level of BALQSOs is not correlated with any of their X-ray properties. A lack of significant short-term and long-term X-ray flux variations in the source may be attributed to a large black-hole mass in CSO 755. We note that another luminous BALQSO, PG 2112+059, has both similar shallow C IV BALs and moderate X-ray absorption.

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

    SciTech Connect

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

    2015-01-14

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

  19. High-resolution soft X-ray beamline ADRESS at the Swiss Light Source for resonant inelastic X-ray scattering and angle-resolved photoelectron spectroscopies

    PubMed Central

    Strocov, V. N.; Schmitt, T.; Flechsig, U.; Schmidt, T.; Imhof, A.; Chen, Q.; Raabe, J.; Betemps, R.; Zimoch, D.; Krempasky, J.; Wang, X.; Grioni, M.; Piazzalunga, A.; Patthey, L.

    2010-01-01

    The concepts and technical realisation of the high-resolution soft X-ray beamline ADRESS operating in the energy range from 300 to 1600 eV and intended for resonant inelastic X-ray scattering (RIXS) and angle-resolved photoelectron spectroscopy (ARPES) are described. The photon source is an undulator of novel fixed-gap design where longitudinal movement of permanent magnetic arrays controls not only the light polarization (including circular and 0–180° rotatable linear polarizations) but also the energy without changing the gap. The beamline optics is based on the well established scheme of plane-grating monochromator operating in collimated light. The ultimate resolving power E/ΔE is above 33000 at 1 keV photon energy. The choice of blazed versus lamellar gratings and optimization of their profile parameters is described. Owing to glancing angles on the mirrors as well as optimized groove densities and profiles of the gratings, the beamline is capable of delivering high photon flux up to 1 × 1013 photons s−1 (0.01% BW)−1 at 1 keV. Ellipsoidal refocusing optics used for the RIXS endstation demagnifies the vertical spot size down to 4 µm, which allows slitless operation and thus maximal transmission of the high-resolution RIXS spectrometer delivering E/ΔE > 11000 at 1 keV photon energy. Apart from the beamline optics, an overview of the control system is given, the diagnostics and software tools are described, and strategies used for the optical alignment are discussed. An introduction to the concepts and instrumental realisation of the ARPES and RIXS endstations is given. PMID:20724785

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  1. Time-resolved x-ray photoelectron spectroscopy techniques for real-time studies of interfacial charge transfer dynamics

    SciTech Connect

    Shavorskiy, Andrey; Hertlein, Marcus; Guo Jinghua; Tyliszczak, Tolek; Cordones, Amy; Vura-Weis, Josh; Siefermann, Katrin; Slaughter, Daniel; Sturm, Felix; Weise, Fabian; Khurmi, Champak; Belkacem, Ali; Weber, Thorsten; Gessner, Oliver; Bluhm, Hendrik; Strader, Matthew; Cho, Hana; Coslovich, Giacomo; Kaindl, Robert A.; Lin, Ming-Fu; and others

    2013-04-19

    X-ray based spectroscopy techniques are particularly well suited to gain access to local oxidation states and electronic dynamics in complex systems with atomic pinpoint accuracy. Traditionally, these techniques are applied in a quasi-static fashion that usually highlights the steady-state properties of a system rather than the fast dynamics that often define the system function on a molecular level. Novel x-ray spectroscopy techniques enabled by free electron lasers (FELs) and synchrotron based pump-probe schemes provide the opportunity to monitor intramolecular and interfacial charge transfer processes in real-time and with element and chemical specificity. Two complementary time-domain xray photoelectron spectroscopy techniques are presented that are applied at the Linac Coherent Light Source (LCLS) and the Advanced Light Source (ALS) to study charge transfer processes in N3 dye-sensitized ZnO semiconductor nanocrystals, which are at the heart of emerging light-harvesting technologies.

  2. Photoelectron diffraction from single oriented molecules: Towards ultrafast structure determination of molecules using x-ray free-electron lasers

    NASA Astrophysics Data System (ADS)

    Kazama, Misato; Fujikawa, Takashi; Kishimoto, Naoki; Mizuno, Tomoya; Adachi, Jun-ichi; Yagishita, Akira

    2013-06-01

    We provide a molecular structure determination method, based on multiple-scattering x-ray photoelectron diffraction (XPD) calculations. This method is applied to our XPD data on several molecules having different equilibrium geometries. Then it is confirmed that, by our method, bond lengths and bond angles can be determined with a resolution of less than 0.1 Å and 10∘, respectively. Differently from any other scenario of ultrafast structure determination, we measure the two- or three-dimensional XPD of aligned or oriented molecules in the energy range from 100 to 200 eV with a 4π detection velocity map imaging spectrometer. Thanks to the intense and ultrashort pulse properties of x-ray free-electron lasers, our approach exhibits the most probable method for obtaining ultrafast real-time structural information on small to medium-sized molecules consisting of light elements, i.e., a “molecular movie.”

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

    SciTech Connect

    Rheinheimer, Vanessa; Casanova, Ignasi

    2014-06-01

    Electron-beam evaporation was used to produce thin films of β-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.

  4. Sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy setup for pulsed and constant wave X-ray light sources.

    PubMed

    Shavorskiy, Andrey; Neppl, Stefan; Slaughter, Daniel S; Cryan, James P; Siefermann, Katrin R; Weise, Fabian; Lin, Ming-Fu; Bacellar, Camila; Ziemkiewicz, Michael P; Zegkinoglou, Ioannis; Fraund, Matthew W; Khurmi, Champak; Hertlein, Marcus P; Wright, Travis W; Huse, Nils; Schoenlein, Robert W; Tyliszczak, Tolek; Coslovich, Giacomo; Robinson, Joseph; Kaindl, Robert A; Rude, Bruce S; Ölsner, Andreas; Mähl, Sven; Bluhm, Hendrik; Gessner, Oliver

    2014-09-01

    An apparatus for sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy studies with pulsed and constant wave X-ray light sources is presented. A differentially pumped hemispherical electron analyzer is equipped with a delay-line detector that simultaneously records the position and arrival time of every single electron at the exit aperture of the hemisphere with ~0.1 mm spatial resolution and ~150 ps temporal accuracy. The kinetic energies of the photoelectrons are encoded in the hit positions along the dispersive axis of the two-dimensional detector. Pump-probe time-delays are provided by the electron arrival times relative to the pump pulse timing. An average time-resolution of (780 ± 20) ps (FWHM) is demonstrated for a hemisphere pass energy E(p) = 150 eV and an electron kinetic energy range KE = 503-508 eV. The time-resolution of the setup is limited by the electron time-of-flight (TOF) spread related to the electron trajectory distribution within the analyzer hemisphere and within the electrostatic lens system that images the interaction volume onto the hemisphere entrance slit. The TOF spread for electrons with KE = 430 eV varies between ~9 ns at a pass energy of 50 eV and ~1 ns at pass energies between 200 eV and 400 eV. The correlation between the retarding ratio and the TOF spread is evaluated by means of both analytical descriptions of the electron trajectories within the analyzer hemisphere and computer simulations of the entire trajectories including the electrostatic lens system. In agreement with previous studies, we find that the by far dominant contribution to the TOF spread is acquired within the hemisphere. However, both experiment and computer simulations show that the lens system indirectly affects the time resolution of the setup to a significant extent by inducing a strong dependence of the angular spread of electron trajectories entering the hemisphere on the retarding ratio. The scaling of the angular spread with

  5. Sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy setup for pulsed and constant wave X-ray light sources.

    PubMed

    Shavorskiy, Andrey; Neppl, Stefan; Slaughter, Daniel S; Cryan, James P; Siefermann, Katrin R; Weise, Fabian; Lin, Ming-Fu; Bacellar, Camila; Ziemkiewicz, Michael P; Zegkinoglou, Ioannis; Fraund, Matthew W; Khurmi, Champak; Hertlein, Marcus P; Wright, Travis W; Huse, Nils; Schoenlein, Robert W; Tyliszczak, Tolek; Coslovich, Giacomo; Robinson, Joseph; Kaindl, Robert A; Rude, Bruce S; Ölsner, Andreas; Mähl, Sven; Bluhm, Hendrik; Gessner, Oliver

    2014-09-01

    An apparatus for sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy studies with pulsed and constant wave X-ray light sources is presented. A differentially pumped hemispherical electron analyzer is equipped with a delay-line detector that simultaneously records the position and arrival time of every single electron at the exit aperture of the hemisphere with ~0.1 mm spatial resolution and ~150 ps temporal accuracy. The kinetic energies of the photoelectrons are encoded in the hit positions along the dispersive axis of the two-dimensional detector. Pump-probe time-delays are provided by the electron arrival times relative to the pump pulse timing. An average time-resolution of (780 ± 20) ps (FWHM) is demonstrated for a hemisphere pass energy E(p) = 150 eV and an electron kinetic energy range KE = 503-508 eV. The time-resolution of the setup is limited by the electron time-of-flight (TOF) spread related to the electron trajectory distribution within the analyzer hemisphere and within the electrostatic lens system that images the interaction volume onto the hemisphere entrance slit. The TOF spread for electrons with KE = 430 eV varies between ~9 ns at a pass energy of 50 eV and ~1 ns at pass energies between 200 eV and 400 eV. The correlation between the retarding ratio and the TOF spread is evaluated by means of both analytical descriptions of the electron trajectories within the analyzer hemisphere and computer simulations of the entire trajectories including the electrostatic lens system. In agreement with previous studies, we find that the by far dominant contribution to the TOF spread is acquired within the hemisphere. However, both experiment and computer simulations show that the lens system indirectly affects the time resolution of the setup to a significant extent by inducing a strong dependence of the angular spread of electron trajectories entering the hemisphere on the retarding ratio. The scaling of the angular spread with

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

    SciTech Connect

    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.

  7. Accretion Shocks in Young Stars: the Role of Local Absorption on the X-ray Emission

    NASA Astrophysics Data System (ADS)

    Bonito, R.; Argiroffi, C.; Orlando, S.; Miceli, M.; Peres, G.; Matsakos, T.; Stehle, C.; Ibgui, L.

    2015-01-01

    We investigate the X-ray emission from accretion shocks in classical T Tauri stars, due to the infalling material impacting the stellar surface. Several aspects in both observations and models of the accretion process are still unclear: the observed X-ray luminosity of the post-shock plasma is below the predicted value, the density vs temperature structure of the shocked plasma, with increasing densities at higher temperature, is opposite of what expected from simple accretion shock models. To address these issues we performed numerical magnetohydrodynamic simulations describing the impact of an accretion stream onto the stellar surface and considered the local absorption due to the surrounding medium. We explored the effects of absorption for different viewing angles and for the He-like line triplets commonly used for density diagnostic. From the model results we synthesize the X-ray emission from the accretion shock, producing maps and spectra. We perform density and temperature diagnostics on the synthetic spectra, and we directly compare our results with the observations. Our model shows that the X-ray fluxes detected are lower than expected because of the local absorption. The emerging spectra suggest a complex density vs temperature distribution proving that a detailed model accounting for a realistic treatment of the local absorption is needed to interpret the observations of X-ray emitting accretion shocks.

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

    SciTech Connect

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

    2009-06-30

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

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

    SciTech Connect

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

    2006-06-15

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

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

    SciTech Connect

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

    1989-09-19

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

  11. Transmission photoemission electron microscopy for lateral mapping of the X-ray absorption structure of a metalloprotein in a liquid cell.

    PubMed

    Panzer, D; Beck, C; Maul, J; Möller, M; Decker, H; Schönhense, G

    2008-11-01

    We use photoemission electron microscopy in an X-ray transmission mode for full-field imaging of the X-ray absorption structure of copper in the respiratory metalloprotein hemocyanin KLH1. It contains 160 oxygen binding sites. Each site reversibly binds one molecule oxygen between two copper atoms. In our setup, hemocyanin is dissolved in aqueous solution and enclosed in an ultra-high vacuum compatible liquid sample cell with silicon nitride membranes. The local X-ray absorption structure of the liquid sample is converted into photoelectrons at the microscope side of the cell acting as a photocathode. In this way, different copper valencies are laterally distinguished under in vivo-like conditions, attributed to Cu(I) in the deoxy-state and Cu(II) in the oxy-state.

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

    PubMed Central

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

    2016-01-01

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

  13. Identification of metal s states in Sn-doped anatase by polarisation dependent hard X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Regoutz, A.; Oropeza, F. E.; Poll, C. G.; Payne, D. J.; Palgrave, R. G.; Panaccione, G.; Borgatti, F.; Agrestini, S.; Utsumi, Y.; Tsuei, K. D.; Liao, Y. F.; Watson, G. W.; Egdell, R. G.

    2016-03-01

    The contributions of Sn 5s and Ti 4s states to the valence band electronic structure of Sn-doped anatase have been identified by hard X-ray photoelectron spectroscopy. The metal s state intensity is strongly enhanced relative to that of O 2p states at high photon energies due to matrix element effects when electrons are detected parallel to the direction of the polarisation vector of the synchrotron beam, but becomes negligible in the perpendicular direction. The experimental spectra in both polarisations are in good agreement with cross section and asymmetry parameter weighted partial densities of states derived from density functional theory calculations.

  14. Structure and Bonding in Chlorine-Functionalized Nanodiamond--Nuclear Magnetic Resonance and X-Ray Photoelectron Spectroscopy Study.

    PubMed

    Panich, Alexander M; Sergeev, Nikolay A; Olszewski, Marcin; Froumin, Natalya; Dideykin, Arthur T; Sokolov, Vasiliy V; Vul', Alexander Ya

    2015-02-01

    We report on investigation of detonation nanodiamond annealed at 800C°in chlorine atmosphere by means of 1H, 13C and 35Cl nuclear magnetic resonance and X-ray photoelectron spectroscopy. The results of these methods are found to be consistent with each other and evidence formation of chlorine-carbon groups and sp2 carbon shell on the nanodiamond surface. The data obtained provide detailed information about the structure and bonding in this diamond nanoparticle. Interaction of nuclear spins with unpaired electron spins of dangling bonds results in fast 13C nuclear spin-lattice relaxation.

  15. X-ray Photoelectron Spectroscopy Analysis of Gold Surfaces after Removal of Thiolated DNA Oligomers by Ultraviolet/Ozone Treatment

    PubMed Central

    Mirsaleh-Kohan, Nasrin; Bass, Andrew D.; Sanche, Léon

    2012-01-01

    Well ordered films of molecular DNA can be formed by the attachment of thiolated DNA oligonucleotides to a supporting gold substrate. The gold substrate represents a significant fraction of the total cost of preparing such films and it is thus important to determine whether such substrates can be reused. Here we investigate with X-ray Photoelectron Spectroscopy the suitability of UV/ozonolysis previously employed to remove alkanethiols from gold, for removing 40-mer, single and double stranded synthetic DNA. We find that while UV/O3 can indeed remove thiolated DNA from gold slides, the treatment times required permit the implantation of additional organic contaminants. PMID:20000594

  16. Application of maximum-entropy spectral estimation to deconvolution of XPS data. [X-ray Photoelectron Spectroscopy

    NASA Technical Reports Server (NTRS)

    Vasquez, R. P.; Klein, J. D.; Barton, J. J.; Grunthaner, F. J.

    1981-01-01

    A comparison is made between maximum-entropy spectral estimation and traditional methods of deconvolution used in electron spectroscopy. The maximum-entropy method is found to have higher resolution-enhancement capabilities and, if the broadening function is known, can be used with no adjustable parameters with a high degree of reliability. The method and its use in practice are briefly described, and a criterion is given for choosing the optimal order for the prediction filter based on the prediction-error power sequence. The method is demonstrated on a test case and applied to X-ray photoelectron spectra.

  17. Soft X-ray absorption excess in gamma-ray burst afterglow spectra: Absorption by turbulent ISM

    NASA Astrophysics Data System (ADS)

    Tanga, M.; Schady, P.; Gatto, A.; Greiner, J.; Krause, M. G. H.; Diehl, R.; Savaglio, S.; Walch, S.

    2016-10-01

    Two-thirds of long duration gamma-ray bursts (GRBs) show soft X-ray absorption in excess of the Milky Way. The column densities of metals inferred from UV and optical spectra differ from those derived from soft X-ray spectra, at times by an order of magnitude, with the latter being higher. The origin of the soft X-ray absorption excess observed in GRB X-ray afterglow spectra remains a heavily debated issue, which has resulted in numerous investigations on the effect of hot material both internal and external to the GRB host galaxy on our X-ray afterglow observations. Nevertheless, all models proposed so far have either only been able to account for a subset of our observations (i.e. at z> 2), or they have required fairly extreme conditions to be present within the absorbing material. In this paper, we investigate the absorption of the GRB afterglow by a collisionally ionised and turbulent interstellar medium (ISM). We find that a dense (3 cm-3) collisionally ionised ISM could produce UV/optical and soft X-ray absorbing column densities that differ by a factor of 10. However the UV/optical and soft X-ray absorbing column densities for such sightlines are 2-3 orders of magnitude lower in comparison to the GRB afterglow spectra. For those GRBs with a larger soft X-ray excess by up to an order of magnitude, the contribution in absorption from a turbulent ISM as considered here would ease the required conditions of additional absorbing components, such as the GRB circumburst medium and intergalactic medium.

  18. Nanocrystalline tin oxide: Possible origin of its weak ferromagnetism deduced from nuclear magnetic resonance and X-ray photoelectron spectroscopies

    NASA Astrophysics Data System (ADS)

    Zhang, Feng; Lian, Yadong; Gu, Min; Yu, Ji; Tang, Tong B.; Sun, Jian; Zhang, Weiyi

    2016-09-01

    Nanocrystalline tin oxide was fabricated, with molar ratio O/Sn determined as 1.40, 1.55, 1.79, 1.92 and 1.96 from X-ray photoelectron spectroscopy. They displayed weak ferromagnetism, the sample with O/Sn = 1.55 showing the maximum saturation magnetization reaching almost 8 ×10-3 emu /g at room temperature. 119Sn nuclear magnetic resonance allowed the deduction, based on four resolved resonance peaks, that their Sn ions had four possible coordination numbers, namely 3, 4, 5 and 6. The relative fraction of 4-coordinated cations was the one found to bear positive linear correlation with saturation magnetization of the sample. It is surmised that magnetism in tin oxide results mainly from 4-coordination Sn ions, of valance about +3, as estimated from the binding energies of their 3d photoelectron emission levels.

  19. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    SciTech Connect

    Fischer, D.A. ); Mitchell, G.E.; Dekoven, B.M. ); Yeh, A.T.; Gland, J.L. ); Moodenbaugh, A.R. )

    1993-01-01

    Direct comparisons between surface and bulk of diverse materials can be made by simultaneous electron yield (5 nm depth sensitivity) and fluorescence yield (200 nm) ultra soft x-ray absorption spectroscopy measurements utilizing a rapid sample interchange apparatus. For example the orientations of functional groups have been characterized at and near the surface of a series of model polymeric materials highlighting the chemical and molecular sensitivity of ultra soft x-ray absorption spectroscopy. In addition we discuss a bulk sensitive use of fluorescence yield to non destructively study a buried metal polymer interface. A second bulk sensitive example is the use of fluorescence yield oxygen K near edge x-ray spectroscopy as a method to determine the hole state density of high Tc materials.

  20. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    SciTech Connect

    Fischer, D.A.; Mitchell, G.E.; Dekoven, B.M.; Yeh, A.T.; Gland, J.L.; Moodenbaugh, A.R.

    1993-06-01

    Direct comparisons between surface and bulk of diverse materials can be made by simultaneous electron yield (5 nm depth sensitivity) and fluorescence yield (200 nm) ultra soft x-ray absorption spectroscopy measurements utilizing a rapid sample interchange apparatus. For example the orientations of functional groups have been characterized at and near the surface of a series of model polymeric materials highlighting the chemical and molecular sensitivity of ultra soft x-ray absorption spectroscopy. In addition we discuss a bulk sensitive use of fluorescence yield to non destructively study a buried metal polymer interface. A second bulk sensitive example is the use of fluorescence yield oxygen K near edge x-ray spectroscopy as a method to determine the hole state density of high Tc materials.

  1. Oxygen, neon, and iron X-ray absorption in the local interstellar medium

    NASA Astrophysics Data System (ADS)

    Gatuzz, Efraín; García, Javier A.; Kallman, Timothy R.; Mendoza, Claudio

    2016-04-01

    Aims: We present a detailed study of X-ray absorption in the local interstellar medium by analyzing the X-ray spectra of 24 galactic sources obtained with the Chandra High Energy Transmission Grating Spectrometer and the XMM-Newton Reflection Grating Spectrometer. Methods: By modeling the continuum with a simple broken power-law and by implementing the new ISMabs X-ray absorption model, we have estimated the total H, O, Ne, and Fe column densities towards the observed sources. Results: We have determined the absorbing material distribution as a function of source distance and galactic latitude-longitude. Conclusions: Direct estimates of the fractions of neutrally, singly, and doubly ionized species of O, Ne, and Fe reveal the dominance of the cold component, thus indicating an overall low degree of ionization. Our results are expected to be sensitive to the model used to describe the continuum in all sources.

  2. Composition of CuAu alloy and changes upon corrosion studied by Hard X-ray Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Rajput, Parasmani; Detlefs, Blanka; Gupta, Ajay; Kolb, Dieter; Zegenhagen, Jorg

    2011-03-01

    Metals and their alloys are highly susceptible to corrosion in wet environment. Dealloying is a particular type of corrosion, attacking practically all metals in industrial use: When an alloy is coming into contact with an electrolyte, the less noble metal may go into solution, typically causing crack formation and subsequent material failure upon stress. We used bulk sensitive Hard X-ray photoelectron spectroscopy (HAXPES) with an excitation energy of 6 keV as a new powerful tool to investigate the chemical composition of alloys and changes upon dealloying, studying Cu x Au (with x = 4.1) alloy films of 9 to 50 nm thickness. Morphology, structure and composition were further characterized by atomic force microscopy, X-ray reflectivity and quantitative X-ray fluorescence. The HAXPES analysis revealed that chemical shifts of metal core-levels, i.e. Au 4 f and Cu 3 s , can be used as a benchmark for the alloy composition. HAXPES as a function of electron emission angle allowed depth sensitive determination of the chemical composition before and after dealloying in sulphuric acid.

  3. Search for correlated UV and x ray absorption of NGC 3516

    NASA Technical Reports Server (NTRS)

    Martin, Christopher; Halpern, Jules P.; Kolman, Michiel

    1991-01-01

    NGC 3516, a low-luminosity Seyfert galaxy, is one of a small fraction of Seyfert galaxies that exhibit broad absorption in a resonance line. In order to determine whether the UV and x ray absorption in NGC 3516 are related, 5 IUE observations were obtained, quasi-simultaneously with 4 Ginga observations. The results are presented and discussed. The following subject areas are covered: short-term UV variability; emission lines; galactic absorption lines; the C IV, N V, and Si IV absorption features; lower limit on the carbon column density; estimate of the distance from the absorber to the continuum source; variability in the continuum and absorption; a comparison with BAL QSO's; and the x ray-UV connection.

  4. Comprehensive X-Ray Absorption Models for Oxygen and Neon

    NASA Astrophysics Data System (ADS)

    Gorczyca, Thomas

    2013-09-01

    We propose to perform state-of-the-art R-matrix calculations for the oxygen and neon photoabsorption cross sections to improve upon earlier, incomplete data. Several important higher-order effects will be addressed: orbital relaxation, Auger line broadening, two-electron shake, and elimination of pseudoresonances. The computed atomic cross sections will first be fit by a recently-developed analytical fitting formula, and then benchmarked further to experimental and Chandra observed absorption lines. The resulting data will be uploaded into the AtomDB, XSPEC, and ISIS databases for spectral modeling use. These definitive cross sections will resolve an outstanding discrepancy between XSTAR and SPEX spectral modeling predictions of molecular (dust and/or ice) abundances in the ISM.

  5. Forward scattering in hard X-ray photoelectron spectroscopy: Structural investigation of buried Mn–Ga films

    SciTech Connect

    ViolBarbosa, Carlos E. Ouardi, Siham; Fecher, Gerhard H. Felser, Claudia; Kubota, Takahide; Mizukami, Shigemi; Miyazaki, Terunobu; Ikenaga, Eiji

    2015-02-02

    X-ray photoelectron diffraction (XPD) in combination with hard X-ray photoelectron spectroscopy (HAXPES) has been used to study the structure of buried layers in thin multilayer films. A detailed layer-by-layer investigation was performed using the element-specific, local-probe character of XPD. In the present work, angular-resolved HAXPES at a photon energy of 7.94 keV photon energy was used to investigate a Cr/Mn{sub 62}Ga{sub 38}/Mg/MgO multilayer system. Differences in the angular distributions of electrons emitted from Mn and Ga atoms revealed that the structure of Mn{sub 62}Ga{sub 38} changes from L1{sub 0} towards D0{sub 22} for increasing annealing temperatures. A c/a ratio of 1.81 ± 0.06 was determined for the buried Mn{sub 62}Ga{sub 38} layer in a D0{sub 22} structure from the XPD experiment. The improvement of the structural order of the Mn{sub 62}Ga{sub 38} layer is accompanied by an improvement of the structure of the overlying MgO layer.

  6. Silicon nanocrystals with high boron and phosphorus concentration hydrophilic shell—Raman scattering and X-ray photoelectron spectroscopic studies

    SciTech Connect

    Fujii, Minoru Sugimoto, Hiroshi; Hasegawa, Masataka; Imakita, Kenji

    2014-02-28

    Boron (B) and phosphorus (P) codoped silicon (Si) nanocrystals, which exhibit very wide range tunable luminescence due to the donor to acceptor transitions and can be dispersed in polar liquids without organic ligands, are studied by Raman scattering and X-ray photoelectron spectroscopies. Codoped Si nanocrystals exhibit a Raman spectrum significantly different from those of intrinsic ones. First, the Raman peak energy is almost insensitive to the size and is very close to that of bulk Si crystal in the diameter range of 2.7 to 14 nm. Second, the peak is much broader than that of intrinsic ones. Furthermore, an additional broad peak, the intensity of which is about 20% of the main peak, appears around 650 cm{sup −1}. The peak can be assigned to local vibrational modes of substitutional B and B-P pairs, B clusters, B-interstitial clusters, etc. in Si crystal. The Raman and X-ray photoelectron spectroscopic studies suggest that a crystalline shell heavily doped with these species is formed at the surface of a codoped Si nanocrystal and it induces the specific properties, i.e., hydrophilicity, high-stability in water, high resistance to hydrofluoric acid, etc.

  7. X-ray photoelectron spectroscopy study of irradiation-induced amorphizaton of Gd2Ti2O7

    NASA Astrophysics Data System (ADS)

    Chen, J.; Lian, J.; Wang, L. M.; Ewing, R. C.; Boatner, L. A.

    2001-09-01

    The radiation-induced evolution of the microstructure of Gd2Ti2O7, an important pyrochlore phase in radioactive waste disposal ceramics and a potential solid electrolyte and oxygen gas sensor, has been characterized using transmission electron microscopy and x-ray photoelectron spectroscopy. Following the irradiation of a Gd2Ti2O7 single crystal with 1.5 MeV Xe+ ions at a fluence of 1.7×1014Xe+/cm2, cross-sectional transmission electron microscopy revealed a 300-nm-thick amorphous layer at the specimen surface. X-ray photoelectron spectroscopy analysis of the Ti 2p and O 1s electron binding energy shifts of Gd2Ti2O7 before and after amorphization showed that the main results of ion-irradiation-induced disorder are a decrease in the coordination number of titanium and a transformation of the Gd-O bond. These features resemble those occurring in titanate glass formation, and they have implications for the chemical stability and electronic properties of pyrochlores subjected to displacive radiation damage.

  8. High Resolution Spectroscopy of X-ray Quasars: Searching for the X-ray Absorption from the Warm-Hot Intergalactic Medium

    NASA Technical Reports Server (NTRS)

    Fang, Taotao; Canizares, Claude R.; Marshall, Herman L.

    2004-01-01

    We present a survey of six low to moderate redshift quasars with Chandra and XMM-Newton. The primary goal is to search for the narrow X-ray absorption lines produced by highly ionized metals in the Warm-Hot Intergalactic Medium. All the X-ray spectra can be well fitted by a power law with neutral hydrogen absorption. Only one feature is detected at above 3-sigma level in all the spectra, which is consistent with statistic fluctuation. We discuss the implications in our understanding of the baryon content of the universe. We also discuss the implication of the non-detection of the local (z approx. 0) X-ray absorption.

  9. Application of x-ray absorption spectroscopy to the study of corrosion and inhibition

    SciTech Connect

    Davenport, A.J.; Isaacs, H.S.

    1991-01-01

    X-ray absorption spectroscopy is a powerful technique for determination of valency and coordination. Measurements can be made in air or in situ under electrochemical control. The technique will be described and its application to the analysis of passive oxide films, corrosion products, and inhibitors will be reviewed.

  10. Characterization of the X-ray absorption in the Galactic ISM

    NASA Astrophysics Data System (ADS)

    Gatuzz, E.; García, J.; Kallman, T.; Mendoza, C.

    2016-06-01

    The physical conditions of the Galactic interstellar medium (ISM) can be studied in detail through the high-resolution X-ray spectroscopy provided by the grating instruments in both Chandra and XMM-Newton. Using an X-ray source, which acts as a lamp, one can analyze the absorption features that are imprinted in the spectra by the gas located between the observer and the X-ray source, which offers the opportunity to study physical properties of the ISM such as ionization degree, column densities, and elemental abundances. We present a detailed analysis of the H, O, Ne, and Fe absorption in the X-ray spectra of 24 bright galactic sources obtained with the Chandra and XMM-Newton observatories. Implementing our new absorption model ISMabs, we have measured column densities, ionization fractions, and abundances for H, O, Ne, and Fe in the direction of each source. We find that the column densities tend to increase with source distance and decrease with galactic latitude, while the ionization fractions and abundances are mostly constant along every line of sight. Finally, we found that molecules and grains are not a major contributor to the absorption features in the O K-edge wavelength region.

  11. Discovery of Broad Soft X-ray Absorption Lines from the Quasar Wind in PDS 456

    NASA Astrophysics Data System (ADS)

    Reeves, J. N.; Braito, V.; Nardini, E.; Behar, E.; O’Brien, P. T.; Tombesi, F.; Turner, T. J.; Costa, M. T.

    2016-06-01

    High-resolution soft X-ray spectroscopy of the prototype accretion disk wind quasar, PDS 456, is presented. Here, the XMM-Newton reflection grating spectrometer spectra are analyzed from the large 2013–2014 XMM-Newton campaign, consisting of five observations of approximately 100 ks in length. During the last observation (OBS. E), the quasar is at a minimum flux level, and broad absorption line (BAL) profiles are revealed in the soft X-ray band, with typical velocity widths of {σ }{{v}}˜ {{10,000}} km s‑1. During a period of higher flux in the third and fourth observations (OBS. C and D, respectively), a very broad absorption trough is also present above 1 keV. From fitting the absorption lines with models of photoionized absorption spectra, the inferred outflow velocities lie in the range ˜ 0.1{--}0.2c. The absorption lines likely originate from He and H-like neon and L-shell iron at these energies. A comparison with earlier archival data of PDS 456 also reveals a similar absorption structure near 1 keV in a 40 ks observation in 2001, and generally the absorption lines appear most apparent when the spectrum is more absorbed overall. The presence of the soft X-ray BALs is also independently confirmed by an analysis of the XMM-Newton EPIC spectra below 2 keV. We suggest that the soft X-ray absorption profiles could be associated with a lower ionization and possibly clumpy phase of the accretion disk wind, where the latter is known to be present in this quasar from its well-studied iron K absorption profile and where the wind velocity reaches a typical value of 0.3c.

  12. Experimental investigation of X-ray spectral absorption coefficients in heated Al and Ge on the Iskra-5 laser facility

    NASA Astrophysics Data System (ADS)

    Bondarenko, S. V.; Garanin, Sergey G.; Zhidkov, N. V.; Pinegin, A. V.; Suslov, N. A.

    2012-01-01

    We set forth the data of experimental investigation of X-ray spectral absorption coefficients in the 1.1 — 1.6 keV photon energy range for Al and Ge specimens bulk heated by soft X-ray radiation. Two experimental techniques are described: with the use of one facility channel and the heating of specimens by the X-ray radiation from a plane burnthrough target, as well as with the use of four channels and the heating by the radiation from two cylindrical targets with internal input of laser radiation. The X-ray radiation absorption coefficients were studied by way of transmission absorption spectroscopy using backlighting X-ray radiation from a point source. The results of investigation of X-ray spectral absorption coefficients on the 1s — 2p transitions in Al atoms and the 2p — 3d transitions in Ge atoms are presented.

  13. Picosecond-resolved X-ray absorption spectroscopy at low signal contrast using a hard X-ray streak camera

    SciTech Connect

    Adams, Bernhard W.; Rose-Petruck, Christoph; Jiao, Yishuo

    2015-06-24

    A picosecond-resolving hard-X-ray streak camera has been in operation for several years at Sector 7 of the Advanced Photon Source (APS). Several upgrades have been implemented over the past few years to optimize integration into the beamline, reduce the timing jitter, and improve the signal-to-noise ratio. These include the development of X-ray optics for focusing the X-rays into the sample and the entrance slit of the streak camera, and measures to minimize the amount of laser light needed to generate the deflection-voltage ramp. For the latter, the photoconductive switch generating the deflection ramp was replaced with microwave power electronics. With these, the streak camera operates routinely at 88 MHz repetition rate, thus making it compatible with all of the APS fill patterns including use of all the X-rays in the 324-bunch mode. Sample data are shown to demonstrate the performance.

  14. Auger electron spectroscopy and x-ray photoelectron spectroscopy of the biocorrosion of copper by Gum Arabic, BCS and Pseudomonas atlantica exopolymer

    SciTech Connect

    Jolley, J.G.; Geesey, G.G.; Hankins, M.R.; Wright, R.B.; Wichlacz, P.L.

    1987-01-01

    Thin films (3.4 nm) of copper on germanium substrates were exposed to 10% Gum Arabic aqueous solution, 1% BCS (aqueous and simulated sea water solutions) and 0.5% Pseudomonas atlantica exopolymer (aqueous and simulated sea water solutions). Pre- and post-exposure characterization were done by Auger electron spectroscopy and x-ray photoelectron spectroscopy. Ancillary graphite furnace atomic absorption spectroscopy was used to monitor the removal process of the copper thin film from the germanium substrate. Results indicate that the copper was oxidized by the Gum Arabic and BCS, and some was removed from the Cu/Ge interface by all three polymers and incorporated into the polymer matrix. Thus biocorrosion of copper was exhibited by the Gum Arabic, BCS and Pseudomonas atlantica exopolymer. 14 refs., 4 figs., 3 tabs.

  15. X-Ray Dichroism in Photoelectron Spectroscopy for Direct Element Specific Surface Magnetometry of Nanomagnetic Structures

    NASA Astrophysics Data System (ADS)

    Tobin, James G.

    1997-03-01

    Element specific surface magnetometry remains a central goal of synchrotron radiation based studies of nanomagnetic structures. One appealing possibility is the combination of xray absorption dichroism measurements and the theoretical framework provided by the "sum rules."[1] Unfortunately, sum rule analyses are hampered by several limitations [2], including delocalization of the final state, multi-electronic phenomena and the presence of surface dipoles. An alternative experiment, Magnetic Xray Dichroism in Photoelectron Spectroscopy, holds out promise based upon its elemental specificity, surface sensitivity and high resolution. Computational simulations by Tamura et al [3] demonstrated the relationship between exchange and spin orbit splittings and experimental data of linear and circular dichroisms. Now we [4] have developed an analytical framework which allows for the direct extraction of core level exchange splittings from circular and linear dichroic photoemission data. By extending a model initially proposed by Venus [5], it is possible to show a linear relation between normalized dichroism peaks in the experimental data and the underlying exchange splitting. Since it is reasonable to expect that exchange splittings and magnetic moments track together [6], this measurement thus becomes a powerful new tool for direct surface magnetometry, without recourse to time consuming and difficult spectral simulations. The theoretical derivation will be supported by high resolution linear and circular dichroism data collected at the Spectromicroscopy Facility of the Advanced Light Source. [7,8] This work was performed under the auspices of the U.S. Department of Energy by LLNL under contract No. W-7405-ENG-48. 1. B.T. Thole et al, Phys. Rev. Lett. 68,1943 (1992); P. Carra et al. Phys. Rev. Lett. 70, 694 (1993). 2. J.G. Tobin et al Phys. Rev. B 52, 6530 (1995). 3. E. Tamura et al, Phys. Rev. Lett 73, 1533 (1994) 4. J.G. Tobin, K.W. Goodman, F.O. Schumann, R.F. Willis, J

  16. Use of X-ray absorption spectroscopy in the search for the best LIGO mirror coatings

    NASA Astrophysics Data System (ADS)

    McGuire, Stephen C.

    2008-03-01

    The Laser Interferometer Gravitational-wave Observatory (LIGO) seeks to improve its sensitivity for gravity-wave detection by a factor of ten during its next phase of operation, Advanced LIGO. In order to achieve this goal it is necessary to design and fabricate test mass mirrors that help minimize the noise in the interferometers and in doing so maximize gravity-wave detection capability. In this talk we will present recent results from our program of X-ray absorption spectroscopy measurements to obtain detailed chemical composition and structure of titania (TiO2)-doped tantala (Ta2O5) multilayers fabricated via ion beam sputtering on SiO2 substrates. Our investigations focus on how the microscopic features of the coatings influence their macroscopic mechanical loss properties. Our goal is to obtain correlations between chemical impurities and/or dopants and the optical absorption and mechanical loss characteristics of these multilayer coatings. To examine our samples we use synchrotron-based X-ray absorption Spectroscopy (XAS) techniques including Extended X-ray Absorption Fine Structure (EXAFS), X-ray Absorption Near Edge Structure (XANES) and X-ray Fluorescence (XRF). We present chemical and structural data obtained at the titanium K-edge and tantalum LIII-edge as well as relative elemental distribution information (Ti/Ta, Fe/Ta, and Cr/Ta) obtained via XRF. Following a brief description of the LIGO experiment, our program of research in optical materials for use in advanced versions of the interferometer will be described.

  17. X-Ray Absorption Spectroscopy Study of Copper Doped ZnO Thin Films

    SciTech Connect

    Ma Qing

    2007-02-02

    X-ray absorption spectroscopy technique is used to study copper-doped ZnO thin films, prepared by pulsed-laser deposition. The samples with various doping levels are examined. It is found that the samples contain metallic clusters with the sizes {<=} 2 nm as well as Cu1+ and Cu2+ states. The Cu1+ states exist as stable oxide clusters, while the Cu2+ ones participate in the ZnO lattice some of which may be pertaining to the surfaces of the Cu clusters as well. The copper clusters of {approx}1 nm are unstable and fragment under monochromatic x-ray beam illumination.

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

    SciTech Connect

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

    2007-02-02

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

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

    DOE PAGESBeta

    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.

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

    SciTech Connect

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

    1985-05-01

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

  1. Femtosecond time-resolved X-ray absorption spectroscopy of liquid using a hard X-ray free electron laser in a dual-beam dispersive detection method.

    PubMed

    Obara, Yuki; Katayama, Tetsuo; Ogi, Yoshihiro; Suzuki, Takayuki; Kurahashi, Naoya; Karashima, Shutaro; Chiba, Yuhei; Isokawa, Yusuke; Togashi, Tadashi; Inubushi, Yuichi; Yabashi, Makina; Suzuki, Toshinori; Misawa, Kazuhiko

    2014-01-13

    We present femtosecond time-resolved X-ray absorption spectroscopy of aqueous solution using a hard x-ray free electron laser (SACLA) and a synchronized Ti:sapphire laser. The instrumental response time is 200 fs, and the repetition rate of measurement is 10 Hz. A cylindrical liquid beam 100 μm in diameter of aqueous ammonium iron(III) oxalate solution is photoexcited at 400 nm, and the transient X-ray absorption spectra are measured in the K-edge region of iron, 7.10 - 7.26 keV, using a dual X-ray beam dispersive detection method. Each of the dual beams has the pulse energy of 1.4 μJ, and pump-induced absorbance change on the order of 10(-3) is successfully detected. The photoexcited iron complex exhibits a red shifted iron K-edge with the appearance time constant of 260 fs. The X-ray absorption difference spectra, with and without the pump pulses, are independent of time delay after 1.5 ps up to 100 ps, indicating that the photoexcited species is long-lived.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    SciTech Connect

    Citron, Robert; Kropf, A.J.

    2008-01-01

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

  4. ISMabs: A Comprehensive X-Ray Absorption Model for the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Gatuzz, E.; García, J.; Kallman, T. R.; Mendoza, C.; Gorczyca, T. W.

    2015-02-01

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

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

    SciTech Connect

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

    2015-02-10

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

  6. The effects of dust scattering on high-resolution X-ray absorption edge structure

    NASA Astrophysics Data System (ADS)

    Corrales, Lia; Garcia, Javier; Wilms, Joern; Baganoff, Frederick K.

    2016-04-01

    In high resolution X-ray spectroscopy, dust scattering significantly enhances the total extinction optical depth and alters the shape of photoelectric absorption edges. This effect is modulated by the dust grain size distribution, spatial location along the line of sight, and the imaging resolution of the X-ray telescope. We focus in particular on the Fe L-edge at 0.7 keV, fitting a template for the total extinction to the high resolution spectrum of three X-ray binaries from the Chandra archive: GX 9+9, XTE J1817-330, and Cyg X-1. In cases where dust is intrinsic to the source, a covering factor based on the angular extent of the dusty material must be applied to the extinction curve, regardless of imaging resolution. We discuss the various astrophysical cases in which scattering effects need to be taken into account.

  7. Gas cell for in situ soft X-ray transmission-absorption spectroscopy of materials

    SciTech Connect

    Drisdell, W. S.; Kortright, J. B.

    2014-07-15

    A simple gas cell design, constructed primarily from commercially available components, enables in situ soft X-ray transmission-absorption spectroscopy of materials in contact with gas at ambient temperature. The cell has a minimum X-ray path length of 1 mm and can hold gas pressures up to ∼300 Torr, and could support higher pressures with simple modifications. The design enables cycling between vacuum and gas environments without interrupting the X-ray beam, and can be fully sealed to allow for measurements of air-sensitive samples. The cell can attach to the downstream port of any appropriate synchrotron beamline, and offers a robust and versatile method for in situ measurements of certain materials. The construction and operation of the cell are discussed, as well as sample preparation and proper spectral analysis, illustrated by examples of spectral measurements. Potential areas for improvement and modification for specialized applications are also mentioned.

  8. Photoelectron interference fringes by super intense x-ray laser pulses

    NASA Astrophysics Data System (ADS)

    Toyota, Koudai; Tolstikhin, Oleg I.; Morishita, Toru; Watanabe, Shinichi

    2009-09-01

    The photoelectron spectra of H- produced by circularly polarized strong high-frequency laser pulses are theoretically studied. An oscillating substructure in the above-threshold ionization (ATI) peaks is observed, which extends the validity of the earlier findings in the 1D calculations [K. Toyota et al., Phys. Rev. A 76, 043418 (2007)] and 3D calculations for linear polarization [O. I. Tolstikhin, Phys. Rev. A 77, 032712 (2008)]. Its origin is due to an interference between a pair of photoelectron wave packets created in the rising and falling part of the pulse, which appears clearly in the stabilization regime.

  9. X-Ray Absorption Toward the Einstein Ring Source PKS 1830-211

    NASA Technical Reports Server (NTRS)

    Mathur, Smita; Nair, Sunita

    1997-01-01

    PKS 1830-211 is an unusually radio-loud gravitationally lensed quasar. In the radio spectrum, the system appears as two compact, dominant features surrounded by relatively extended radio emission that forms an Einstein ring. As the line of sight to it passes close to our Galactic center, PKS 1830-211 has not been detected in wave bands other than the radio and X-ray so far. Here we present X-ray data of PKS 1830-211 observed with ROSAT Position Sensitive Proportional Counter. The X-ray spectrum shows that absorption in excess of the Galactic contribution is highly likely, which at the redshift of the lensing galaxy (z(sub t)=0.886) corresponds to N(sub H)=3.5((sup 0.6)(sub -0.5))x10(exp 22) atoms sq cm. The effective optical extinction is large, A(sub V)(observed) is greater than or approximately 5.8. When corrected for this additional extinction, the two-point optical to X-ray slope alpha(sub ox) of PKS 1830-211 lies just within the observed range of quasars. It is argued here that both compact images must be covered by the X-ray absorber(s) that we infer to be the lensing galaxy (galaxies). The dust-to-gas ratio along the line of sight within the lensing galaxy is likely to be somewhat larger than for our Galaxy.

  10. Understanding Electrocatalytic Pathways in Low and Medium Temperature Fuel Cells: Synchrotron-based In Situ X-Ray Absorption Spectroscopy

    SciTech Connect

    Mukerjee, S.; Ziegelbauer, J; Arruda, T; Ramaker, D; Shyam, B

    2008-01-01

    transmission beams respectively. When the energy of the incident X-rays exceed the electron binding energy (E{sub 0}) of the element under investigation, the electron is ejected from the core to available excited states in the form of a photoelectron with kinetic energy: E{sub k} = h? - E{sub 0} (2) with, E{sub k} being the kinetic energy of the released photoelectron and h? the energy of the incident beam. In general, the X-ray absorption spectrum is broken down into two distinct energy regions: the X-ray absorption near-edge structure or XANES (-50eV {le} E{sub 0} {le} 50eV) and the extended X-ray absorption fine-structure or EXAFS (50eV {le} E{sub 0} {le} {approx}1000eV). The XANES region is dominated by low-energy photoelectrons which undergo multiple scattering events. As such, it can reveal information about oxidation state, local symmetry, electronic structure, and the extent of oxidation of a material. Due to this complex multiple scattering, there is no simple XANES equation to describe it quantitatively. However, recent advancements in computers and the evolution of numerical methods such as the FEFF code have made possible reliable XANES simulations. Photoelectrons in the EXAFS region have high enough E{sub k} to undergo primarily single back-scattering events. These back-scattered photoelectrons interfere with the outgoing photoelectrons, causing the oscillations in the absorption spectrum. Using the previously developed EXAFS equations it is now possible to model EXAFS data to determine coordination numbers, bond distances, and mean-square disorder (commonly referred to as Debye-Waller factor). EXAFS data is often shown by Fourier Transforming KSpace into distance, r, space where the total magnitude is plotted against the radial coordinates. This allow for easy qualitative comparison of samples. Employing EXAFS on nanoscale materials has the added advantage that it can quantitatively illustrate changes in atom-atom coordination, which can be related to particle

  11. A X-Ray Absorption Spectroscopy Study of Manganese Containing Compounds and Photosynthetic Spinach Chloroplasts.

    NASA Astrophysics Data System (ADS)

    Kirby, Jon Allan

    The manganese sites in chloroplasts, long thought to be involved in photosynthetic oxygen evolution have been examined and partially characterized by X-ray Absorption Spectroscopy (XAS) using synchrotron radiation. The local environment about the manganese atoms is estimated from an analysis of the extended X-ray Absorption Fine Structure (EXAFS). Comparisons with and simulations of the manganese EXAFS for several reference compounds leads to a model in which the chloroplast manganese atoms are contained in a binuclear complex similar to di-u-oxo -tetrakis-(2,2'-bipyridine) dimanganese. It is suggested that the partner metal is another manganese. The bridging ligands are most probably oxygen. The remaining manganese ligands are carbon, oxygen, or nitrogen. A roughly linear correlation between the X-ray K edge onset energy and the "coordination charge" of a large number of manganese coordination complexes and compounds has been developed. Entry of the chloroplast manganese edge energy onto this correlation diagram establishes that the active pool of manganese is in an oxidation state greater than +2. If the manganese is in a dimeric form the oxidation states are most probably (II,III). Underlying these results is an extensive data analysis methodology. The method developed involves the use of many different background removal techniques, Fourier transforms and ultimately curve fitting to the modulations in the x-ray absorption cross sections. A large number of model compounds were used to evaluate the analysis method. These analyses are used to show that the two major curve fitting models available are essentially equivalent. Due to its greater versatility, the theoretical model of Teo and Lee is preferred (J. Am. Chem. Soc. (1979), 101, 2815). The results are also used to determine the informational limitations of XAS within the limits of the present understanding of X-ray absorption phenomena by inner shell electrons for atoms with atomic number greater than that

  12. Determination of the texture of arrays of aligned carbon nanotubes from the angular dependence of the X-ray emission and X-ray absorption spectra

    SciTech Connect

    Okotrub, A. V. Belavin, V. V.; Bulusheva, L. G.; Gusel'nikov, A. V.; Kudashov, A. G.; Vyalikh, D. V.; Molodtsov, S. L.

    2008-09-15

    The properties of materials containing carbon nanotubes depend on the degree of alignment and the internal structure of nanotubes. It is shown that the degree of misorientation of carbon nanotubes in samples can be evaluated from the measurements of the angular dependences of the carbon X-ray emission and carbon X-ray absorption spectra. The CK{sub {alpha}} emission and CK X-ray absorption spectra of the array of multiwalled carbon nanotubes synthesized by catalytic thermolysis of a mixture of fullerene and ferrocene are measured. A comparison of the calculated model dependences of the relative intensities of the {pi} and {sigma} bands in the spectra with the experimental results makes it possible to evaluate the degree of misorientation of nanotubes in the sample and their internal texture.

  13. Structural characterisation of Ni clusters in AlN via X-ray absorption, X-ray diffraction and transmission electron microscopy

    NASA Astrophysics Data System (ADS)

    Zanghi, D.; Traverse, A.; Dallas, J.-P.; Snoeck, E.

    Ni ions were implanted in bulk AlN with the goal to form embedded metallic clusters. Combining several characterisation techniques such as X-ray absorption spectroscopy, X-ray diffraction and high resolution transmission electron microscopy, we determined the lattice parameter of the Ni clusters that display a fcc crystalline structure. The average size increases when the ion fluence is increased or after a thermal treatment. Thanks to moiré fringes observed by high resolution transmission electron microscopy and to satellite peaks seen on the diffraction patterns, we concluded that the annealed Ni clusters orientate their (002) planes on the (101) of AlN. Moreover, the satellite positions allowed us to calculate Ni cluster average diameters, that are in agreement with average sizes deduced by X-ray absorption spectroscopy.

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

    SciTech Connect

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

    2009-01-01

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

  15. Soft X-Ray Absorption Spectroscopy of High-Abrasion-Furnace Carbon Black

    SciTech Connect

    Muramatsu, Yasuji; Harada, Ryusuke; Gullikson, Eric M.

    2007-02-02

    The soft x-ray absorption spectra of high-abrasion-furnace carbon black were measured to obtain local-structure/chemical-states information of the primary particles and/or crystallites. The soft x-ray absorption spectral features of carbon black represent broader {pi}* and {sigma}* peak structures compared to highly oriented pyrolytic graphite (HOPG). The subtracted spectra between the carbon black and HOPG, (carbon black) - (HOPG), show double-peak structures on both sides of the {pi}* peak. The lower-energy peak, denoted as the 'pre-peak', in the subtracted spectra and the {pi}*/{sigma}* peak intensity ratio in the absorption spectra clearly depend on the specific surface area by nitrogen adsorption (NSA). Therefore, it is concluded that the pre-peak intensity and the {pi}*/{sigma}* ratio reflect the local graphitic structure of carbon black.

  16. X-ray absorption spectroscopy on the basis of hybrid X-pinch radiation

    SciTech Connect

    Tilikin, I. N. Shelkovenko, T. A.; Pikuz, S. A.; Knapp, P. F.; Hammer, D. A.

    2015-07-15

    Results of experiments on X-ray absorption spectroscopy carried out at the BIN (270 kA, 100 ns) and XP (450 kA, 45 ns) facilities are presented. Continuum radiation of a Mo hybrid X-pinch was used as probing radiation, against which absorption lines of the plasma of exploded Al wires placed in the return current circuit of a hybrid X-pinch, as well as in a two- and four-wire array, were observed. The experiments have demonstrated that the radiation of a hybrid X-pinch hot spot can be used as probing radiation for X-ray absorption spectroscopy and that, in many parameters, such a source surpasses those on the basis of laser-produced plasma. The plasma parameters in arrays made of two and four Al wires were studied experimentally.

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

    SciTech Connect

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

    2008-03-08

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

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

    SciTech Connect

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

    2009-05-27

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

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

    PubMed

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

    2014-09-15

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

  20. Investigations on surface chemical analysis using X-ray photoelectron spectroscopy and optical properties of Dy3+-doped LiNa3P2O7 phosphor

    NASA Astrophysics Data System (ADS)

    Munirathnam, K.; Dillip, G. R.; Chaurasia, Shivanand; Joo, S. W.; Deva Prasad Raju, B.; John Sushma, N.

    2016-08-01

    Near white-light emitting LiNa3P2O7:Dy3+ phosphors were prepared by a conventional solid-state reaction method. The orthorhombic crystal structure of the phosphors was confirmed using X-ray diffraction (XRD), and the valence states of the surface elements were determined from the binding energies of Li 1s, O 1s, Na 1s, P 2p, and Dy 3d by X-ray photoelectron spectroscopy (XPS). Attenuated total reflectance (ATR) - Fourier transform infrared (FT-IR) spectroscopy was employed to identify the pyrophosphate groups in the phosphors. Diffuse reflectance spectra (DRS) show the absorption bands of the Dy3+ ions in the host material. Intense blue (481 nm) and yellow (575 nm) emissions were obtained at an excitation wavelength of 351 nm and are attributed to the 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transitions of Dy3+ ions, respectively. The combination of these two intense bands generates light emission in the near-white region of the chromaticity diagram.

  1. A novel X-ray photoelectron spectroscopy study of the Al/SiO2 interface

    NASA Technical Reports Server (NTRS)

    Hecht, M. H.; Vasquez, R. P.; Grunthaner, F. J.; Zamani, N.; Maserjian, J.

    1985-01-01

    The nondestructive measurement of the chemical and physical characteristics of the interface between bulk SiO2 and thick aluminum films is reported. Both X-ray phototelectron spectroscopy (XPS) and electrical measurements of unannealed, resistively evaporated Al films on thermal SiO2 indicate an atomically abrupt interface. Post metallization annealing at 450 C induces reduction of the SiO2 by the aluminum, at a rate consistent with the bulk reaction rate. The XPS measurement is performed from the SiO2 side after the removal of the Si substrate with XeF2 gas and thinning of the SiO2 layer with HF:ETOH. This represents a powerful new approach to the study of metal-insulator and related interfaces.

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

    PubMed

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

    2007-04-10

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

  3. Measurement of c-axis angular orientation in calcite (CaCO3) nanocrystals using X-ray absorption spectroscopy

    PubMed Central

    Gilbert, P. U. P. A.; Young, Anthony; Coppersmith, Susan N.

    2011-01-01

    We demonstrate that the ability to manipulate the polarization of synchrotron radiation can be exploited to enhance the capabilities of X-ray absorption near-edge structure (XANES) spectroscopy, to include linear dichroism effects. By acquiring spectra at the same photon energies but different polarizations, and using a photoelectron emission spectromicroscope (PEEM), one can quantitatively determine the angular orientation of micro- and nanocrystals with a spatial resolution down to 10 nm. XANES-PEEM instruments are already present at most synchrotrons, hence these methods are readily available. The methods are demonstrated here on geologic calcite (CaCO3) and used to investigate the prismatic layer of a mollusk shell, Pinctada fucata. These XANES-PEEM data reveal multiply oriented nanocrystals within calcite prisms, previously thought to be monocrystalline. The subdivision into multiply oriented nanocrystals, spread by more than 50°, may explain the excellent mechanical properties of the prismatic layer, known for decades but never explained. PMID:21693647

  4. Complex X-ray Absorption and the Fe K(alpha) Profile in NGC 3516

    NASA Technical Reports Server (NTRS)

    Turner, T. J.; Kraemer, S. B.; George, I. M.; Reeves, J. N.; Botorff, M. C.

    2004-01-01

    We present data from simultaneous Chandra, XMM-Newton and BeppoSAX observations of the Seyfert 1 galaxy NGC 3516, taken during 2001 April and November. We have investigated the nature of the very flat observed X-ray spectrum. Chandra grating data show the presence of X-ray absorption lines, revealing two distinct components of the absorbing gas, one which is consistent with our previous model of the UV/X-ray absorber while the other, which is outflowing at a velocity of approximately 1100 kilometers per second, has a larger column density and is much more highly ionized. The broad-band spectral characteristics of the X-ray continuum observed with XMM during 2001 April, reveal the presence of a third layer of absorption consisting of a very large column (approximately 2.5 x 10(exp 23) per square centimeter) of highly ionized gas with a covering fraction approximately 50%. This low covering fraction suggests that the absorber lies within a few 1t-days of the X-ray source and/or is filamentary in structure. Interestingly, these absorbers are not in thermal equilibrium with one another. The two new components are too highly ionized to be radiatively accelerated, which we suggest is evidence for a hydromagnetic origin for the outflow. Applying our model to the November dataset, we can account for the spectral variability primarily by a drop in the ionization states of the absorbers, as expected by the change in the continuum flux. When this complex absorption is accounted for we find the underlying continuum to be typical of Seyfert 1 galaxies. The spectral curvature attributed to the high column absorber, in turn, reduces estimates of the flux and extent of any broad Fe emission line from the accretion disk.

  5. X-ray photoelectron spectroscopy analysis of cleaning procedures for synchrotron radiation beamline materials at the Advanced Photon Source

    SciTech Connect

    Li, Y.; Ryding, D.; Liu, C.; Kuzay, T.M.; McDowell, M.W.; Rosenberg, R.A.

    1995-05-01

    TZM (a high-temperature molybdenum alloy), machinable tungsten, and 304 stainless steel were cleaned using environmentally safe, commercially available cleaning detergents. The surface cleanliness was evaluated by x-ray photoelectron spectroscopy. It was found that a simple alkaline detergent is very effective at removal of organic and inorganic surface contaminants or foreign particle residue from machining processes. The detergent can be used with ultrasonic agitation at 140 {degree}F to clean the TZM molybdenum, machinable tungsten, and 304 stainless steel. A citric-acid-based detergent was also found to be effective at cleaning metal oxides, such as iron oxide, molybdenum oxide, as well as tungsten oxides, at mild temperatures with ultrasonic agitation, and it can be used to replace strong inorganic acids to improve cleaning safety and minimize waste disposal and other environmental problems. The efficiency of removing the metal oxides depends on both cleaning temperature and time. {copyright} {ital 1995} {ital American} {ital Vacuum} {ital Society}

  6. X-Ray Photoelectron Spectroscopy Depth Profiling of Electrochemically Prepared Thin Oxide Layers on Duplex Stainless Steel

    NASA Astrophysics Data System (ADS)

    Donik, Črtomir; Kocijan, Aleksandra; Mandrino, Djordje; Jenko, Monika

    2011-10-01

    The surface oxidation of duplex stainless steel (DSS 2205) was studied by X-ray photoelectron spectroscopy (XPS). The experiments were performed on the alloy after controlled oxidation in a chloride-enriched solution at controlled potentials. The evolution of the passive film formed on the DSS in a chloride solution was studied using cyclic voltammetry with XPS surface characterization at selected potentials. The evolution of the oxide films and its specific compositions formed on the DSS was studied as a function of depth. Fe/Cr oxidized layers and oxide thicknesses were observed and correlated with the various potentiostatic potentials. The importance of Mo and Cr inside the oxide films in this article is studied and described, whereas their role in the protective layer, as oxides, is significant.

  7. Understanding Chemical versus Electrostatic Shifts in X-ray Photoelectron Spectra of Organic Self-Assembled Monolayers

    PubMed Central

    2016-01-01

    The focus of the present article is on understanding the insight that X-ray photoelectron spectroscopy (XPS) measurements can provide when studying self-assembled monolayers. Comparing density functional theory calculations to experimental data on deliberately chosen model systems, we show that both the chemical environment and electrostatic effects arising from a superposition of molecular dipoles influence the measured core-level binding energies to a significant degree. The crucial role of the often overlooked electrostatic effects in polar self-assembled monolayers (SAMs) is unambiguously demonstrated by changing the dipole density through varying the SAM coverage. As a consequence of this effect, care has to be taken when extracting chemical information from the XP spectra of ordered organic adsorbate layers. Our results, furthermore, imply that XPS is a powerful tool for probing local variations in the electrostatic energy in nanoscopic systems, especially in SAMs. PMID:26937264

  8. X-ray photoelectron spectroscopy study on the chemistry involved in tin oxide film growth during chemical vapor deposition processes

    SciTech Connect

    Mannie, Gilbere J. A.; Gerritsen, Gijsbert; Abbenhuis, Hendrikus C. L.; Deelen, Joop van; Niemantsverdriet, J. W.; Thuene, Peter C.

    2013-01-15

    The chemistry of atmospheric pressure chemical vapor deposition (APCVD) processes is believed to be complex, and detailed reports on reaction mechanisms are scarce. Here, the authors investigated the reaction mechanism of monobutyl tinchloride (MBTC) and water during SnO{sub 2} thin film growth using x-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). XPS results indicate an acid-base hydrolysis reaction mechanism, which is tested with multilayer experiments, demonstrating self-terminating growth. In-house developed TEM wafers are used to visualize nucleation during these multilayer experiments, and results are compared with TEM results of APCVD samples. Results show almost identical nucleation behavior implying that their growth mechanism is identical. Our experiments suggest that in APCVD, when using MBTC and water, SnO{sub 2} film growth occurs via a heterolytic bond splitting of the Sn-Cl bonds without the need to invoke gas-phase radical or coordination chemistry of the MBTC precursor.

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

    SciTech Connect

    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.

  10. Employing X-ray Photoelectron Spectroscopy for Determining Layer Homogeneity in Mixed Polar Self-Assembled Monolayers

    PubMed Central

    2016-01-01

    Self-assembled monolayers (SAMs) containing embedded dipolar groups offer the particular advantage of changing the electronic properties of a surface without affecting the SAM–ambient interface. Here we show that such systems can also be used for continuously tuning metal work functions by growing mixed monolayers consisting of molecules with different orientations of the embedded dipolar groups. To avoid injection hot-spots when using the SAM-modified electrodes in devices, a homogeneous mixing of the two components is crucial. We show that a combination of high-resolution X-ray photoelectron spectroscopy with state-of-the-art simulations is an ideal tool for probing the electrostatic homogeneity of the layers and thus for determining phase separation processes in polar adsorbate assemblies down to inhomogeneities at the molecular level. PMID:27429041

  11. Band alignment of Ga2O3/Si heterojunction interface measured by X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Zhengwei; Nishihagi, Kazuo; Wang, Xu; Saito, Katsuhiko; Tanaka, Tooru; Nishio, Mitsuhiro; Arita, Makoto; Guo, Qixin

    2016-09-01

    Ga2O3 thin films were deposited on (111) Si substrate by pulsed laser deposition method. X-ray photoelectron spectroscopy has been used to determine the valence band offset at Ga2O3/Si heterojunction interface. We measured the binding energies of Si 2p and Ga 2p3/2 core levels and the valence band maxima energies. The valence band offset is determined to be 3.5 ± 0.1 eV. As a consequence a type Ι heterojunction with a conduction band offset of 0.2 ± 0.1 eV is found. The determination of the band alignment of Ga2O3/Si heterojunction facilitates the design of optical and electronic devices based on the Ga2O3/Si structure.

  12. X-ray photoelectron spectroscopy analysis of cleaning procedures for synchrotron radiation beamline materials at the Advanced Photon Source

    SciTech Connect

    Li, Y.; Ryding, D.; Liu, C.; Kuzay, T.M.; McDowell, M.W.; Rosenberg, R.A.

    1994-12-31

    TZM (a high temperature molybdenum alloy), machinable tungsten, and 304 stainless steel were cleaned using environmentally safe, commercially available cleaning detergents. The surface cleanliness was evaluated by x-ray photoelectron spectroscopy (XPS). It was found that a simple alkaline detergent is very effective at removal of organic and inorganic surface contaminants or foreign particle residue from machining processes. The detergent can be used with ultrasonic agitation at 140 F to clean the TZM molybdenum, machinable tungsten, and 304 stainless steel. A citric-acid-based detergent was also found to be effective at cleaning metal oxides, such as iron oxide, molybdenum oxide, as well as tungsten oxides at mild temperatures with ultrasonic agitation, and it can be used to replace strong inorganic acids to improve cleaning safety and minimize waste disposal and other environmental problems. The efficiency of removing the metal oxides depends on both cleaning temperature and time.

  13. Thermal stability of electron-irradiated poly(tetrafluoroethylene) - X-ray photoelectron and mass spectroscopic study

    NASA Technical Reports Server (NTRS)

    Wheeler, Donald R.; Pepper, Stephen V.

    1990-01-01

    Polytetrafluoroethylene (PTFE) was subjected to 3 keV electron bombardment and then heated in vacuum to 300 C. The behavior of the material as a function of radiation dose and temperature was studied by X-ray photoelectron spectroscopy (XPS) of the surface and mass spectroscopy of the species evolved. Lightly damaged material heated to 300 C evolved saturated fluorocarbon species, whereas unsaturated fluorocarbon species were evolved from heavily damaged material. After heating the heavily damaged material, those features in the XPS spectrum that were associated with damage diminished, giving the appearance that the radiation damage had annealed. The observations were interpreted by incorporating mass transport of severed chain fragments and thermal decomposition of severely damaged material into the branched and cross-linked network model of irradiated PTFE. The apparent annealing of the radiation damage was due to covering of the network by saturated fragments that easily diffused through the decomposed material to the surface region upon heating.

  14. Band alignment at a MgO/GaSb heterointerface using x-ray photoelectron spectroscopy measurements

    NASA Astrophysics Data System (ADS)

    Li, Ruxue; Wei, Zhipeng; Liu, Xue; Li, Yongfeng; Fang, Xuan; Tang, Jilong; Fang, Dan; Gao, Xian; Wang, Dengkui; Hao, Yongqin; Yao, Bin; Ma, Xiaohui; Wang, Xiaohua

    2016-07-01

    The valence band offset (ΔE V) of a MgO/GaSb heterostructure was determined using x-ray photoelectron spectroscopy measurements. A ΔE V value of 2.84 ± 0.10 eV was calculated by using Ga 3d3/2 and Mg 2p1/2 binding energies as references. Taking the empirical band gaps of 7.83 eV and 0.73 eV for MgO and GaSb thin films into consideration, respectively, we obtained the type-I band alignment of a MgO/GaSb heterostructure with a conduction band offset (ΔE c) of 4.26 ± 0.10 eV, suggesting a nested interface band alignment.

  15. Application of ESCA to the determination of stoichiometry in sputtered coatings and interface regions. [X-ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Wheeler, D. R.

    1978-01-01

    X-ray Photoelectron Spectroscopy (XPS) was used to characterize radiofrequency sputter deposited films of several refractory compounds. Both the bulk film properties such as purity and stoichiometry and the character of the interfacial region between the film and substrate were examined. The materials were CrB2, MoS2, Mo2C, and Mo2B5 deposited on 440C steel. It was found that oxygen from the sputtering target was the primary impurity in all cases. Biasing improves the film purity. The effect of biasing on film stoichiometry is different for each compound. Comparison of the interfacial composition with friction data suggests that adhesion of these films is improved if a region of mixed film and iron oxides can be formed.

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

    SciTech Connect

    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.

  17. Probing buried organic-organic and metal-organic heterointerfaces by hard x-ray photoelectron spectroscopy

    SciTech Connect

    Shibuta, Masahiro; Eguchi, Toyoaki; Watanabe, Yoshio; Nakajima, Atsushi; Son, Jin-Young; Oji, Hiroshi

    2012-11-26

    We present a nondestructive characterization method for buried hetero-interfaces for organic/organic and metal/organic systems using hard x-ray photoelectron spectroscopy (HAXPES) which can probe electronic states at depths deeper than {approx}10 nm. A significant interface-derived signal showing a strong chemical interaction is observed for Au deposited onto a C{sub 60} film, while there is no such additional feature for copper phthalocyanine deposited onto a C{sub 60} film reflecting the weak interaction between the molecules in the latter case. A depth analysis with HAXPES reveals that a Au-C{sub 60} intermixed layer with a thickness of 5.1 nm is formed at the interface.

  18. X-ray photoelectron spectroscopy study of cubic boron nitride single crystals grown under high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Hou, Lixin; Chen, Zhanguo; Liu, Xiuhuan; Gao, Yanjun; Jia, Gang

    2012-02-01

    The defects, impurities and their bonding states of unintentionally doped cubic boron nitride (cBN) single crystals were investigated by X-ray photoelectron spectroscopy (XPS). The results indicate that nitrogen vacancy (VN) is the main native defect of the cBN crystals since the atomic ratio of B:N is always larger than 1 before Ar ion sputtering. After sputter cleaning, around 6 at% carbon, which probably comes from the growth chamber, remains in the samples as the main impurity. Carbon can substitute nitrogen lattice site and form the bonding states of Csbnd Bsbnd N or Csbnd B, which can be verified by the XPS spectra of C1s, B1s and N1s. The C impurity (acceptor) and N vacancy (donor) can compose the donor-acceptor complex to affect the electrical and optical properties of cBN crystals.

  19. X-ray photoelectron spectroscopy study of para-substituted benzoic acids chemisorbed to aluminum oxide thin films

    SciTech Connect

    Kreil, Justin; Ellingsworth, Edward; Szulczewski, Greg

    2013-11-15

    A series of para-substituted, halogenated (F, Cl, Br, and I) benzoic acid monolayers were prepared on the native oxide of aluminum surfaces by solution self-assembly and spin-coating techniques. The monolayers were characterized by x-ray photoelectron spectroscopy (XPS) and water contact angles. Several general trends are apparent. First, the polarity of the solvent is critical to monolayer formation. Protic polar solvents produced low coverage monolayers; in contrast, nonpolar solvents produced higher coverage monolayers. Second, solution deposition yields a higher surface coverage than spin coating. Third, the thickness of the monolayers determined from XPS suggests the plane of the aromatic ring is perpendicular to the surface with the carboxylate functional group most likely binding in a bidentate chelating geometry. Fourth, the saturation coverage (∼2.7 × 10{sup 14} molecules cm{sup −2}) is independent of the para-substituent.

  20. Effects of proton irradiation on single-stranded DNA studied by using X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Lee, E.; Lee, Cheol Eui; Han, J. H.

    2016-08-01

    X-ray photoelectron spectroscopy (XPS) has been employed in order to study the effects of proton irradiation on herring sperm single-stranded DNA. Systematic changes of the chemical shifts in the C, N, O, and P XPS line components as functions of the irradiation dose were observed, indicative of the bonding configurations in the DNA system. While the C 1 s XPS lines showed weak blueshifts, the N 1 s, O 1 s, and P 2 p XPS lines showed blueshifts with a marked dependence on the irradiation dose in a prominent manner. Our results show that linear energy transfer by charged particles and photons may have distinct molecular-level effects as the C 1 s, N 1 s, O 1 s, and P 2 p XPS lines showed redshifts in our previous study of effects of the γ-ray irradiation on the same system.

  1. X-ray photoelectron spectroscopy study of disordering in Gd2(Ti1-xZrx)2O7 pyrochlores.

    PubMed

    Chen, J; Lian, J; Wang, L M; Ewing, R C; Wang, R G; Pan, W

    2002-03-11

    The dramatic increases in ionic conductivity in Gd2(Ti1-xZrx)2O7 solid solution are related to disordering on the cation and anion lattices. Disordering in Gd2(Ti1-xZrx)2O7 was characterized using x-ray photoelectron spectroscopy (XPS). As Zr substitutes for Ti in Gd2Ti2O7 to form Gd2(Ti1-xZrx)2O7 (0.25 < x < or =0.75), the corresponding O 1s XPS spectrum merges into a single symmetric peak. This confirms that the cation antisite disorder occurs simultaneously with anion disorder. Furthermore, the O 1s XPS spectrum of Gd2Zr2O7 experimentally suggests the formation of a split vacancy.

  2. X-ray Photoelectron Spectroscopy Study of Disordering in Gd2(Ti1-xZrx)2O7 Pyrochlores

    NASA Astrophysics Data System (ADS)

    Chen, J.; Lian, J.; Wang, L. M.; Ewing, R. C.; Wang, R. G.; Pan, W.

    2002-03-01

    The dramatic increases in ionic conductivity in Gd2(Ti1-xZrx)2O7 solid solution are related to disordering on the cation and anion lattices. Disordering in Gd2(Ti1-xZrx)2O7 was characterized using x-ray photoelectron spectroscopy (XPS). As Zr substitutes for Ti in Gd2Ti2O7 to form Gd2(Ti1-xZrx)2O7 (0.25

  3. Employing X-ray Photoelectron Spectroscopy for Determining Layer Homogeneity in Mixed Polar Self-Assembled Monolayers.

    PubMed

    Hehn, Iris; Schuster, Swen; Wächter, Tobias; Abu-Husein, Tarek; Terfort, Andreas; Zharnikov, Michael; Zojer, Egbert

    2016-08-01

    Self-assembled monolayers (SAMs) containing embedded dipolar groups offer the particular advantage of changing the electronic properties of a surface without affecting the SAM-ambient interface. Here we show that such systems can also be used for continuously tuning metal work functions by growing mixed monolayers consisting of molecules with different orientations of the embedded dipolar groups. To avoid injection hot-spots when using the SAM-modified electrodes in devices, a homogeneous mixing of the two components is crucial. We show that a combination of high-resolution X-ray photoelectron spectroscopy with state-of-the-art simulations is an ideal tool for probing the electrostatic homogeneity of the layers and thus for determining phase separation processes in polar adsorbate assemblies down to inhomogeneities at the molecular level. PMID:27429041

  4. X-ray photoelectron spectroscopy as a probe of the interaction between rhodium acetate and ionic liquids

    NASA Astrophysics Data System (ADS)

    Men, Shuang; Jiang, Jing

    2016-02-01

    X-ray photoelectron spectroscopy (XPS) is used as a probe of the interaction between rhodium acetate ([Rh2(OAc)4]) and ionic liquids. Due to the impact of the anion of ionic liquids on the electronic environment of the rhodium centre, the measured Rh 3d binding energies of [Rh2(OAc)4] dissolved in a series of ionic liquids were found to decrease along with the increasing of the basicity of anions. The reduction of Rh(II) to Rh(0) in 1-octyl-3methylimidazolium acetate ([C8C1Im][OAc]) under UHV condition was monitored by XPS. The intensity of the new formed metallic Rh(0) peak was found increased along with time. The surface enrichment of the new formed Rh(0) species in the system was also concluded.

  5. XPS studies of structure-induced radiation effects at the Si/SiO2 interface. [X ray Photoelectron Spectroscopy

    NASA Technical Reports Server (NTRS)

    Grunthaner, F. J.; Lewis, B. F.; Zamini, N.; Maserjian, J.; Madhukar, A.

    1980-01-01

    The interfacial structures of radiation hard and soft oxides grown by dry and wet processes on silicon substrates have been examined by high-resolution X-ray photoelectron spectroscopy. It is found that the primary difference in the local atomic structure at the Si/SiO2 interface is the significantly higher concentration of strained 120 deg SiO2 bonds and SiO interfacial species in soft samples. Results of in situ radiation damage experiments using low energy electrons (0-20 eV) are reported which correlate with the presence of a strained layer of SiO2 (20 A) at the interface. The results are interpreted in terms of a structural model for hole and electron trap generation by ionizing radiation.

  6. Mixed adlayer of alkanethiol and peptide on GaAs(100): quantitative characterization by X-ray photoelectron spectroscopy.

    PubMed

    Wampler, Heeyeon P; Zemlyanov, Dmitry Y; Lee, Kangho; Janes, David B; Ivanisevic, Albena

    2008-04-01

    Homogeneous and mixed adlayers composed of an alkanethiol (1-octadecanethiol, ODT) and a peptide (CGISYGRKKRRQRRR) on GaAs(100) were formed in two different solvent systems: phosphate-buffered saline (PBS) and N,N-dimethylformamide (DMF). The chemical composition of each adlayer was characterized by X-ray photoelectron spectroscopy (XPS). The data showed that the makeup of the adlayer and its stability largely depends on the solvent used. Angle-resolved XPS also revealed that the adlayer thickness and tilt angles were different from values obtained from ellipsometry measurements and vastly varied between the two solvents used. The coverage data extracted from the XPS measurements indicated that homogeneous adlayers of peptide in PBS buffer form a multilayered film. Homogeneous alkanethiol adlayers exhibited monolayer coverage under all solvent treatments. Coadsorbed layers containing both alkanethiol and peptide have fractional monolayer coverage in both solvents. PMID:18275237

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  8. Surface relaxation in liquid water and methanol studied by x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Wilson, Kevin R.; Schaller, R. D.; Co, D. T.; Saykally, R. J.; Rude, Bruce S.; Catalano, T.; Bozek, J. D.

    2002-10-01

    X-ray absorption spectroscopy is a powerful probe of local electronic structure in disordered media. By employing extended x-ray absorption fine structure spectroscopy of liquid microjets, the intermolecular O-O distance has been observed to undergo a 5.9% expansion at the liquid water interface, in contrast to liquid methanol for which there is a 4.6% surface contraction. Despite the similar properties of liquid water and methanol (e.g., abnormal heats of vaporization, boiling points, dipole moments, etc.), this result implies dramatic differences in the surface hydrogen bond structure, which is evidenced by the difference in surface tension of these liquids. This result is consistent with surface vibrational spectroscopy, which indicates both stronger hydrogen bonding and polar ordering at the methanol surface as a consequence of "hydrophobic packing" of the methyl group.

  9. Chemical Sensitivity of the Sulfur K-Edge X-ray Absorption Spectra of Organic Disulfides.

    PubMed

    Pickering, Ingrid J; Barney, Monica; Cotelesage, Julien J H; Vogt, Linda; Pushie, M Jake; Nissan, Andrew; Prince, Roger C; George, Graham N

    2016-09-22

    Sulfur K-edge X-ray absorption spectroscopy increasingly is used as a tool to provide speciation information about the sulfur chemical form in complex samples, with applications ranging from fossil fuels to soil science to health research. As part of an ongoing program of systematic investigations of the factors that affect the variability of sulfur K near-edge spectra, we have examined the X-ray absorption spectra of a series of organic symmetric disulfide compounds. We have used polarized sulfur K-edge spectra of single crystals of dibenzyl disulfide to confirm the assignments of the major transitions in the spectrum as 1s → (S-S)σ* and 1s → (S-C)σ*. We also have examined the solution spectra of an extended series of disulfides and show that the spectra change in a systematic and predictable manner with the nature of the external group. PMID:27571342

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

    PubMed

    Dimakis, Nicholas; Bunker, Grant

    2006-12-01

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

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

    PubMed

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

    2016-09-14

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

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

    PubMed

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

    2016-09-14

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

  13. Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy

    SciTech Connect

    Schwanke, C.; Lange, K. M.; Golnak, R.; Xiao, J.

    2014-10-15

    A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl{sub 2} aqueous solution by X-ray absorption and emission spectroscopy is presented.

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

    SciTech Connect

    Westre, T.E.

    1996-01-01

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

  15. Picosecond time-resolved X-ray absorption spectroscopy of ultrafast aluminum plasmas.

    PubMed

    Audebert, P; Renaudin, P; Bastiani-Ceccotti, S; Geindre, J-P; Chenais-Popovics, C; Tzortzakis, S; Nagels-Silvert, V; Shepherd, R; Matsushima, I; Gary, S; Girard, F; Peyrusse, O; Gauthier, J-C

    2005-01-21

    We have used point-projection K-shell absorption spectroscopy to infer the ionization and recombination dynamics of transient aluminum plasmas. Two femtosecond beams of the 100 TW laser at the LULI facility were used to produce an aluminum plasma on a thin aluminum foil (83 or 50 nm), and a picosecond x-ray backlighter source. The short-pulse backlighter probed the aluminum plasma at different times by adjusting the delay between the two femtosecond driving beams. Absorption x-ray spectra at early times are characteristic of a dense and rather homogeneous plasma. Collisional-radiative atomic physics coupled with hydrodynamic simulations reproduce fairly well the measured average ionization as a function of time. PMID:15698184

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    SciTech Connect

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

    1996-07-01

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

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

    SciTech Connect

    Paesler, M.; Sayers, D.

    1988-12-01

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

  19. X-ray absorption spectroscopy beyond the core-hole lifetime

    SciTech Connect

    Haemaelaeinen, K.; Hastings, J.B.; Siddons, D.P.; Berman, L.

    1992-10-01

    A new technique to overcome the core-hole lifetime broadening in x-ray absorption spectroscopy is presented. It utilizes a high resolution fluorescence spectrometer which can be used to analyze the fluorescence photon energy with better resolution than the natural lifetime width. Furthermore, the high resolution spectrometer can also be used to select the final state in the fluorescence process which can offer spin selectivity even without long range magnetic order in the sample.

  20. X-ray absorption spectroscopy beyond the core-hole lifetime

    SciTech Connect

    Haemaelaeinen, K.; Hastings, J.B.; Siddons, D.P.; Berman, L.

    1992-01-01

    A new technique to overcome the core-hole lifetime broadening in x-ray absorption spectroscopy is presented. It utilizes a high resolution fluorescence spectrometer which can be used to analyze the fluorescence photon energy with better resolution than the natural lifetime width. Furthermore, the high resolution spectrometer can also be used to select the final state in the fluorescence process which can offer spin selectivity even without long range magnetic order in the sample.

  1. X-ray absorption spectroscopy studies on magnetic tunnel junctions with AlO and AlN tunnel barriers

    SciTech Connect

    Mun, B. S.; Moon, J. C.; Hong, S. W.; Kang, K. S.; Kim, K.; Kim, T. W.; Ju, H. L.

    2006-04-15

    X-ray photoelectron spectroscopy (XPS) and x-ray absorption spectroscopy (XAS) measurements of the optimized magnetic tunnel junctions (MTJs) with AlO and AlN barriers have been performed to study the chemical structures of the barrier and the underlying layer. These MTJs with AlO and AlN barriers exhibited increased tunneling magnetoresistance (TMR) after annealing at 200 deg. C from 27% to 45% and from 25% to 33%, respectively. Surprisingly, the XPS and XAS measurements confirmed that both the as-grown and the annealed MTJs had metallic Co and Fe at the interface between the barrier and the underlying CoFe layer. After annealing, under-stoichiometric AlO{sub x} and AlN{sub x} phases in MTJs with AlO and AlN barriers partially transformed into stoichiometric Al{sub 2}O{sub 3} and AlN phases, respectively. Thus the increase in TMR after annealing for MTJs with clean interface between the barrier and the underlying layer is believed due to the anion redistribution inside the barrier layer, not from back diffusion from pinned magnetic layer to barrier layer.

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

    SciTech Connect

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

    1998-02-15

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

  3. On the relation between X-ray absorption and optical extinction in AGN

    NASA Astrophysics Data System (ADS)

    Ordovás-Pascual, Ignacio; Mateos, Silvia; Carrera, Francisco J.; Wiersema, Klaas; Caccianiga, Alessandro; Severgnini, Paola; Della Ceca, Roberto; Ballo, Lucia; Moretti, Alberto

    2016-08-01

    According to the Unified Model of Active Galactic Nuclei (AGN), an X-ray unabsorbed AGN should appear as unobscured in the optical (Type-1) and viceversa (Type-2). However, there is an important fraction (10-30%) of AGN whose optical and X-ray classifications do not match. To provide insight into the origin of such apparent discrepancies, we have conducted two analyses: 1) a detailed study of the UV-to-near-IR emission of two X-ray unabsorbed Type-2 AGN drawn from the Bright Ultra-Hard XMM-Newton Survey (BUXS); 2) a statistical analysis of the optical obscuration and X-ray absorption properties of 159 Type-1 AGN drawn from BUXS to determine the distribution of dust-to-gas ratios in AGN over a broad range of luminosities and redshifts. In our works we have also determined the impact of contamination from the AGN hosts in the optical classification of AGNs. Our studies are already provided very exciting results such as the detection of objects with extreme dust-to-gas ratios, between 300-10000 times below the Galactic dust-to-gas ratio.

  4. Toward picosecond time-resolved X-ray absorption studies of interfacial photochemistry

    NASA Astrophysics Data System (ADS)

    Gessner, Oliver; Mahl, Johannes; Neppl, Stefan

    2016-05-01

    We report on the progress toward developing a novel picosecond time-resolved transient X-ray absorption spectroscopy (TRXAS) capability for time-domain studies of interfacial photochemistry. The technique is based on the combination of a high repetition rate picosecond laser system with a time-resolved X-ray fluorescent yield setup that may be used for the study of radiation sensitive materials and X-ray spectroscopy compatible photoelectrochemical (PEC) cells. The mobile system is currently deployed at the Advanced Light Source (ALS) and may be used in all operating modes (two-bunch and multi-bunch) of the synchrotron. The use of a time-stamping technique enables the simultaneous recording of TRXAS spectra with delays between the exciting laser pulses and the probing X-ray pulses spanning picosecond to nanosecond temporal scales. First results are discussed that demonstrate the viability of the method to study photoinduced dynamics in transition metal-oxide semiconductor (SC) samples under high vacuum conditions and at SC-liquid electrolyte interfaces during photoelectrochemical water splitting. Opportunities and challenges are outlined to capture crucial short-lived intermediates of photochemical processes with the technique. This work was supported by the Department of Energy Office of Science Early Career Research Program.

  5. X-Ray Absorption Spectroscopy Of Thin Foils Irradiated By An Ultra-short Laser Pulse

    NASA Astrophysics Data System (ADS)

    Renaudin, P.; Lecherbourg, L.; Blancard, C.; Cossé, P.; Faussurier, G.; Audebert, P.; Bastiani-Ceccotti, S.; Geindre, J.-P.; Shepherd, R.

    2007-08-01

    Point-projection K-shell absorption spectroscopy has been used to measure absorption spectra of transient plasma created by an ultra-short laser pulse. The 1s-2p and 1s-3p absorption lines of weakly ionized aluminum and the 2p-3d absorption lines of bromine were measured over an extended range of densities in a low-temperature regime. Independent plasma characterization was obtained using frequency domain interferometry diagnostic (FDI) that allows the interpretation of the absorption spectra in terms of spectral opacities. Assuming local thermodynamic equilibrium, spectral opacity calculations have been performed using the density and temperature inferred from the FDI diagnostic to compare to the measured absorption spectra. A good agreement is obtained when non-equilibrium effects due to non-stationary atomic physics are negligible at the x-ray probe time.

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

    PubMed

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

    2007-07-15

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

  7. Redox Chemisty of Tantalum Clusters on Silica Characterized by X-ray Absorption Spectroscopy

    SciTech Connect

    Nemana,S.; Gates, B.

    2006-01-01

    SiO{sub 2}-supported clusters of tantalum were synthesized from adsorbed Ta(CH{sub 2}Ph){sub 5} by treatment in H{sub 2} at 523 K. The surface species were characterized by X-ray absorption spectroscopy (extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES)) and ultraviolet-visible spectroscopy. The EXAFS data show that SiOO{sub 2}-supported tantalum clusters were characterized by a Ta-Ta coordination number of approximately 2, consistent with the presence of tritantalum clusters, on average. When these were reduced in H{sub 2} and reoxidized in O{sub 2}, the cluster nuclearity remained essentially unchanged, although reduction and oxidation occurred, respectively, as shown by XANES and UV-vis spectra; in the reoxidation, the tantalum oxidation state change was approximately two electronic charges per tritantalum cluster. The data demonstrate an analogy between the chemistry of group 5 metals on the SiO{sub 2} support and their chemistry in solution, as determined by the group of Cotton.

  8. STRONG EVOLUTION OF X-RAY ABSORPTION IN THE TYPE IIn SUPERNOVA SN 2010jl

    SciTech Connect

    Chandra, Poonam; Chevalier, Roger A.; Irwin, Christopher M.; Chugai, Nikolai; Fransson, Claes; Soderberg, Alicia M.

    2012-05-01

    We report two epochs of Chandra-ACIS X-ray imaging spectroscopy of the nearby bright Type IIn supernova SN 2010jl, taken around two months and then a year after the explosion. The majority of the X-ray emission in both spectra is characterized by a high temperature ({approx}> 10 keV) and is likely to be from the forward shocked region resulting from circumstellar interaction. The absorption column density in the first spectrum is high ({approx}10{sup 24} cm{sup -2}), more than three orders of magnitude higher than the Galactic absorption column, and we attribute it to absorption by circumstellar matter. In the second epoch observation, the column density has decreased by a factor of three, as expected for shock propagation in the circumstellar medium. The unabsorbed 0.2-10 keV luminosity at both epochs is {approx}7 Multiplication-Sign 10{sup 41} erg s{sup -1}. The 6.4 keV Fe line clearly present in the first spectrum is not detected in the second spectrum. The strength of the fluorescent line is roughly that expected for the column density of circumstellar gas, provided the Fe is not highly ionized. There is also evidence for an absorbed power-law component in both spectra, which we attribute to a background ultraluminous X-ray source.

  9. The effects of dust scattering on high-resolution X-ray absorption edge structure

    NASA Astrophysics Data System (ADS)

    Corrales, L.; García, J.; Wilms, J.; Baganoff, F.

    2016-06-01

    High energy studies of astrophysical dust complement observations of dusty interstellar gas at other wavelengths. With high resolution X-ray spectroscopy, dust scattering significantly enhances the total extinction optical depth and alters the shape of photoelectric absorption edges. This effect is modulated by the dust grain size distribution, spatial location along the line of sight, and the imaging resolution of the X-ray telescope. At soft energies, the spectrum of scattered light is likely to have significant features at the 0.3 keV (C-K), 0.5 keV (O-K), and 0.7 keV (Fe-L) photoelectric absorption edges. This direct probe of ISM dust grain elements will be important for (i) understanding the relative abundances of graphitic grains or PAHs versus silicates, and (ii) measuring the depletion of gas phase elements into solid form. We focus in particular on the Fe-L edge, fitting a template for the total extinction to the high resolution spectrum of three X-ray binaries from the Chandra archive: GX 9+9, XTE J1817-330, and Cyg X-1. We discuss ways in which spectroscopy with XMM can yield insight into dust obscured objects such as stars, binaries, AGN, and foreground quasar absorption line systems.

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

    SciTech Connect

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

    2009-06-03

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

  11. Dissociation of strong acid revisited: X-ray photoelectron spectroscopy and molecular dynamics simulations of HNO3 in water

    SciTech Connect

    Lewis, Tanza; Winter, Berndt; Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.; Hemminger, J. C.

    2011-08-04

    Molecular-level insight into the dissociation of nitric acid in water is obtained from photoelectron X-ray spectroscopy and first-principles molecular dynamics (MD) simulations. Our combined studies reveal surprisingly abrupt changes in solvation configurations of undissociated nitric acid at approximately 4 M concentration. Experimentally, this is inferred from N1s binding energy shifts of HNO3(aq) as a function of concentration, and is associated with variations in the local electronic structure of the nitrogen atom. It also shows up as a discontinuity in the degree of dissociation as a function of concentration, determined here from the N1s photoelectron signal intensity, which can be separately quantified for undissociated HNO3(aq) and dissociated NO3-(aq). Intermolecular interactions within the nitric acid solution are discussed on the basis of MD simulations, which reveal that molecular HNO3 interacts remarkably weakly with solvating water molecules at low concentration; around 4 M there is a turnover to a more structured solvation shell, accompanied by an increase in hydrogen bonding between HNO3 and water. We suggest that the driving force behind the more structured solvent configuration of HNO3 is the overlap of nitric acid solvent shells that sets in around 4 M concentration. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

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

    PubMed

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

    2014-07-29

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

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

    PubMed

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

    2014-07-29

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

  14. An in situ cell for characterization of solids by soft x-ray absorption

    NASA Astrophysics Data System (ADS)

    Drake, Ian J.; Liu, Teris C. N.; Gilles, Mary; Tyliszczak, Tolek; Kilcoyne, A. L. David; Shuh, David K.; Mathies, Richard A.; Bell, Alexis T.

    2004-10-01

    A cell has been designed and fabricated for in situ characterization of catalysts and environmental materials using soft x-ray absorption spectroscopy and spectromicroscopy at photon energies above 250 eV. "Lab-on-a-chip" technologies were used to fabricate the cell on a glass wafer. The sample compartment is 1.0 mm in diameter and has a gas path length of 0.8 mm to minimize x-ray absorption in the gas phase. The sample compartment can be heated to 533 K by an Al resistive heater and gas flows up to 5.0 cm3 min-1 can be supplied to the sample compartment through microchannels. The performance of the cell was tested by acquiring Cu L3-edge x-ray appearance near-edge structure (XANES) data during the reduction and oxidation of a silica-supported Cu catalyst using the beam line 11.0.2 scanning transmission x-ray microscope (STXM) at the Advanced Light Source of Lawrence Berkeley National Laboratory (Berkeley, CA). Two-dimensional images of individual catalyst particles were recorded at photon energies between 926 and 937 eV, the energy range in which the Cu(II) and Cu(I) L3 absorption edges are observed. Oxidation state specific images of the catalyst clearly show the disappearance of Cu(II) species during the exposure of the oxidized sample to 4% CO in He while increasing the temperature from 308 to 473 K. Reoxidation restores the intensity of the image associated with Cu(II). Cu L3-edge XANES spectra obtained from stacks of STXM images show that with increasing temperature the Cu(II) peak intensity decreases as the Cu(I) peak intensity increases.

  15. A Differential Absorption/Emission Analysis of the Galactic Central Diffuse X-ray Enhancement

    NASA Astrophysics Data System (ADS)

    Yao, Yangsen; Wang, Q.

    2007-05-01

    The soft X-ray background shows a general enhancement toward the inner region of the Galaxy. But whether this enhancement is a local feature (e.g., a superbubble within a distance of 200 pc or a phenomenon related to energetic outflows from the Galactic center/bulge remains unclear. Here we report a comparative X-ray emission and absorption study of diffuse hot gas along the sight lines toward 3C 273 and Mrk 421, on and off the enhancement, but at similar Galactic latitudes. The diffuse 3/4-keV emission intensity, as estimated from the ROSAT All Sky Survey, is about three times higher toward 3C 273 than toward Mrk 421. Based on archival Chandra grating observations of these two AGNs, we detect z 0 X-ray absorption lines (e.g., OVII Kalpha, Kbeta, and OVIII Kalpha transitions) and find that the mean hot gas thermal and kinematic properties along the two sight lines are significantly different. By subtracting the background contribution, as determined along the Mrk 421 sight line, we isolate the net X-ray absorption and emission produced by the hot gas associated with the enhancement in the direction of 3C 273. From a joint analysis of these differential data sets, we obtain the temperature, dispersion velocity, and hydrogen column density as 2.0E6 K, 200 km/s, and 2E19 cm^{-2}, respectively, assuming that the gas is approximately isothermal, solar in metal abundances, and in collisional ionization equilibrium. We also constrain the effective extent of the gas to be 3.4 kpc, strongly suggesting that the enhancement most likely represents a Galactic central phenomenon.

  16. The Galactic Central Diffuse X-Ray Enhancement: A Differential Absorption/Emission Analysis

    NASA Astrophysics Data System (ADS)

    Yao, Yangsen; Wang, Q. Daniel

    2007-09-01

    The soft X-ray background shows a general enhancement toward the inner region of the Galaxy. But whether this enhancement is a local feature (e.g., a superbubble within a distance of <~200 pc) and/or a phenomenon related to energetic outflows from the Galactic center/bulge remains unclear. Here we report a comparative X-ray emission and absorption study of diffuse hot gas along the sight lines toward 3C 273 and Mrk 421, on and off the enhancement, but at similar Galactic latitudes. The diffuse 3/4 keV emission intensity, as estimated from the ROSAT All Sky Survey, is about 3 times higher toward 3C 273 than toward Mrk 421. Based on archival Chandra grating observations of these two AGNs, we detect X-ray absorption lines (e.g., O VII Kα, Kβ, and O VIII Kα transitions at z~0) and find that the mean hot gas thermal and kinematic properties along the two sight lines are significantly different. By subtracting the foreground and background contribution, as determined along the Mrk 421 sight line, we isolate the net X-ray absorption and emission produced by the hot gas associated with the enhancement in the direction of 3C 273. From a joint analysis of these differential data sets, we obtain the temperature, dispersion velocity, and hydrogen column density as 2.0(1.6,2.3)×106 K, 216(104, 480) km s-1, and 2.2(1.4,4.1)×1019 cm-2, respectively (90% confidence intervals), assuming that the gas is approximately isothermal, solar in metal abundances, and equilibrium in collisional ionization. We also constrain the effective line-of-sight extent of the gas to be 3.4(1.0, 10.1) kpc, strongly suggesting that the enhancement most likely represents a Galactic central phenomenon.

  17. Epitaxy of CoSix (1x-ray-absorption fine-structure techniques

    NASA Astrophysics Data System (ADS)

    Pirri, C.; Hong, S.; Tuilier, M. H.; Wetzel, P.; Gewinner, G.; Cortès, R.

    1996-01-01

    Electronic and structural properties of epitaxial CoSix layers have been investigated by means of core-level and valence-band photoemission, x-ray photoelectron diffraction, and extended x-ray-absorption fine-structure (EXAFS) experiments. CoSix layers of various x compositions have been grown on silicon by low rate Co and Si co-deposition onto room-temperature Si(111) substrates, with film thicknesses ranging from 30 to 100 Å. Photoemission shows substantial differences in valence and core-level spectra with respect to those of stable fluorite-type CoSi2 and ɛ-CoSi and indicate that well-defined metastable phases are formed. In particular, core-level photoemission experiments performed with a monochromatized x-ray source show large Si 2p binding-energy shifts (~0.4 eV) in the room-temperature deposited CoSix (1X-ray photoelectron diffraction as well as extended x-ray-absorption fine-structure measurements suggest that these pseudomorphic phases have a cubic structure, over a wide composition range. EXAFS measurements reveal that Co atoms are coordinated with eight Si atoms with a bond length of ~2.33 Å and with Co atoms with bond lengths in the 2.67-2.68 Å range. Such short Co-Co bond lengths show that the structure is definitively different from the stable CaF2-type CoSi2, even at the CoSi2 composition. All experimental data indicate that CoSix silicides crystallize in a cubic lattice close to that of pseudomorphic FeSix silicides, namely, a CsCl-type derived structure.

  18. Insights into the mechanism of X-ray-induced disulfide-bond cleavage in lysozyme crystals based on EPR, optical absorption and X-ray diffraction studies

    SciTech Connect

    Sutton, Kristin A.; Black, Paul J.; Mercer, Kermit R.; Garman, Elspeth F.; Owen, Robin L.; Snell, Edward H.; Bernhard, William A.

    2013-12-01

    Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage, to confirm a multi-track radiation-damage process and to develop a model of that process. Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage. Online UV–visible spectroscopy showed that upon X-irradiation, disulfide radicalization appeared to saturate at an absorbed dose of approximately 0.5–0.8 MGy, in contrast to the saturating dose of ∼0.2 MGy observed using EPR at much lower dose rates. The observations suggest that a multi-track model involving product formation owing to the interaction of two separate tracks is a valid model for radiation damage in protein crystals. The saturation levels are remarkably consistent given the widely different experimental parameters and the range of total absorbed doses studied. The results indicate that even at the lowest doses used for structural investigations disulfide bonds are already radicalized. Multi-track considerations offer the first step in a comprehensive model of radiation damage that could potentially lead to a combined computational and experimental approach to identifying when damage is likely to be present, to quantitate it and to provide the ability to recover the native unperturbed structure.

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

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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 Si2+ and Al2+ cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.

  1. Oscillator strength of the peptide bond {pi}* resonances at all relevant x-ray absorption edges

    SciTech Connect

    Kummer, K.; Vyalikh, D. V.; Molodtsov, S. L.; Sivkov, V. N.; Nekipelov, S. V.; Maslyuk, V. V.; Mertig, I.; Blueher, A.; Mertig, M.; Bredow, T.

    2009-10-15

    Absolute x-ray absorption cross sections of a regular bacterial surface-layer protein deposited on a naturally oxidized silicon substrate were determined experimentally. Upon separation of the partial cross sections of the three relevant 1s absorption edges, the oscillator strengths of the 1s{yields}{pi}* excitations within the peptide-backbone unit were extracted. Comparison with results of first-principles calculations revealed their close correlation to the topology of {pi}{sub peptide}* orbitals of the peptide backbone.

  2. Microscopic nonlinear relativistic quantum theory of absorption of powerful x-ray radiation in plasma.

    PubMed

    Avetissian, H K; Ghazaryan, A G; Matevosyan, H H; Mkrtchian, G F

    2015-10-01

    The microscopic quantum theory of plasma nonlinear interaction with the coherent shortwave electromagnetic radiation of arbitrary intensity is developed. The Liouville-von Neumann equation for the density matrix is solved analytically considering a wave field exactly and a scattering potential of plasma ions as a perturbation. With the help of this solution we calculate the nonlinear inverse-bremsstrahlung absorption rate for a grand canonical ensemble of electrons. The latter is studied in Maxwellian, as well as in degenerate quantum plasma for x-ray lasers at superhigh intensities and it is shown that one can achieve the efficient absorption coefficient in these cases.

  3. Synchrotron Radiation X-Ray Spectroscopy for Investigations of Intracellular Metallointercalators: X-Ray Fluorescence Imaging and X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Dillon, Carolyn T.

    In an effort to determine the therapeutic feasibility of DNA metallointercalators as potential anticancer drugs it is important to confirm that they are capable of targeting DNA in cancer cells or tumours - as is the intended purpose of their design. Microprobe synchrotron radiation X-ray fluorescence (micro-SRXRF) spectroscopy is an ideal technique for investigating the cellular uptake and distribution of metallointercalators. The technique is capable of submicron elemental imaging so that samples as small as individual cells (~10 μm diameter), and the features within them, can be resolved. Consequently, the technique can ascertain whether intracellular metallointercalators colocalise with DNA; namely, in the nucleus during interphase or at the chromosomes during middle prophase to late anaphase. Metals, such as those commonly incorporated into metallointercalators (e.g., Cr, Ni, Co, Pd, Pt, Ru, Rh), are often naturally present in negligible quantities in cancer cells. This fact, together with their higher atomic number, Z, makes them ideal for direct probing using hard X-ray microprobes (as discussed in Sect. 11.2). There is no need for the incorporation of fluorescent tracker dyes or radioactive labels into their chemical structure. This is advantageous since it is unknown whether such chemical modifications alter the uptake kinetics of the metallointercalator [1, 2].

  4. Bandpass x-ray diode and x-ray multiplier detector

    DOEpatents

    Wang, C.L.

    1982-09-27

    An absorption-edge of an x-ray absorption filter and a quantum jump of a photocathode determine the bandpass characteristics of an x-ray diode detector. An anode, which collects the photoelectrons emitted by the photocathode, has enhanced amplification provided by photoelectron-multiplying means which include dynodes or a microchannel-plate electron-multiplier. Suppression of undesired high frequency response for a bandpass x-ray diode is provided by subtracting a signal representative of energies above the passband from a signal representative of the overall response of the bandpass diode.

  5. In Situ X-Ray Absorption Spectroscopy Study of the LiNiO2 Electrode

    NASA Astrophysics Data System (ADS)

    Mansour, A. N.; McBreen, J.; Melendres, C. A.

    1997-03-01

    LiNiO2 is one of the most promising active material for the development of novel 4V rechargeable lithium batteries. Recent x-ray diffraction studies showed that the electrochemical reactivity of this electrode is sensitive to the structure of the starting material as well as the charged products. To further examine this material, we have conducted an x-ray absorption spectroscopy (XAS) study to determine the structure of this electrode as a function of its charge state. Specifically, the x-ray absorption Ni K-edge energy, the pre-edge structure, and local structure parameters such as bond lengths, coordination numbers and disorders were investigated at various states of charge corresponding to Li_(1-x)NiO2 for x values of 0.0, 0.11, 0.23, 0.34, 0.45, 0.82, and 0.99. The charging which proceeds via lithium de-intercalation was conducted using constant current anodization at 0.5 mA in a non aqueous electrolyte consisting of 1M LiPF6 in 1:1:3 propylene ! carbonate, ethylene carbonate and dimethyl carbonate. The XAS results for this electrode will be compared with those of γ-NiOOH and KNiIO_6, the latter being used as a reference for quadrivalent nickel.

  6. Use of X-ray absorption imaging to examine heterogeneous diffusion in fractured crystalline rocks.

    PubMed

    Altman, Susan J; Uchida, Masahiro; Tidwell, Vincent C; Boney, Craig M; Chambers, Bryan P

    2004-03-01

    Heterogeneous diffusion in different regions of a fractured granodiorite from Japan has been observed and measured through the use of X-ray absorption imaging. These regions include gouge-filled fractures, recrystallized fracture-filling material and hydrothermally altered matrix. With the X-ray absorption imaging technique, porosity, relative concentration, and relative mass of an iodine tracer were imaged in two dimensions with a sub-millimeter pixel size. Because portions of the samples analyzed have relatively low porosity values, imaging errors can potentially impact the results. For this reason, efforts were made to better understand and quantify this error. Based on the X-ray data, pore diffusion coefficients (Dp) for the different regions were estimated assuming a single diffusion rate and a lognormal multirate distribution of Dp. Results show Dp for the gouge-filled fractures are over an order of magnitude greater than those of the recrystallized fracture-filling material, which in turn is approximately two times greater than those for the altered matrix. The recrystallized fracture-filling material was found to exhibit the greatest degree of variability. The results of these experiments also provide evidence that diffusion from advective zones in fractures through the gouge-filled fractures and recrystallized fracture-filling material could increase the pore space available for matrix diffusion. This evidence is important for understanding the performance of potential nuclear waste repositories in crystalline rocks as diffusion is thought to be an important retardation mechanism for radionuclides.

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

    PubMed Central

    2015-01-01

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

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

    PubMed

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

    2015-10-01

    X-ray micro-computed tomography (μCT) 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 μCT 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 Corumbá (Brazil). Different tomographic setups were tested to visualize the fossilized inner structures: a commercial laboratory-based μCT 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.

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

    SciTech Connect

    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.

  10. Time-resolved X-ray Absorption Spectroscopy for Electron Transport Study in Warm Dense Gold

    NASA Astrophysics Data System (ADS)

    Lee, Jong-Won; Bae, Leejin; Engelhorn, Kyle; Heimann, Philip; Ping, Yuan; Barbrel, Ben; Fernandez, Amalia; Beckwith, Martha Anne; Cho, Byoung-Ick; GIST Team; IBS Team; LBNL Collaboration; SLAC Collaboration; LLNL Collaboration

    2015-11-01

    The warm dense Matter represents states of which the temperature is comparable to Fermi energy and ions are strongly coupled. One of the experimental techniques to create such state in the laboratory condition is the isochoric heating of thin metal foil with femtosecond laser pulses. This concept largely relies on the ballistic transport of electrons near the Fermi-level, which were mainly studied for the metals in ambient conditions. However, they were barely investigated in warm dense conditions. We present a time-resolved x-ray absorption spectroscopy measured for the Au/Cu dual layered sample. The front Au layer was isochorically heated with a femtosecond laser pulse, and the x-ray absorption changes around L-edge of Cu, which was attached on the backside of Au, was measured with a picosecond resolution. Time delays between the heating of the `front surface' of Au layer and the alternation of x-ray spectrum of Cu attached on the `rear surface' of Au indicate the energetic electron transport mechanism through Au in the warm dense conditions. IBS (IBS-R012-D1) and the NRF (No. 2013R1A1A1007084) of Korea.

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

    SciTech Connect

    Kirby, J.A.

    1981-05-01

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

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

    PubMed

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

    2015-10-01

    X-ray micro-computed tomography (μCT) 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 μCT 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 Corumbá (Brazil). Different tomographic setups were tested to visualize the fossilized inner structures: a commercial laboratory-based μCT 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. PMID:26306692

  13. Atmospheric pressure X-ray photoelectron spectroscopy apparatus: Bridging the pressure gap.

    PubMed

    Velasco-Vélez, J J; Pfeifer, V; Hävecker, M; Wang, R; Centeno, A; Zurutuza, A; Algara-Siller, G; Stotz, E; Skorupska, K; Teschner, D; Kube, P; Braeuninger-Weimer, P; Hofmann, S; Schlögl, R; Knop-Gericke, A

    2016-05-01

    One of the main goals in catalysis is the characterization of solid/gas interfaces in a reaction environment. The electronic structure and chemical composition of surfaces become heavily influenced by the surrounding environment. However, the lack of surface sensitive techniques that are able to monitor these modifications under high pressure conditions hinders the understanding of such processes. This limitation is known throughout the community as the "pressure gap." We have developed a novel experimental setup that provides chemical information on a molecular level under atmospheric pressure and in presence of reactive gases and at elevated temperatures. This approach is based on separating the vacuum environment from the high-pressure environment by a silicon nitride grid-that contains an array of micrometer-sized holes-coated with a bilayer of graphene. Using this configuration, we have investigated the local electronic structure of catalysts by means of photoelectron spectroscopy and in presence of gases at 1 atm. The reaction products were monitored online by mass spectrometry and gas chromatography. The successful operation of this setup was demonstrated with three different examples: the oxidation/reduction reaction of iridium (noble metal) and copper (transition metal) nanoparticles and with the hydrogenation of propyne on Pd black catalyst (powder). PMID:27250406

  14. Atmospheric pressure X-ray photoelectron spectroscopy apparatus: Bridging the pressure gap.

    PubMed

    Velasco-Vélez, J J; Pfeifer, V; Hävecker, M; Wang, R; Centeno, A; Zurutuza, A; Algara-Siller, G; Stotz, E; Skorupska, K; Teschner, D; Kube, P; Braeuninger-Weimer, P; Hofmann, S; Schlögl, R; Knop-Gericke, A

    2016-05-01

    One of the main goals in catalysis is the characterization of solid/gas interfaces in a reaction environment. The electronic structure and chemical composition of surfaces become heavily influenced by the surrounding environment. However, the lack of surface sensitive techniques that are able to monitor these modifications under high pressure conditions hinders the understanding of such processes. This limitation is known throughout the community as the "pressure gap." We have developed a novel experimental setup that provides chemical information on a molecular level under atmospheric pressure and in presence of reactive gases and at elevated temperatures. This approach is based on separating the vacuum environment from the high-pressure environment by a silicon nitride grid-that contains an array of micrometer-sized holes-coated with a bilayer of graphene. Using this configuration, we have investigated the local electronic structure of catalysts by means of photoelectron spectroscopy and in presence of gases at 1 atm. The reaction products were monitored online by mass spectrometry and gas chromatography. The successful operation of this setup was demonstrated with three different examples: the oxidation/reduction reaction of iridium (noble metal) and copper (transition metal) nanoparticles and with the hydrogenation of propyne on Pd black catalyst (powder).

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

    NASA Astrophysics Data System (ADS)

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

    1998-04-01

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

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

    PubMed

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

    2013-09-19

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

  17. Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Edwards, Nicholas P.; van Veelen, Arjen; Anné, Jennifer; Manning, Phillip L.; Bergmann, Uwe; Sellers, William I.; Egerton, Victoria M.; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Wakamatsu, Kazumasa; Ito, Shosuke; Wogelius, Roy A.

    2016-09-01

    Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms.

  18. Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy

    PubMed Central

    Edwards, Nicholas P.; van Veelen, Arjen; Anné, Jennifer; Manning, Phillip L.; Bergmann, Uwe; Sellers, William I.; Egerton, Victoria M.; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Wakamatsu, Kazumasa; Ito, Shosuke; Wogelius, Roy A.

    2016-01-01

    Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms. PMID:27658854

  19. Saturable Absorption of an X-Ray Free-Electron-Laser Heated Solid-Density Plasma

    NASA Astrophysics Data System (ADS)

    Wark, J. S.; Rackstraw, D. S.; Ciricosta, O.; Vinko, S. M.; Burian, T.; Chalupsky, J.; Hajkova, V.; Juha, L.; Barbrel, B.; Engelhorn, K.; Cho, B.-I.; Chung, H.-K.; Dakovski, G.; Krzywinski, J.; Heimann, P.; Holmes, M.; Turner, J.; Lee, R. W.; Toleikis, S.; Zastrau, U.

    2015-11-01

    High-intensity ~1017 Wcm-2, short duration (100 fsec) x-ray pulses from the LCLS x-ray free-electron laser, with photon energies ranging from below to above the K-edge of cold Al (1560 eV), are used to generate and probe a solid-density aluminum plasma. The photon-energy-dependent transmission of the heating beam is studied through the use of a photodiode. Saturable absorption is observed, with the resulting transmission differing significantly from the cold case, with the increased transmission being due to the K-edge energy of the dominant ion species shifting in time as the solid-density target is heated, in good agreement with atomic-kinetics simulations.

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

    SciTech Connect

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

    2007-07-15

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

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

    PubMed Central

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

    2015-01-01

    We report time-resolved X-ray absorption measurements after photolysis of carbonmonoxy myoglobin performed at the LCLS X-ray free electron laser with nearly 100 fs (FWHM) time resolution. Data at the Fe K-edge reveal that the photoinduced structural changes at the heme occur in two steps, with a faster (∼70 fs) relaxation preceding a slower (∼400 fs) one. We tentatively attribute the first relaxation to a structural rearrangement induced by photolysis involving essentially only the heme chromophore and the second relaxation to a residual Fe motion out of the heme plane that is coupled to the displacement of myoglobin F-helix. PMID:26798812

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

    SciTech Connect

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

    2014-12-01

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

  3. Detection, identification and mapping of iron anomalies in brain tissue using X-ray absorption spectroscopy

    SciTech Connect

    Mikhaylova, A.; Davidson, M.; Toastmann, H.; Channell, J.E.T.; Guyodo, Y.; Batich, C.; Dobson, J.

    2008-06-16

    This work describes a novel method for the detection, identification and mapping of anomalous iron compounds in mammalian brain tissue using X-ray absorption spectroscopy. We have located and identified individual iron anomalies in an avian tissue model associated with ferritin, biogenic magnetite and haemoglobin with a pixel resolution of less than 5 {micro}m. This technique represents a breakthrough in the study of both intra- and extra-cellular iron compounds in brain tissue. The potential for high-resolution iron mapping using microfocused X-ray beams has direct application to investigations of the location and structural form of iron compounds associated with human neurodegenerative disorders - a problem which has vexed researchers for 50 years.

  4. Scanning electron and atomic force microscopy, and raman and x-ray photoelectron spectroscopy characterization of near-isogenic soft and hard wheat kernels and corresponding flours

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) are used to investigate vitreous (hard) and non-vitreous (soft) wheat kernels and their corresponding wheat flours. AFM data reveal two different microstructures. The vitreous kernel reveals a granular text...

  5. X-Ray Photoelectron Spectroscopy Study of the Effect of Hydrocarbon Contamination on Poly(Tetrafluoroethylene) Exposed to a Nitrogen Plasma

    NASA Technical Reports Server (NTRS)

    Golub, Morton A.; Lopata, Eugene S.; Finney, Lorie S.

    1993-01-01

    In this note, we show that X-ray photoelectron Spectroscopy (XPS) data and the changes in surface properties attending exposure of poly(tetrafluoroethylene) (PTFE) films to a nitrogen plasma can likewise be misinterpreted when the interfering role of minor surface hydrocarbon contamination is not taken into account.

  6. X-Ray Photoelectron Spectroscopy Study of the Effect of Hydrocarbon Contamination on Poly(Tetrafluoroethylene) Exposed to a Nitrogen Plasma

    NASA Technical Reports Server (NTRS)

    Golub, Morton A.; Lopata, Eugene S.; Finney, Lorie S.

    1993-01-01

    It has been shown that unless the surface of poly(tetrafluoroethylene)(PTFE) is free of hydrocarbon contamination, anomalous changes in the oxygen and fluorine contents, as measured by X-ray photoelectron spectroscopy (XPS), and hence also the surface properties, may be improperly ascribed to a PTFE film exposed to a oxygen plasma.

  7. X-Ray Absorption, Nuclear Infrared Emission, and Dust Covering Factors of AGNs: Testing Unification Schemes

    NASA Astrophysics Data System (ADS)

    Mateos, S.; Carrera, F. J.; Alonso-Herrero, A.; Hernán-Caballero, A.; Barcons, X.; Asensio Ramos, A.; Watson, M. G.; Blain, A.; Caccianiga, A.; Ballo, L.; Braito, V.; Ramos Almeida, C.

    2016-03-01

    We present the distributions of the geometrical covering factors of the dusty tori (f2) of active galactic nuclei (AGNs) using an X-ray selected complete sample of 227 AGNs drawn from the Bright Ultra-hard XMM-Newton Survey. The AGNs have z from 0.05 to 1.7, 2-10 keV luminosities between 1042 and 1046 erg s-1, and Compton-thin X-ray absorption. Employing data from UKIDSS, 2MASS, and the Wide-field Infrared Survey Explorer in a previous work, we determined the rest-frame 1-20 μm continuum emission from the torus, which we model here with the clumpy torus models of Nenkova et al. Optically classified type 1 and type 2 AGNs are intrinsically different, with type 2 AGNs having, on average, tori with higher f2 than type 1 AGNs. Nevertheless, ˜20% of type 1 AGNs have tori with large covering factors, while ˜23%-28% of type 2 AGNs have tori with small covering factors. Low f2 are preferred at high AGN luminosities, as postulated by simple receding torus models, although for type 2 AGNs the effect is certainly small. f2 increases with the X-ray column density, which implies that dust extinction and X-ray absorption take place in material that share an overall geometry and most likely belong to the same structure, the putative torus. Based on our results, the viewing angle, AGN luminosity, and also f2 determine the optical appearance of an AGN and control the shape of the rest-frame ˜1-20 μm nuclear continuum emission. Thus, the torus geometrical covering factor is a key ingredient of unification schemes.

  8. Density Measurement for MORB Melts by X-ray Absorption Method

    NASA Astrophysics Data System (ADS)

    Sakamaki, T.; Urakawa, S.; Suzuki, A.; Ohtani, E.; Katayama, Y.

    2006-12-01

    Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the top anvil sizes of 6 mm and 4 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 5 GPa, from 300 to 2000 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

  9. Density Measurement for MORB Melts by X-ray Absorption Method

    NASA Astrophysics Data System (ADS)

    Sakamaki, T.; Urakawa, S.; Ohtani, E.; Suzuki, A.; Katayama, Y.

    2005-12-01

    Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the edge-length of 6 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 4 GPa, from 300 to 2200 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

  10. Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy.

    PubMed

    Shelby, Megan L; Lestrange, Patrick J; Jackson, Nicholas E; Haldrup, Kristoffer; Mara, Michael W; Stickrath, Andrew B; Zhu, Diling; Lemke, Henrik T; Chollet, Matthieu; Hoffman, Brian M; Li, Xiaosong; Chen, Lin X

    2016-07-20

    Photoexcited Nickel(II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through multiple electronic states following an initial porphyrin-based excitation, some involving metal centered electronic configuration changes that could be harnessed catalytically before excited state relaxation. While a NiTMP excited state present at 100 ps was previously identified by X-ray transient absorption (XTA) spectroscopy at a synchrotron source as a relaxed (d,d) state, the lowest energy excited state (J. Am. Chem. Soc., 2007, 129, 9616 and Chem. Sci., 2010, 1, 642), structural dynamics before thermalization were not resolved due to the ∼100 ps duration of the available X-ray probe pulse. Using the femtosecond (fs) X-ray pulses of the Linac Coherent Light Source (LCLS), the Ni center electronic configuration from the initial excited state to the relaxed (d,d) state has been obtained via ultrafast Ni K-edge XANES (X-ray absorption near edge structure) on a time scale from hundreds of femtoseconds to 100 ps. This enabled the identification of a short-lived Ni(I) species aided by time-dependent density functional theory (TDDFT) methods. Computed electronic and nuclear structure for critical excited electronic states in the relaxation pathway characterize the dependence of the complex's geometry on the electron occupation of the 3d orbitals. Calculated XANES transitions for these excited states assign a short-lived transient signal to the spectroscopic signature of the Ni(I) species, resulting from intramolecular charge transfer on a time scale that has eluded previous synchrotron studies. These combined results enable us to examine the excited state structural dynamics of NiTMP prior to thermal relaxation and to capture intermediates of potential photocatalytic significance.

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

    PubMed

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

    2015-09-01

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

  12. X-ray absorption of cadmium in the L-edge region

    SciTech Connect

    Padeznik Gomilsek, J.; Kodre, A.; Arcon, I.; Bratina, G.

    2011-11-15

    Atomic x-ray absorption of cadmium in the energy region of L edges was measured on the vapor of the element, in parallel with the absorption of Cd metal foil. Ionization thresholds of the three subshells are determined from the edge profiles, through the energies of pre-edge resonances and indium optical levels in the Z + 1 approximation. A purely experimental result, without extraneous data and with an accuracy of 0.2 eV, is the energy difference between the pre-edge resonance and the threshold energy of the metallic state. Some multielectron-excitation resonances are identified within 30 eV above the edges. The metal foil absorption is used for absolute determination of Cd absorption coefficient.

  13. X-ray absorption toward the red quasar 3C 212

    NASA Technical Reports Server (NTRS)

    Elvis, Martin; Fiore, Fabrizio; Mathur, Smita; Wilkes, Belinda J.

    1994-01-01

    A Roentgen Satellite (ROSAT) X-ray spectrum of the z = 1.049 'red quasar' 3C 212 has a strong low-energy cutoff. The spectrum can be fitted with a power law (of energy index 1.4(+0.8, -0.6) with low-energy photoelectric absorption in excess of the Galactic value that, if at the redhsift of the quasar, would have a column density of (0.9(+0.8, -0.6)) x 10(exp 22) atoms/sq cm. Possible sites for the absorption are a nuclear torus, an intervening damped Lyman-alpha system, or intracluster material (e.g., a cooling flow) around the quasar. The implied absorbing column density is sufficient to redden a normal quasar spectrum to the observed steep optical slope. The observed continuum, if dereddened by this amount, can produce the observed emission line fluxes and ratios. The absence of the graphite lambda-2175 feature in 3C 212 however, requires dust different from the local Milky Way composition, or an intervening absorber with z less than 0.4. Alternative acceptable fits to the X-ray spectrum are (1) a blackbody with a temperature of 0.7 keV (in the quasar frame) modified only by Galactic absorption, and (2) an optically thin thermal plasma with excess absorption. Although a blackbody spectrum would be unprecedented, the model is consistent with all the available X-ray and optical data and cannot be ruled out. We discuss possible observations that can discriminate among the above models.

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

    PubMed

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

    2001-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  16. In Situ Density Measurement of Basaltic Melts at High Pressure by X-ray Absorption Method

    NASA Astrophysics Data System (ADS)

    Ando, R.; Ohtani, E.; Suzuki, A.; Urakawa, S.; Katayama, Y.

    2004-12-01

    Density of silicate melt at high pressure is one of the most important properties to understand magma migration in the planetary interior. However, because of experimental difficulties, the density of magma at high pressure is poorly known. Katayama et al. (1996) recently developed a new in situ density measurement method for metallic melts, based on the density dependency of X-ray absorption in the sample. In this study, we tried to measure the density of basaltic melt by this absorption method. When X-ray is transmitted to the sample, the intensity of the transmitted X-ray beam (I) is expressed as follows; I=I0exp(-μ ρ t), where I0 is the intensity of incident X-ray beam, μ is the mass absorption coefficient, ρ is the density of the sample, and t is the thickness of the sample. If t and μ are known, we can determine the density of the sample by measuring I and I0. This is the principle of the absorption method for density measurement. In this study, in order to determine t, we used a single crystalline diamond cylinder as a sample capsule, diamond is less compressive and less deformable so that even at high pressure t (thickness of the sample at the point x) is expressed as follows; t = 2*(R02-x2)1/2, R0 is the inner radius of cylinder at the ambient condition, and x is distance from a center of the capsule. And diamond also shows less absorption so that this make it possible to measure the density of silicate melt with smaller absorption coefficient than metallic melts. In order to know the μ of the sample, we measured both densities (ρ ) and absorptions (I/I0) for some glasses and crystals with same composition of the sample at the ambient condition, and calculated as fallows; μ =ln(I/I0)/ρ . Experiments were made at the beamline (BL22XU) of SPring-8. For generation of high pressure and high temperature, we used DIA-type cubic anvil apparatus (SMAP180) there. We used tungsten carbide anvils with the edge-length of 6 mm. The energy of monochromatic X-ray

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

    NASA Astrophysics Data System (ADS)

    Johnson, Phillip S.

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

  18. A variable absorption feature in the X-ray spectrum of a magnetar.

    PubMed

    Tiengo, Andrea; Esposito, Paolo; Mereghetti, Sandro; Turolla, Roberto; Nobili, Luciano; Gastaldello, Fabio; Götz, Diego; Israel, Gian Luca; Rea, Nanda; Stella, Luigi; Zane, Silvia; Bignami, Giovanni F

    2013-08-15

    Soft-γ-ray repeaters (SGRs) and anomalous X-ray pulsars (AXPs) are slowly rotating, isolated neutron stars that sporadically undergo episodes of long-term flux enhancement (outbursts) generally accompanied by the emission of short bursts of hard X-rays. This behaviour can be understood in the magnetar model, according to which these sources are mainly powered by their own magnetic energy. This is supported by the fact that the magnetic fields inferred from several observed properties of SGRs and AXPs are greater than-or at the high end of the range of-those of radio pulsars. In the peculiar case of SGR 0418+5729, a weak dipole magnetic moment is derived from its timing parameters, whereas a strong field has been proposed to reside in the stellar interior and in multipole components on the surface. Here we show that the X-ray spectrum of SGR 0418+5729 has an absorption line, the properties of which depend strongly on the star's rotational phase. This line is interpreted as a proton cyclotron feature and its energy implies a magnetic field ranging from 2 × 10(14) gauss to more than 10(15) gauss. PMID:23955229

  19. A variable absorption feature in the X-ray spectrum of a magnetar.

    PubMed

    Tiengo, Andrea; Esposito, Paolo; Mereghetti, Sandro; Turolla, Roberto; Nobili, Luciano; Gastaldello, Fabio; Götz, Diego; Israel, Gian Luca; Rea, Nanda; Stella, Luigi; Zane, Silvia; Bignami, Giovanni F

    2013-08-15

    Soft-γ-ray repeaters (SGRs) and anomalous X-ray pulsars (AXPs) are slowly rotating, isolated neutron stars that sporadically undergo episodes of long-term flux enhancement (outbursts) generally accompanied by the emission of short bursts of hard X-rays. This behaviour can be understood in the magnetar model, according to which these sources are mainly powered by their own magnetic energy. This is supported by the fact that the magnetic fields inferred from several observed properties of SGRs and AXPs are greater than-or at the high end of the range of-those of radio pulsars. In the peculiar case of SGR 0418+5729, a weak dipole magnetic moment is derived from its timing parameters, whereas a strong field has been proposed to reside in the stellar interior and in multipole components on the surface. Here we show that the X-ray spectrum of SGR 0418+5729 has an absorption line, the properties of which depend strongly on the star's rotational phase. This line is interpreted as a proton cyclotron feature and its energy implies a magnetic field ranging from 2 × 10(14) gauss to more than 10(15) gauss.

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

    NASA Astrophysics Data System (ADS)

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

    1996-09-01

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

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

    PubMed

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

    2016-07-28

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  3. Hard X-ray Photoelectron Spectroscopy (HAXPES) Investigation of the Silicon Solid Electrolyte Interphase (SEI) in Lithium-Ion Batteries.

    PubMed

    Young, Benjamin T; Heskett, David R; Nguyen, Cao Cuong; Nie, Mengyun; Woicik, Joseph C; Lucht, Brett L

    2015-09-16

    Binder-free silicon (BF-Si) nanoparticle anodes were cycled with 1.2 M LiPF6 in ethylene carbonate (EC), fluoroethylene carbonate (FEC), or EC with 15% FEC (EC:FEC), extracted from cells and analyzed by Hard X-ray Photoelectron Spectroscopy (HAXPES). All of the electrolytes generate an SEI which is integrated with Si containing species. The EC and EC:FEC electrolytes result in the generation of LixSiOy after the first cycle while LixSiOy is only observed after five cycles for the FEC electrolyte. The SEI initially generated from the EC electrolyte is primarily composed of lithium ethylene dicarbonate (LEDC) and LiF. However, after five cycles, the composition changes, especially near the surface of silicon because of decomposition of the LEDC. The SEI generated from the EC:FEC electrolytes contains LEDC, LiF, and poly(FEC) and small changes are observed upon additional cycling. The SEI generated with the FEC electrolyte contains LiF and poly(FEC) and small changes are observed upon additional cycling. The stability of the SEI correlates with the observed capacity retention of the cells.

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

    SciTech Connect

    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.

  5. Band alignment of ZnO/multilayer MoS2 interface determined by x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Xinke; Zhang, Yuan; Liu, Qiang; He, Jiazhu; Chen, Le; Li, Kuilong; Jia, Fang; Zeng, Yuxiang; Lu, Youming; Yu, Wenjie; Zhu, Deliang; Liu, Wenjun; Wu, Jing; He, Zhubing; Ang, Kah-Wee

    2016-08-01

    The energy band alignment between ZnO and multilayer (ML)-MoS2 was characterized using high-resolution x-ray photoelectron spectroscopy. The ZnO film was deposited using an atomic layer deposition tool, and ML-MoS2 was grown by chemical vapor deposition. A valence band offset (VBO) of 3.32 eV and a conduction band offset (CBO) of 1.12 eV were obtained for the ZnO/ML-MoS2 interface without any treatment. With CHF3 plasma treatment, a VBO and a CBO across the ZnO/ML-MoS2 interface were found to be 3.54 eV and 1.34 eV, respectively. With the CHF3 plasma treatment, the band alignment of the ZnO/ML-MoS2 interface has been changed from type II or staggered band alignment to type III or misaligned one, which favors the electron-hole pair separation. The band alignment difference is believed to be dominated by the down-shift in the core level of Zn 2p or the interface dipoles, which is caused by the interfacial layer rich in F.

  6. In situ x-ray photoelectron spectroscopy studies of gas/solidinterfaces at near-ambient conditions

    SciTech Connect

    Bluhm, Hendrik; Havecker, Michael; Knop-Gericke, Axel; Kiskinova,Maya; Schlogl, Robert; Salmeron, Miquel

    2007-12-03

    X-ray photoelectron spectroscopy (XPS) is a quantitative, chemically specific technique with a probing depth of a few angstroms to a few nanometers. It is therefore ideally suited to investigate the chemical nature of the surfaces of catalysts. Because of the scattering of electrons by gas molecules, XPS is generally performed under vacuum conditions. However, for thermodynamic and/or kinetic reasons, the catalyst's chemical state observed under vacuum reaction conditions is not necessarily the same as that of a catalyst under realistic operating pressures. Therefore, investigations of catalysts should ideally be performed under reaction conditions, i.e., in the presence of a gas or gas mixtures. Using differentially pumped chambers separated by small apertures, XPS can operate at pressures of up to 1 Torr, and with a recently developed differentially pumped lens system, the pressure limit has been raised to about 10 Torr. Here, we describe the technical aspects of high-pressure XPS and discuss recent applications of this technique to oxidation and heterogeneous catalytic reactions on metal surfaces.

  7. In-situ X-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions

    SciTech Connect

    Salmeron, Miquel; Yamamoto, S.; Bluhm, H.; Andersson, K.; Ketteler, G.; Ogasawara, H.; Salmeron, M.; Nilsson, A.

    2007-10-29

    X-ray photoelectron spectroscopy (XPS) is a powerful tool for surface and interface analysis, providing the elemental composition of surfaces and the local chemical environment of adsorbed species. Conventional XPS experiments have been limited to ultrahigh vacuum (UHV) conditions due to a short mean free path of electrons in a gas phase. The recent advances in instrumentation coupled with third-generation synchrotron radiation sources enables in-situ XPS measurements at pressures above 5 Torr. In this review, we describe the basic design of the ambient pressure XPS setup that combines differential pumping with an electrostatic focusing. We present examples of the application of in-situ XPS to studies of water adsorption on the surface of metals and oxides including Cu(110), Cu(111), TiO2(110) under environmental conditions of water vapor pressure. On all these surfaces we observe a general trend where hydroxyl groups form first, followed by molecular water adsorption. The importance of surface OH groups and their hydrogen bonding to water molecules in water adsorption on surfaces is discussed in detail.

  8. X-ray Photoelectron Spectroscopy of Pyridinium-Based Ionic Liquids: Comparison to Imidazolium- and Pyrrolidinium-Based Analogues.

    PubMed

    Men, Shuang; Mitchell, Daniel S; Lovelock, Kevin R J; Licence, Peter

    2015-07-20

    We investigate eight 1-alkylpyridinium-based ionic liquids of the form [Cn Py][A] by using X-ray photoelectron spectroscopy (XPS). The electronic environment of each element of the ionic liquids is analyzed. In particular, a reliable fitting model is developed for the C 1s region that applies to each of the ionic liquids. This model allows the accurate charge correction of binding energies and the determination of reliable and reproducible binding energies for each ionic liquid. Shake-up/off phenomena are determinedfor both C 1s and N 1s spectra. The electronic interaction between cations and anions is investigated for both simple ionic liquids and an example of an ionic-liquid mixture; the effect of the anion on the electronic environment of the cation is also explored. Throughout the study, a detailed comparison is made between [C8 Py][A] and analogues including 1-octyl-1-methylpyrrolidinium- ([C8 C1 Pyrr][A]), and 1-octyl-3-methylimidazolium- ([C8 C1 Im][A]) based samples, where X is common to all ionic liquids.

  9. Quantitative determination of the oxidation state of iron in biotite using x-ray photoelectron spectroscopy: II. In situ analyses

    SciTech Connect

    Raeburn, S.P. |; Ilton, E.S.; Veblen, D.R.

    1997-11-01

    X-ray photoelectron spectroscopy (XPS) was used to determine Fe(III)/{Sigma}Fe in individual biotite crystals in thin sections of ten metapelites and one syenite. The in situ XPS analyses of Fe(III)/{Sigma}Fe in biotite crystals in the metapelites were compared with published Fe(III)/{Sigma}Fe values determined by Moessbauer spectroscopy (MS) for mineral separates from the same hand samples. The difference between Fe(III)/{Sigma}Fe by the two techniques was greatest for samples with the lowest Fe(III)/{Sigma}Fe (by MS). For eight metamorphic biotites with Fe(III)/{Sigma}Fe = 9-27% comparison of the two techniques yielded a linear correlation of r = 0.94 and a statistically acceptable fit of [Fe(III)/{Sigma}Fe]{sub xps} = [Fe(III)/{Sigma}Fe]{sub ms}. The difference between Fe(III)/{Sigma}Fe by the two techniques was greater for two samples with Fe(III)/{Sigma}Fe {le} 6% (by MS). For biotite in the syenite sample, Fe(III)/{Sigma}Fe determined by both in situ XPS and bulk wet chemistry/electron probe microanalysis were similar. This contribution demonstrates that XPS can be used to analyze bulk Fe(III)/{Sigma}Fe in minerals in thin sections when appropriate precautions taken to avoid oxidation of the near-surface during preparation of samples. 25 refs., 3 figs., 4 tabs.

  10. Band offsets of TiZnSnO/Si heterojunction determined by x-ray photoelectron spectroscopy

    SciTech Connect

    Sun, R. J.; Jiang, Q. J.; Yan, W. C.; Feng, L. S.; Lu, B.; Ye, Z. Z.; Li, X. F.; Li, X. D.; Lu, J. G.

    2014-09-28

    X-ray photoelectron spectroscopy (XPS) was utilized to measure the valence band offset (ΔE{sub V}) of the TiZnSnO (TZTO)/Si heterojunction. TZTO films were deposited on Si (100) substrates using magnetron sputtering at room temperature. By using the Zn 2p{sub 3/2} and Sn 3d{sub 5/2} energy levels as references, the value of ΔE{sub V} was calculated to be 2.69 ± 0.1 eV. Combining with the experimental optical energy band gap of 3.98 eV for TZTO extracted from the UV-vis transmittance spectrum, the conduction band offset (ΔE{sub C}) was deduced to be 0.17 ± 0.1 eV at the interface. Hence, the energy band alignment of the heterojunction was determined accurately, showing a type-I form. This will be beneficial for the design and application of TZTO/Si hybrid devices.

  11. Quantitative determination of the oxidation state of iron in biotite using x-ray photoelectron spectroscopy: I. Calibration

    SciTech Connect

    Raeburn, S.P.; Ilton, E.S.; Veblen, D.R.

    1997-11-01

    X-ray photoelectron spectroscopy (XPS) analyses of Fe(III)/{Sigma}Fe were calibrated with nine single crystals of biotite of known Fe(III)/{Sigma}Fe content. Peak shape parameters for the component Fe{sup 2+} and Fe{sup 3+} Fe 3p peaks were obtained by a constrained lease squares fitting method that minimized the difference between Fe(III)/{Sigma}Fe determined by XPS and wet chemistry/electron microprobe (WCEM) analyses. Fe{sup 2+} and Fe{sup 3+} peak separation was estimated from the separation of minima in the second derivative of Fe 3p spectra. The single set of derived peak parameters yielded a good linear correlation (r = 0.87) between XPS and WCEM values over the sample displaying progressive oxidation during XPS analysis resulted in Fe{sup 2} and Fe{sup 3+} component peak shapes largely consistent with the constrained least squares fitting methods. Beam damage, which appeared to be restricted to three single crystals with low {Sigma}Fe, low Fe/Mg, and high Fe(II)/{Sigma}Fe, caused increases in Fe(III)/{Sigma}Fe that were proportional to the duration of sample exposure. 60 refs., 6 figs., 7 tabs.

  12. An XPS study of the stability of Fomblin Z25 on the native oxide of aluminum. [x ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Herrera-Fierro, Pilar; Pepper, Stephen V.; Jones, William R.

    1991-01-01

    Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum and sapphire surfaces, and their behavior at different temperatures was studied using x ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). It was found that the interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. Our conclusion is that the native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At high temperatures (150 C) degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formulation of a debris layer.

  13. X-ray photoelectron spectroscopy study of the stability of Fomblin Z25 on the native oxide of aluminum

    NASA Technical Reports Server (NTRS)

    Herrera-Fierro, Pilar; Pepper, Stephen V.; Jones, William R.

    1992-01-01

    Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum, and onto sapphire surfaces, and their behavior at different temperatures was studied using X-ray photoelectron spectroscopy and temperature desorption spectroscopy (TDS). The interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on the clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. The native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At higher temperatures (150 C), degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formation of a debris layer.

  14. Interaction between M/CuO (M = Ti, V, Cr, Mn) as studied by X-ray Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Chourasia, Anil; Stahl, Jacob

    2014-03-01

    The technique of x-ray photoelectron spectroscopy has been utilized to investigate the chemical reactivity between metal M (where M is Ti, V, Cr, or Mn) and copper oxide at the M/CuO interface. Thin films of copper (about 20 nm) were deposited on silicon substrates by the e-beam method. Such samples were oxidized in an oxygen environment in a quartz tube furnace at 400°C. The formation of CuO was checked by the XPS spectral data. Thin films of the metal M were then deposited on these CuO sample. The M 2p, oxygen 1s and copper 2p regions were investigated by XPS. The magnesium anode (energy = 1253.6 eV) has been used for this purpose. The metal 2p peaks shift to the high binding energy side while the satellites associated with the copper core level peaks disappear. The shifting of the metal 2p peaks is associated with the formation of the oxide. The disappearance of the satellites in the copper 2p region is associated with the reduction of copper oxide to elemental copper. The spectral data show chemical reactivity at the M/CuO interface. Supported by Organized Reseach, TAMU-Commerce.

  15. X-Ray Photoelectron Spectroscopy Study of the Heating Effects on Pd/6H-SiC Schottky Structure

    NASA Technical Reports Server (NTRS)

    Chen, Liang-Yu; Hunter, Gary W.; Neudeck, Philip G.; Knight, Dak

    1998-01-01

    X-ray photoelectron spectroscopy is used to study the effects of heat treatment on the Pd/6H-SiC Schottky diode structure. After heating the structure at 425 C for 140 h, a very thin surface layer of PdO mixed with SiO(x) formed on the palladium surface of the Schottky structure. Heat treatment promoted interfacial diffusion and reaction which significantly broadened the interfacial region. In the interfacial region, the palladium concentration decreases with depth, and the interfacial products are Pd(x)Si (x = 1,2,3,4). In the high Pd concentration regions, Pd4Si is the major silicide component while gr and Pd2Si are major components in the low Pd concentration region. At the center of the interface, where the total palladium concentration equals that of silicon, the concentrations of palladium associated with various palladium silicides (Pd(x)Si, x= 1,2,3,4) are approximately equal. The surface passivation layer composed of PdO and SiO, may significantly affect the electronic and catalytic properties of the surface of the Schottky diode which plays a major role in gas detection. The electronic properties of the Schottky structure may be dominated by a (Pd+Pd(x)Si)/SiC interface. In order to stabilize the properties of the Schottky structure the surface and interface diffusion and reactions must be controlled.

  16. UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

    SciTech Connect

    Tewell, Craig R.

    2002-08-19

    X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl{sub 4} and a Al(Et){sub 3} co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl{sub 2} and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl{sub 4} in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl{sub 2} by TiCl{sub 4} resulting in a thin film of MgCl{sub 2}/TiCl{sub x}, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl{sub 2}/TiCl{sub x} on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to {approx}1 Torr of Al(Et){sub 3}.

  17. X-ray photoelectron spectroscopy analysis of boron defects in silicon crystal: A first-principles study

    NASA Astrophysics Data System (ADS)

    Yamauchi, Jun; Yoshimoto, Yoshihide; Suwa, Yuji

    2016-05-01

    We carried out a comprehensive study on the B 1s core-level X-ray photoelectron spectroscopy (XPS) binding energies and formation energies for boron defects in crystalline silicon by first-principles calculation with careful evaluation of the local potential boundary condition for the model system using the supercell corresponding to 1000 Si atoms. It is reconfirmed that the cubo-octahedral B12 cluster in silicon crystal is unstable and exists at the saddle point decaying to the icosahedral and S4 B12 clusters. The electrically active clusters without any postannealing of ion-implanted Si are identified as icosahedral B12 clusters. The experimentally proposed threefold coordinated B is also identified as a ⟨ 001 ⟩ B - Si defect. For an as-doped sample prepared by plasma doping, the calculated XPS spectra for complexes consisting of vacancies and substitutional B atoms are consistent with the experimental spectra. It is proposed that, assuming that the XPS peak at 187.1 eV is due to substitutional B (Bs), the experimental XPS peaks at 187.9 and 186.7 eV correspond to interstitial B at the H-site and ⟨ 001 ⟩ B - Si defects, respectively. In the annealed samples, the complex of Bs and interstitial Si near the T-site is proposed as a candidate for the experimental XPS peak at 188.3 eV.

  18. Time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analyses of Bixa orellana seeds.

    PubMed

    Felicissimo, Marcella P; Bittencourt, Carla; Houssiau, Laurent; Pireaux, Jean-Jacques

    2004-04-01

    Three different experiments were performed in order to obtain the major carotenoid composition of the natural colorant annatto (E160b) through ToF-SIMS (time-of-flight secondary ion mass spectrometry) and XPS (X-ray photoelectron spectroscopy) analyses. In the first experiment, Bixa orellana seeds aril as well as its interior part were analyzed. The analysis of the seeds aril by ToF-SIMS gives the colorant fingerprint without any sample treatment, showing the presence of bixin and its characteristic fragments. The analysis performed in the interior part of the seeds indicates the presence of Fe. The second set of measurements was conducted on the seeds organic extract right after extraction revealing the same components observed by in situ measurement. A third set of measurements was performed aiming to determine the reason for the organic extract color shift observed after 3 months of exposure to ambient light at room temperature. In this case, it was possible to evidence the degradation of bixin by the loss of xylene molecules through ToF-SIMS and the probable carotenoid oxidation based on the C1s XPS spectrum of the degraded extract. PMID:15053514

  19. Uniqueness plots: A simple graphical tool for identifying poor peak fits in X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Singh, Bhupinder; Diwan, Anubhav; Jain, Varun; Herrera-Gomez, Alberto; Terry, Jeff; Linford, Matthew R.

    2016-11-01

    Peak fitting is an essential part of X-ray photoelectron spectroscopy (XPS) narrow scan analysis, and the Literature contains both good and bad examples of peak fitting. A common cause of poor peak fitting is the inclusion of too many fit parameters, often without a sound chemical and/or physical basis for them, and/or the failure to reasonably constrain them. Under these conditions, fit parameters are often correlated, and therefore lacking in statistical meaning. Here we introduce the uniqueness plot as a simple graphical tool for identifying bad peak fits in XPS, i.e., fit parameter correlation. These plots are widely used in spectroscopic ellipsometry. We illustrate uniqueness plots with two data sets: a C 1s narrow scan from ozone-treated carbon nanotube forests and an Si 2p narrow scan from an air-oxidized silicon wafer. For each fit, we consider different numbers of parameters and constraints on them. As expected, the uniqueness plots are parabolic when fewer fit parameters and/or more constraints are applied. However, they fan out and eventually become horizontal lines as more unconstrained parameters are included in the fits. Uniqueness plots are generated by plotting the chi squared (χ2) value for a fit vs. a systematically varied value of a parameter in the fit. The Abbe criterion is also considered as a figure of merit for uniqueness plots in the Supporting Information. We recommend that uniqueness plots be used by XPS practitioners for identifying inappropriate peak fits.

  20. Compositional depth profile of a native oxide LPCVD MNOS structure using X-ray photoelectron spectroscopy and chemical etching

    NASA Technical Reports Server (NTRS)

    Wurzbach, J. A.; Grunthaner, F. J.

    1983-01-01

    It is pointed out that there is no report of an unambiguous analysis of the composition and interfacial structure of MNOS (metal-nitride oxide semiconductor) systems, despite the technological importance of these systems. The present investigation is concerned with a study of an MNOS structure on the basis of a technique involving the use of X-ray photoelectron spectroscopy (XPS) with a controlled stopped-flow chemical-etching procedure. XPS is sensitive to the structure of surface layers, while stopped-flow etching permits the controlled removal of overlying material on a scale of atomic layers, to expose new surface layers as a function of thickness. Therefore, with careful analysis of observed intensities at measured depths, this combination of techniques provides depth resolution between 5 and 10 A. According to the obtained data there is intact SiO2 at the substrate interface. There appears to be a thin layer containing excess bonds to silicon on top of the SiO2.

  1. Photoelectric characteristics of silicon P—N junction with nanopillar texture: Analysis of X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Jing; Wang, Jia-Ou; Yi, Fu-Ting; Wu, Rui; Zhang, Nian; Ibrahim, Kurash

    2014-09-01

    Silicon nanopillars are fabricated by inductively coupled plasma (ICP) dry etching with the cesium chloride (CsCl) islands as masks originally from self-assembly. Wafers with nanopillar texture or planar surface are subjected to phosphorus (P) diffusion by liquid dopant source (POCl3) at 870 °C to form P—N junctions with a depth of 300 nm. The X-ray photoelectron spectroscopy (XPS) is used to measure the Si 2p core levels of P—N junction wafer with nanopillar texture and planar surface. With a visible light excitation, the P—N junction produces a new electric potential for photoelectric characteristic, which causes the Si 2p core level to have a energy shift compared with the spectrum without the visible light. The energy shift of the Si 2p core level is -0.27 eV for the planar P—N junction and -0.18 eV for the nanopillar one. The difference in Si 2p energy shift is due to more space lattice defects and chemical bond breaks for nanopillar compared with the planar one.

  2. Investigation of composition and chemical state of elements in iron boride by the method of X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Alyoshin, V. G.; Kharlamov, A. I.; Prokopenko, V. M.

    1981-06-01

    The composition and chemical state of iron and boron in the surface layer of iron boride under different kinds of pretreatment of samples have been investigated by the method of X-ray photo-electron spectroscopy. It has been found that in the initial sample there is oxygen chemically combined with iron and boron atoms. Upon heating (450°C) in hydrogen, in argon, and in vacuo there occurs removal of oxygen only from iron atoms (no pure iron was found to be formed). Boron oxidizes and there probably appears a new surface combination of boron with oxygen in which the bonding energy of 1 s electrons is higher than that in B 2O 3. Treatment of the iron boride surface with argon ions and with protons ensures uniform removal of oxygen from iron and boron atoms. It has been found that thermal treatment of iron boride leads to depletion of iron atoms from the sample surface layer, and pickling with argon ions and with protons leads to strong enrichment. Iron boride samples subjected to Ar + and H + bombardment tend to undergo significant oxidation when subsequently exposed to air at room temperature.

  3. Three-Dimensional Electron Realm in VSe2 by Soft-X-Ray Photoelectron Spectroscopy: Origin of Charge-Density Waves

    NASA Astrophysics Data System (ADS)

    Strocov, Vladimir N.; Shi, Ming; Kobayashi, Masaki; Monney, Claude; Wang, Xiaoqiang; Krempasky, Juraj; Schmitt, Thorsten; Patthey, Luc; Berger, Helmuth; Blaha, Peter

    2012-08-01

    The resolution of angle-resolved photoelectron spectroscopy (ARPES) in three-dimensional (3D) momentum k is fundamentally limited by ill defined surface-perpendicular wave vector k⊥ associated with the finite photoelectron mean free path. Pushing ARPES into the soft-x-ray energy region sharpens the k⊥ definition, allowing accurate electronic structure investigations in 3D materials. We apply soft-x-ray ARPES to explore the 3D electron realm in a paradigm transition metal dichalcogenide VSe2. Essential to break through the dramatic loss of the valence band photoexcitation cross section at soft-x-ray energies is the advanced photon flux performance of our synchrotron instrumentation. By virtue of the sharp 3D momentum definition, the soft-x-ray ARPES experimental band structure and Fermi surface of VSe2 show a textbook clarity. We identify pronounced 3D warping of the Fermi surface and show that its concomitant nesting acts as the precursor for the exotic 3D charge-density waves in VSe2. Our results demonstrate the immense potential of soft-x-ray ARPES to explore details of 3D electronic structure.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  5. Iron location in O-carboxymethyl chitosans determined by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Klepka, Marcin T.; Lawniczak-Jablonska, Krystyna; Wolska, Anna; Slawska-Waniewska, Anna; Rodrigues, Clóvis A.; Lorini, Josiane; Cruz, Karianne Araujo da

    2011-01-01

    Chitosans represent a class of functional natural polymers. Their unique attribute is the capability to bind metal ions into their structure. This property can be exploited in many biomedical applications, but before that, some questions about metal binding mechanism must be answered. O-carboxymethyl chitosans with accumulated Fe atoms were studied by X-ray absorption spectroscopy. It was shown that iron bonding depends on the technological processes used in chitosan production. The applied technology allows for the selective introduction of either oxygen alone or of nitrogen and oxygen into the nearest neighbourhood of Fe. Therefore, it is possible to control the surroundings of a metal atom depending on requirements.

  6. Extension to Low Energies (<7keV) of High Pressure X-Ray Absorption Spectroscopy

    SciTech Connect

    Itie, J.-P.; Flank, A.-M.; Lagarde, P.; Idir, M.; Polian, A.; Couzinet, B.

    2007-01-19

    High pressure x-ray absorption has been performed down to 3.6 keV, thanks to the new LUCIA beamline (SLS, PSI) and to the use of perforated diamonds or Be gasket. Various experimental geometries are proposed, depending on the energy of the edge and on the concentration of the studied element. A few examples will be presented: BaTiO3 at the titanium K edge, Zn0.95 Mn0.05O at the manganese K edge, KCl at the potassium K edge.

  7. Comparison Between X-rays Absorption and Emission Spectroscopy Measurements on a Ceramic Envelop Lamp

    NASA Astrophysics Data System (ADS)

    Lafitte, Bruno; Aubes, Michel; Zissis, Georges

    2007-12-01

    Burners of metal halide lamps used for illumination are generally made of polycrystalline alumina ceramic (PCA) which is translucent to visible light. We show that the difficulty of selecting a line of sight through the lamp prevents the use of optical emission diagnostic. X-rays photons are mainly absorbed and not scattered by PCA. Absorption by mercury atoms contributing to the discharge allowed us to determine the density of mercury in the lamp. By comparing diagnostic methods, we put in evidence the difficulty of taking into account the scattering of light mathematically.

  8. An x-ray absorption spectroscopy study of Cd binding onto a halophilic archaeon

    NASA Astrophysics Data System (ADS)

    Showalter, Allison R.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Bunker, Bruce A.

    2016-05-01

    X-ray absorption spectroscopy (XAS) and cadmium (Cd) isotherm experiments determine how Cd adsorbs to the surface of halophilic archaeon Halobacterium noricense. This archaeon, isolated from the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico could be involved with the transport of toxic metals stored in the transuranic waste in the salt mine. The isotherm experiments show that adsorption is relatively constant across the tolerable pH range for H. noricense. The XAS results indicate that Cd adsorption occurs predominately via a sulfur site, most likely sulfhydryl, with the same site dominating all measured pH values.

  9. Direct measurement of the soil water retention curve using X-ray absorption

    NASA Astrophysics Data System (ADS)

    Bayer, A.; Vogel, H.-J.; Roth, K.

    X-ray absorption measurements have been explored as a fast experimental approach to determine soil hydraulic properties and to study rapid dynamic processes. As examples, the pressure-saturation relation θ(Ψ) for a uniform sand column has been considered as has capillary rise in an initially dry sintered glass column. The θ(Ψ)-relation is in reasonable agreement with that obtained by inverting a traditional multi-step outflow experiment. Monitoring the initial phase of capillary rise reveals behaviour that deviates qualitatively from the single-phase, local-equilibrium regime described by Richards’ equation.

  10. X-ray absorption study of pulsed laser deposited boron nitride films

    SciTech Connect

    Chaiken, A.; Terminello, L.J.; Wong, J.; Doll, G.L.; Sato, T.

    1994-02-02

    B and N K-edge x-ray absorption spectroscopy measurements have been performed on three BN thin films grown on Si substrates using ion- assisted pulsed laser deposition. Comparison of the films` spectra to those of several single-phase BN powder standards shows that the films consist primarily of sp{sup 2} bonds. Other features in the films`s spectra suggest the presence of secondary phases, possibly cubic or rhombohedral BN. Films grown at higher deposition rates and higher ion-beam voltages are found to be more disordered, in agreement with previous work.

  11. X-Ray Absorption Spectroscopy of Cuprous-Thiolate Clusters in Saccharomyces Cerevisiae Metallothionein

    SciTech Connect

    Zhang, L.; Pickering, I.J.; Winge, D.R.; George, G.N.

    2009-05-28

    Copper (Cu) metallothioneins are cuprous-thiolate proteins that contain multimetallic clusters, and are thought to have dual functions of Cu storage and Cu detoxification. We have used a combination of X-ray absorption spectroscopy (XAS) and density-functional theory (DFT) to investigate the nature of Cu binding to Saccharomyces cerevisiae metallothionein. We found that the XAS of metallothionein prepared, containing a full complement of Cu, was quantitatively consistent with the crystal structure, and that reconstitution of the apo-metallothionein with stoichiometric Cu results in the formation of a tetracopper cluster, indicating cooperative binding of the Cu ions by the metallothionein.

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

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  13. In-situ x-ray absorption study of copper films in ground watersolutions

    SciTech Connect

    Kvashnina, K.O.; Butorin, S.M.; Modin, A.; Soroka, I.; Marcellini, M.; Nordgren, J.; Guo, J.-H.; Werme, L.

    2007-10-29

    This study illustrates how the damage from copper corrosion can be reduced by modifying the chemistry of the copper surface environment. The surface modification of oxidized copper films induced by chemical reaction with Cl{sup -} and HCO{sub 3}{sup -} in aqueous solutions was monitored by in situ X-ray absorption spectroscopy. The results show that corrosion of copper can be significantly reduced by adding even a small amount of sodium bicarbonate. The studied copper films corroded quickly in chloride solutions, whereas the same solution containing 1.1 mM HCO{sub 3}{sup -} prevented or slowed down the corrosion processes.

  14. Automated system for x-ray absorption spectroscopy of nanoparticle nucleation and growth

    SciTech Connect

    Calvin, S.; Carpenter, E.E.; Cestone, V.; Kurihara, L.K.; Harris, V.G.; Brown, E.C.

    2005-01-01

    X-ray absorption spectroscopy (XAS) is a useful tool for studying nanoparticle synthesis and growth. Described here is a system for automating synthesis and data collection, allowing time-resolved XAS measurements at a synchrotron to be accurately combined with measurements made under identical conditions elsewhere, and promising the ability to use XAS with experiments in combinatorial chemistry. The primary components of this system are a commercial parallel processor and a custom flow cell. The system has been used to collect data on the synthesis of iron oxides from iron(II) acetylacetonate.

  15. Improvement of filling bismuth for x-ray absorption gratings through the enhancement of wettability

    NASA Astrophysics Data System (ADS)

    Lei, Yaohu; Liu, Xin; Li, Ji; Guo, Jinchuan; Niu, Hanben

    2016-06-01

    Filling materials with high x-ray linear absorption coefficients in high aspect-ratio (HAR) structures is a key process for the fabrication of absorption gratings used in x-ray differential phase-contrast imaging. Bismuth has been chosen as an effective filling material in micro-casting technology, because of its low cost both in price and facility use. However, repellence on structure surfaces against molten bismuth leads to an obstacle in terms of completely filling bismuth into the small-aperture and HAR microstructure formed by photo-assisted electrochemical etching in 5 inch silicon wafers. We propose and implement a novel method of surface modification to completely fill bismuth into these structures with periods of 3 μm and 42 μm, respectively, and as deep as 150 μm. The modified surface with a Bi2O3 layer covering the structure surface, including the side walls, induces an enhanced bismuth filling ratio. The superiority of the method is demonstrated by micrographs which show filled microstructures compared to the previously used method, where only a layer of 100 nm SiO2 was covered. Furthermore, we have observed that the improved micro-casting makes the absorption gratings clean surfaces, and no post treatment is needed.

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

    SciTech Connect

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

    1994-11-01

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

  17. Joint absorption and phase retrieval in grating-based x-ray radiography.

    PubMed

    Nilchian, Masih; Bostan, Emrah; Wang, Zhentian; Nilchiyan, Mohammad Reza; Stampanoni, Marco; Unser, Michael

    2016-04-01

    Given the raw absorption and differential phase-contrast images obtained from a grating-based x-ray radiography, we formulate the joint denoising of the absorption image and retrieval of the non-differential phase image as a regularized inverse problem. The choice of the regularizer is driven by the existing correlation between absorption and differential phase; it leads to the linear combination of a total-variation norm with a total-variation nuclear norm. We then develop the corresponding algorithm to efficiently solve this inverse problem. We evaluate our method using different experiments, including mammography data. We conclude that our method provides useful information in the context of mammography screening and diagnosis.

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

    PubMed

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

    2013-02-13

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

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

    PubMed

    Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

    2015-11-01

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

  20. Excited-state molecular structures captured by X-ray transient absorption spectroscopy: a decade and beyond.

    PubMed

    Chen, Lin X; Zhang, Xiaoyi; Lockard, Jenny V; Stickrath, Andrew B; Attenkofer, Klaus; Jennings, Guy; Liu, Di-Jia

    2010-03-01

    Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes have been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled. PMID:20164647

  1. First-principles calculations of K-shell X-ray absorption spectra for warm dense nitrogen

    NASA Astrophysics Data System (ADS)

    Li, Zi; Zhang, Shen; Wang, Cong; Kang, Wei; Zhang, Ping

    2016-05-01

    X-ray absorption spectrum is a powerful tool for atomic structure detection on warm dense matter. Here, we perform first-principles molecular dynamics and X-ray absorption spectrum calculations on warm dense nitrogen along a Hugoniot curve. From the molecular dynamics trajectory, the detailed atomic structures are examined for each thermodynamical condition. The K-shell X-ray absorption spectrum is calculated, and its changes with temperature and pressure along the Hugoniot curve are discussed. The warm dense nitrogen systems may contain isolated nitrogen atoms, N2 molecules, and nitrogen clusters, which show quite different contributions to the total X-ray spectrum due to their different electron density of states. The changes of X-ray spectrum along the Hugoniot curve are caused by the different nitrogen structures induced by the temperature and the pressure. Some clear signatures on X-ray spectrum for different thermodynamical conditions are pointed out, which may provide useful data for future X-ray experiments.

  2. Excited-state molecular structures captured by x-ray transient absorption spectroscopy : a decade and beyond.

    SciTech Connect

    Chen, L. X.; Zhang, X.; Lockard, J. V.; Stickrath, A. B.; Attenkofer, K.; Jennings, G.; Liu, D.-J.; Northwestern Univ.

    2010-03-02

    Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes have been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled.

  3. Valence band offset of β-Ga2O3/wurtzite GaN heterostructure measured by X-ray photoelectron spectroscopy

    PubMed Central

    2012-01-01

    A sample of the β-Ga2O3/wurtzite GaN heterostructure has been grown by dry thermal oxidation of GaN on a sapphire substrate. X-ray diffraction measurements show that the β-Ga2O3 layer was formed epitaxially on GaN. The valence band offset of the β-Ga2O3/wurtzite GaN heterostructure is measured by X-ray photoelectron spectroscopy. It is demonstrated that the valence band of the β-Ga2O3/GaN structure is 1.40 ± 0.08 eV. PMID:23046910

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

    PubMed Central

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

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

    SciTech Connect

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

    1994-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    SciTech Connect

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

    1998-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

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

    PubMed

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

    2016-09-01

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

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

    SciTech Connect

    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

  13. Interface electronic properties of co-evaporated MAPbI3 on ZnO(0001): In situ X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy study

    NASA Astrophysics Data System (ADS)

    Zhou, Xianzhong; Li, Xiaoli; Liu, Yuan; Huang, Feng; Zhong, Dingyong

    2016-03-01

    In this work, the interface electronic properties of ZnO(0001)/CH3NH3PbI3 were investigated by both X-ray and ultraviolet photoelectron spectroscopy. The CH3NH3PbI3 thin films were grown on single crystalline ZnO(0001) substrate in situ by co-evaporation of PbI2 and CH3NH3I at room temperature with various thickness from 1.5 nm to 190 nm. It was found that the conduction band minimum of ZnO lies 0.3 eV below that of CH3NH3PbI3, while the valence band maximum of ZnO lies 2.1 eV below that of CH3NH3PbI3, implying that the electrons can be effectively transported from CH3NH3PbI3 to ZnO, and the holes can be blocked in the same time. A PbI2 rich layer was initially formed at the interface of ZnO(0001)/CH3NH3PbI3 during the growth. As a consequence, an interface barrier was built up which may prevent the electron transport at the interface.

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

    PubMed

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

    2014-05-01

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

  15. Characterization of metalloproteins by high-throughput X-ray absorption spectroscopy.

    PubMed

    Shi, Wuxian; Punta, Marco; Bohon, Jen; Sauder, J Michael; D'Mello, Rhijuta; Sullivan, Mike; Toomey, John; Abel, Don; Lippi, Marco; Passerini, Andrea; Frasconi, Paolo; Burley, Stephen K; Rost, Burkhard; Chance, Mark R

    2011-06-01

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

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

    SciTech Connect

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

    2011-12-31

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

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

    USGS Publications Warehouse

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

    2000-01-01

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

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

    SciTech Connect

    Andrews, J.C. |

    1995-08-01

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

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

    PubMed

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

    2011-11-01

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

  20. Femtosecond X-ray absorption study of electron localization in photoexcited anatase TiO2

    PubMed Central

    Santomauro, F. G.; Lübcke, A.; Rittmann, J.; Baldini, E.; Ferrer, A.; Silatani, M.; Zimmermann, P.; Grübel, S.; Johnson, J. A.; Mariager, S. O.; Beaud, P.; Grolimund, D.; Borca, C.; Ingold, G.; Johnson, S.L.; Chergui, M.

    2015-01-01

    Transition metal oxides are among the most promising solar materials, whose properties rely on the generation, transport and trapping of charge carriers (electrons and holes). Identifying the latter’s dynamics at room temperature requires tools that combine elemental and structural sensitivity, with the atomic scale resolution of time (femtoseconds, fs). Here, we use fs Ti K-edge X-ray absorption spectroscopy (XAS) upon 3.49 eV (355 nm) excitation of aqueous colloidal anatase titanium dioxide nanoparticles to probe the trapping dynamics of photogenerated electrons. We find that their localization at Titanium atoms occurs in <300 fs, forming Ti3+ centres, in or near the unit cell where the electron is created. We conclude that electron localization is due to its trapping at pentacoordinated sites, mostly present in the surface shell region. The present demonstration of fs hard X-ray absorption capabilities opens the way to a detailed description of the charge carrier dynamics in transition metal oxides. PMID:26437873

  1. Femtosecond X-ray absorption study of electron localization in photoexcited anatase TiO2.

    PubMed

    Santomauro, F G; Lübcke, A; Rittmann, J; Baldini, E; Ferrer, A; Silatani, M; Zimmermann, P; Grübel, S; Johnson, J A; Mariager, S O; Beaud, P; Grolimund, D; Borca, C; Ingold, G; Johnson, S L; Chergui, M

    2015-10-06

    Transition metal oxides are among the most promising solar materials, whose properties rely on the generation, transport and trapping of charge carriers (electrons and holes). Identifying the latter's dynamics at room temperature requires tools that combine elemental and structural sensitivity, with the atomic scale resolution of time (femtoseconds, fs). Here, we use fs Ti K-edge X-ray absorption spectroscopy (XAS) upon 3.49 eV (355 nm) excitation of aqueous colloidal anatase titanium dioxide nanoparticles to probe the trapping dynamics of photogenerated electrons. We find that their localization at Titanium atoms occurs in <300 fs, forming Ti(3+) centres, in or near the unit cell where the electron is created. We conclude that electron localization is due to its trapping at pentacoordinated sites, mostly present in the surface shell region. The present demonstration of fs hard X-ray absorption capabilities opens the way to a detailed description of the charge carrier dynamics in transition metal oxides.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  3. X-ray absorption Studies of Zinc species in Centella asiatica

    NASA Astrophysics Data System (ADS)

    Dehipawala, Sunil; Cheung, Tak; Hogan, Clayton; Agoudavi, Yao; Dehipawala, Sumudu

    2013-03-01

    Zinc is a very important mineral present in a variety of vegetables. It is an essential element in cellular metabolism and several bodily functions. We used X-ray fluorescence, and X-ray Absorption near Edge structure(XANES) to study the amount of zinc present in several leafy vegetables as well as its chemical environment within the plant. Main absorption edge position of XANES is sensitive to the oxidation state of zinc and is useful when comparing the type of zinc present in different vegetables to the standard zinc present in supplements. Normalized main edge height is proportional to the amount of zinc present in the sample. Several leafy greens were used in this study, such as Spinacia oleracea, Basella alba, Brassica oleracea, Cardiospermum halicacabumand Centella asiatica. All of these plant leaves contained approximately the same amount of zinc in the leaf portion of the plant and a slightly lower amount in the stems, except Centella asiatica. Both leaves and stems of the plant Centella asiatica contained nearly two times the zinc compared to other plants. Further investigation of zinc's chemical environment within Centella asiatica could lead to a much more efficient dietary consumption of zinc. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886

  4. Strontium localization in bone tissue studied by X-ray absorption spectroscopy.

    PubMed

    Frankær, Christian Grundahl; Raffalt, Anders Christer; Stahl, Kenny

    2014-02-01

    Strontium has recently been introduced as a pharmacological agent for the treatment and prevention of osteoporosis. We determined the localization of strontium incorporated into bone matrix from dogs treated with Sr malonate by X-ray absorption spectroscopy. A new approach for analyzing the X-ray absorption spectra resulted in a compositional model and allowed the relative distribution of strontium in the different bone components to be estimated. Approximately 35-45% of the strontium present is incorporated into calcium hydroxyapatite (CaHA) by substitution of some of the calcium ions occupying highly ordered sites, and at least 30% is located at less ordered sites where only the first solvation shell is resolved, suggesting that strontium is surrounded by only oxygen atoms similar to Sr(2+) in solution. Strontium was furthermore shown to be absorbed in collagen in which it obtains a higher structural order than when present in serum but less order than when it is incorporated into CaHA. The total amount of strontium in the samples was determined by inductively coupled plasma mass spectrometry, and the amount of Sr was found to increase with increasing dose levels and treatment periods, whereas the relative distribution of strontium among the different components appears to be independent of treatment period and dose level.

  5. X-ray absorption spectroscopy as a probe of dissolved polysulfides in lithium sulfur batteries

    NASA Astrophysics Data System (ADS)

    Pascal, Tod; Prendergast, David

    2015-03-01

    There has been enormous interest lately in lithium sulfur batteries, since they have 5 times the theoretical capacity of lithium ion batteries. Large-scale adoption of this technology has been hampered by numerous shortcomings, chiefly the poor utilization of the active cathode material and rapid capacity fading during cycling. Overcoming these limitations requires methods capable of identifying and quantifying the products of the poorly understood electrochemical reactions. One recent advance has been the use of X-ray absorption spectroscopy (XAS), an element-specific probe of the unoccupied energy levels around an excited atom upon absorption of an X-ray photon, to identify the reaction products and intermediates. In this talk, we'll present first principles molecular dynamics and spectral simulations of dissolved lithium polysulfide species, showing how finite temperature dynamics, molecular geometry, molecular charge state and solvent environment conspire to determine the peak positions and intensity of the XAS. We'll present a spectral analysis of the radical (-1e charge) species, and reveal a unique low energy feature that can be used to identify these species from their more common dianion (-2e charge) counterparts.

  6. X-ray absorption spectroscopy on magnetic nanoscale systems for modern applications

    NASA Astrophysics Data System (ADS)

    Schmitz-Antoniak, Carolin

    2015-06-01

    X-ray absorption spectroscopy facilitated by state-of-the-art synchrotron radiation technology is presented as a powerful tool to study nanoscale systems, in particular revealing their static element-specific magnetic and electronic properties on a microscopic level. A survey is given on the properties of nanoparticles, nanocomposites and thin films covering a broad range of possible applications. It ranges from the ageing effects of iron oxide nanoparticles in dispersion for biomedical applications to the characterisation on a microscopic level of nanoscale systems for data storage devices. In this respect, new concepts for electrically addressable magnetic data storage devices are highlighted by characterising the coupling in a BaTiO3/CoFe2O4 nanocomposite as prototypical model system. But classical magnetically addressable devices are also discussed on the basis of tailoring the magnetic properties of self-assembled ensembles of FePt nanoparticles for data storage and the high-moment material Fe/Cr/Gd for write heads. For the latter cases, the importance is emphasised of combining experimental approaches in x-ray absorption spectroscopy with density functional theory to gain a more fundamental understanding.

  7. X-ray fluorescence and absorption analysis of krypton in irradiated nuclear fuel

    NASA Astrophysics Data System (ADS)

    Degueldre, Claude; Mieszczynski, Cyprian; Borca, Camelia; Grolimund, Daniel; Martin, Matthias; Bertsch, Johannes

    2014-10-01

    The analysis of krypton in irradiated uranium dioxide fuel has been successfully achieved by X-ray fluorescence and X-ray absorption. The present study focuses on the analytical challenge of sample and sub-sample production to perform the analysis with the restricted conditions dictated by the radioprotection regulations. It deals also with all potential interferences that could affect the quality of the measurement in fluorescence as well as in absorption mode. The impacts of all dissolved gases in the fuel matrix are accounted for the analytical result quantification. The krypton atomic environment is ruled by the presence of xenon. Other gases such as residual argon and traces of helium or hydrogen are negligible. The results are given in term of density for krypton (∼3 nm-3) and xenon (∼20 nm-3). The presence of dissolved, interstitial and nano-phases are discussed together with other analytical techniques that could be applied to gain information on fission gas behaviour in nuclear fuels.

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

    SciTech Connect

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

    2007-05-07

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

  9. Strontium localization in bone tissue studied by X-ray absorption spectroscopy.

    PubMed

    Frankær, Christian Grundahl; Raffalt, Anders Christer; Stahl, Kenny

    2014-02-01

    Strontium has recently been introduced as a pharmacological agent for the treatment and prevention of osteoporosis. We determined the localization of strontium incorporated into bone matrix from dogs treated with Sr malonate by X-ray absorption spectroscopy. A new approach for analyzing the X-ray absorption spectra resulted in a compositional model and allowed the relative distribution of strontium in the different bone components to be estimated. Approximately 35-45% of the strontium present is incorporated into calcium hydroxyapatite (CaHA) by substitution of some of the calcium ions occupying highly ordered sites, and at least 30% is located at less ordered sites where only the first solvation shell is resolved, suggesting that strontium is surrounded by only oxygen atoms similar to Sr(2+) in solution. Strontium was furthermore shown to be absorbed in collagen in which it obtains a higher structural order than when present in serum but less order than when it is incorporated into CaHA. The total amount of strontium in the samples was determined by inductively coupled plasma mass spectrometry, and the amount of Sr was found to increase with increasing dose levels and treatment periods, whereas the relative distribution of strontium among the different components appears to be independent of treatment period and dose level. PMID:24101232

  10. Evolution of Silver Nanoparticles in the Rat Lung Investigated by X-ray Absorption Spectroscopy

    PubMed Central

    2015-01-01

    Following a 6-h inhalation exposure to aerosolized 20 and 110 nm diameter silver nanoparticles, lung tissues from rats were investigated with X-ray absorption spectroscopy, which can identify the chemical state of silver species. Lung tissues were processed immediately after sacrifice of the animals at 0, 1, 3, and 7 days post exposure and the samples were stored in an inert and low-temperature environment until measured. We found that it is critical to follow a proper processing, storage and measurement protocol; otherwise only silver oxides are detected after inhalation even for the larger nanoparticles. The results of X-ray absorption spectroscopy measurements taken in air at 85 K suggest that the dominating silver species in all the postexposure lung tissues were metallic silver, not silver oxide, or solvated silver cations. The results further indicate that the silver nanoparticles in the tissues were transformed from the original nanoparticles to other forms of metallic silver nanomaterials and the rate of this transformation depended on the size of the original nanoparticles. We found that 20 nm diameter silver nanoparticles were significantly modified after aerosolization and 6-h inhalation/deposition, whereas larger, 110 nm diameter nanoparticles were largely unchanged. Over the seven-day postexposure period the smaller 20 nm silver nanoparticles underwent less change in the lung tissue than the larger 110 nm silver nanoparticles. In contrast, silica-coated gold nanoparticles did not undergo any modification processes and remained as the initial nanoparticles throughout the 7-day study period. PMID:25517690

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

    PubMed

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

    2011-11-01

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

  12. High temperature emissivity, reflectivity, and x-ray absorption of BiFeO3

    NASA Astrophysics Data System (ADS)

    Massa, Néstor E.; del Campo, Leire; de Souza Meneses, Domingos; Echegut, Patrick; Fabbris, Gilberto F. L.; Azevedo, G. de M.; Martínez-Lope, María Jesús; Alonso, José Antonio

    2010-10-01

    We report on the lattice evolution of BiFeO3 as function of temperature using far infrared emissivity, reflectivity, and x-ray absorption local structure. A power law fit to the lowest frequency soft phonon in the magnetic ordered phase yields an exponent β =0.25 as for a tricritical point. At about 200 K below TN˜640 K it ceases softening as consequence of BiFeO3 metastability. We identified this temperature as corresponding to a crossover transition to an order-disorder regime. Above ˜700 K strong band overlapping, merging, and smearing of modes are consequence of thermal fluctuations and chemical disorder. Vibrational modes show band splits in the ferroelectric phase as emerging from triple degenerated species as from a paraelectric cubic phase above TC˜1090 K. Temperature dependent x-ray absorption near edge structure (XANES) at the Fe K edge shows that lower temperature Fe3+ turns into Fe2+. While this matches the FeO wüstite XANES profile, the Bi LIII-edge downshift suggests a high temperature very complex bond configuration at the distorted A perovskite site. Overall, our local structural measurements reveal high temperature defect-induced irreversible lattice changes, below, and above the ferroelectric transition, in an environment lacking of long-range coherence. We did not find an insulator to metal transition prior to melting.

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

    SciTech Connect

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

    2013-01-07

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

  14. Melting of iron determined by X-ray absorption spectroscopy to 100 GPa

    PubMed Central

    Aquilanti, Giuliana; Trapananti, Angela; Karandikar, Amol; Kantor, Innokenty; Marini, Carlo; Mathon, Olivier; Pascarelli, Sakura; Boehler, Reinhard

    2015-01-01

    Temperature, thermal history, and dynamics of Earth rely critically on the knowledge of the melting temperature of iron at the pressure conditions of the inner core boundary (ICB) where the geotherm crosses the melting curve. The literature on this subject is overwhelming, and no consensus has been reached, with a very large disagreement of the order of 2,000 K for the ICB temperature. Here we report new data on the melting temperature of iron in a laser-heated diamond anvil cell to 103 GPa obtained by X-ray absorption spectroscopy, a technique rarely used at such conditions. The modifications of the onset of the absorption spectra are used as a reliable melting criterion regardless of the solid phase from which the solid to liquid transition takes place. Our results show a melting temperature of iron in agreement with most previous studies up to 100 GPa, namely of 3,090 K at 103 GPa. PMID:26371317

  15. Calibration and analysis of spatially resolved x-ray absorption spectra from a nonuniform plasma

    SciTech Connect

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

    2012-07-15

    We report here the calibration and analysis techniques used to obtain spatially resolved density and temperature measurements of a pair of imploding aluminum wires from x-ray absorption spectra. A step wedge is used to measure backlighter fluence at the film, allowing transmission through the sample to be measured with an accuracy of {+-}14% or better. A genetic algorithm is used to search the allowed plasma parameter space and fit synthetic spectra with 20 {mu}m spatial resolution to the measured spectra, taking into account that the object plasma nonuniformity must be physically reasonable. The inferred plasma conditions must be allowed to vary along the absorption path in order to obtain a fit to the spectral data. The temperature is estimated to be accurate to within {+-}25% and the density to within a factor of two. This information is used to construct two-dimensional maps of the density and temperature of the object plasma.

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

    SciTech Connect

    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.

  17. Melting of iron determined by X-ray absorption spectroscopy to 100 GPa.

    PubMed

    Aquilanti, Giuliana; Trapananti, Angela; Karandikar, Amol; Kantor, Innokenty; Marini, Carlo; Mathon, Olivier; Pascarelli, Sakura; Boehler, Reinhard

    2015-09-29

    Temperature, thermal history, and dynamics of Earth rely critically on the knowledge of the melting temperature of iron at the pressure conditions of the inner core boundary (ICB) where the geotherm crosses the melting curve. The literature on this subject is overwhelming, and no consensus has been reached, with a very large disagreement of the order of 2,000 K for the ICB temperature. Here we report new data on the melting temperature of iron in a laser-heated diamond anvil cell to 103 GPa obtained by X-ray absorption spectroscopy, a technique rarely used at such conditions. The modifications of the onset of the absorption spectra are used as a reliable melting criterion regardless of the solid phase from which the solid to liquid transition takes place. Our results show a melting temperature of iron in agreement with most previous studies up to 100 GPa, namely of 3,090 K at 103 GPa.

  18. Atomic absorption spectrophotometric and X-ray studies of respirable dusts in Indian coal mines

    SciTech Connect

    Rawat, N.S.; Sinha, J.D.; Sahoo, B.

    1982-01-01

    Quantitative determination of 10 minor and 8 trace elements in respirable coal dust by atomic absorption spectrophotometry is described herein. The coal dust samples were collected in the mine atmosphere during drilling in coal seams. A ''Hexhlet'' appratus specially designed and fitted with a horizontal elutriator was used to collect the respirable coal dust fraction. After destruction of organic matter by wet oxidation and filtering off the clay and silica, iron, calcium, magnesium, sodium, potassium, manganese, zinc, copper, cadmium, and nickel were determined directly in the resulting solution by atomic absorption spectrophotometry. The studies relate to a respiratoy disease-pneumoconiosis-affecting coal mine workers. X-Ray diffraction studies have shown the presence of kaolin, quartz, pirrsonite and beidellite clay minerals in the coal dust.

  19. Effects of dispersion and absorption in resonant Bragg diffraction of x-rays.

    PubMed

    Lovesey, S W; Scagnoli, V; Dobrynin, A N; Joly, Y; Collins, S P

    2014-03-26

    Resonant diffraction of x-rays by crystals with anisotropic optical properties is investigated theoretically, to assess how the intensity of a Bragg spot is influenced by effects related to dispersion (birefringence) and absorption (dichroism). Starting from an exact but opaque expression, simple analytic results are found to expose how intensity depends on dispersion and absorption in the primary and secondary beams and, also, the azimuthal angle (rotation of the crystal about the Bragg wavevector). If not the full story for a given application, our results are more than adequate to explore consequences of dispersion and absorption in the intensity of a Bragg spot. Results are evaluated for antiferromagnetic copper oxide, and low quartz. For CuO, one of our results reproduces all salient features of a previously published simulation of the azimuthal-angle dependence of a magnetic Bragg peak. It is transparent in our analytic result that dispersion and absorption effects alone cannot reproduce published experimental data. Available data for the azimuthal-angle dependence of space-group forbidden reflections (0,0, l), with l ≠ 3n, of low quartz depart from symmetry imposed by the triad axis of rotation symmetry. The observed asymmetry can be induced by dispersion and absorption even though absorption coefficients are constant, independent of the azimuthal angle, in this class of reflections.

  20. Effects of dispersion and absorption in resonant Bragg diffraction of x-rays.

    PubMed

    Lovesey, S W; Scagnoli, V; Dobrynin, A N; Joly, Y; Collins, S P

    2014-03-26

    Resonant diffraction of x-rays by crystals with anisotropic optical properties is investigated theoretically, to assess how the intensity of a Bragg spot is influenced by effects related to dispersion (birefringence) and absorption (dichroism). Starting from an exact but opaque expression, simple analytic results are found to expose how intensity depends on dispersion and absorption in the primary and secondary beams and, also, the azimuthal angle (rotation of the crystal about the Bragg wavevector). If not the full story for a given application, our results are more than adequate to explore consequences of dispersion and absorption in the intensity of a Bragg spot. Results are evaluated for antiferromagnetic copper oxide, and low quartz. For CuO, one of our results reproduces all salient features of a previously published simulation of the azimuthal-angle dependence of a magnetic Bragg peak. It is transparent in our analytic result that dispersion and absorption effects alone cannot reproduce published experimental data. Available data for the azimuthal-angle dependence of space-group forbidden reflections (0,0, l), with l ≠ 3n, of low quartz depart from symmetry imposed by the triad axis of rotation symmetry. The observed asymmetry can be induced by dispersion and absorption even though absorption coefficients are constant, independent of the azimuthal angle, in this class of reflections. PMID:24599265

  1. X-ray magnetic circular dichroism and x-ray absorption spectroscopy of novel magnetic thin films

    SciTech Connect

    Brewer, M.A.; Ju, H.L.; Krishnan, K.M.

    1997-04-01

    The optimization of the magnetic properties of materials for a wide range of applications requires a dynamic iteration between synthesis, property measurements and characterization at appropriate length scales. The authors interest arises both from the increased appreciation of the degree to which magnetic properties can be influenced by tailored microstructures and the ability to characterize them by x-ray scattering/dichroism techniques. Preliminary results of this work at the ALS on `giant` moment in {alpha}{double_prime}-Fe{sub 16}N{sub 2} and `colossal` magnetoresistance in manganite perovskites is presented here. It has recently been claimed that {alpha}{double_prime}-Fe{sub 16}N{sub 2} possesses a giant magnetization of 2.9 T ({approximately}2300 emu/cc) when grown on lattice-matched In{sub 0.2}Ga{sub 0.8}As(001) and Fe/GaAs(001). However, attempts at growth on simpler substrates have resulted in only a modest enhancement in moment and often in multiphase mixtures. Theoretical calculations based on the band structure of Fe{sub 16}N{sub 2} predict values for the magnetization around 2.3 T ({approximately}1780 emu/cc), well below Sugita`s claims, but consistent with the magnetization reported by several other workers. Using appropriate sum rules applied to the integrated MCD spectrum, they hope to determine the magnetic moment of the iron species in the {alpha}{double_prime}-Fe{sub 16}N{sub 2} films and other phases and resolve the orbital and spin contributions to the moment. There is also rapidly growing interest in the `colossal magnetoresistance` effect observed in manganese oxides for both fundamental and commercial applications. To address some of these issues the authors have measured the electron energy loss spectra (EELS) of manganese perovskites at room temperature.

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

    SciTech Connect

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

    2008-10-14

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

  3. Medieval glass from the Cathedral in Paderborn: a comparative study using X-ray absorption spectroscopy, X-ray fluorescence, and inductively coupled laser ablation mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hormes, J.; Roy, A.; Bovenkamp, G.-L.; Simon, K.; Kim, C.-Y.; Börste, N.; Gai, S.

    2013-04-01

    We have investigated four stained glass samples recovered from an archaeological excavation at the Cathedral in Paderborn (Germany) between 1978 and 1980. On two of the samples there are parts of paintings. Concentrations of major elements were determined using two independent techniques: LA-ICP-MS (a UV laser ablation microsampler combined with an inductively coupled plasma mass spectrometer) and synchrotron radiation X-ray excited X-ray fluorescence (SR-XRF). The SR-XRF data were quantified by using the program package PyMCA developed by the software group of the ESRF in Grenoble. Significant differences were found between the concentrations determined by the two techniques that can be explained by concentration gradients near the surface of the glasses caused, for example, by corrosion/leaching processes and the different surface sensitivities of the applied techniques. For several of the elements that were detected in the glass and in the colour pigments used for the paintings X-ray absorption near edge structure (XANES) spectra were recorded in order to determine the chemical speciation of the elements of interest. As was expected, most elements in the glass were found as oxides in their most stable form. Two notable exceptions were observed: titanium was not found as rutile—the most stable form of TiO2—but in the form of anatase, and lead was not found in one defined chemical state but as a complex mixture of oxide, sulphate, and other compounds.

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

    SciTech Connect

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

    2011-04-25

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-04-01

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

  6. Correlated single-crystal electronic absorption spectroscopy and X-ray crystallography at NSLS beamline X26-C

    SciTech Connect

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

    2011-05-01

    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.

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

    SciTech Connect

    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.

  8. Study of Surface Cleaning Methods and Pyrolysis Temperature on Nano-Structured Carbon Films using X-ray Photoelectron Spectroscopy

    SciTech Connect

    Kerber, Pranita B.; Porter, Lisa M.; McCullough, L. A.; Kowalewski, Tomasz; Engelhard, Mark H.; Baer, Donald R.

    2012-10-12

    Nanostructured carbon (ns-C) films fabricated by stabilization and pyrolysis of di-block copolymers are of interest for a variety of electrical/electronic applications due to their chemical inertness, high-temperature insensitivity, very high surface area, and tunable electrical resistivity over a wide range [Kulkarni et al., Synth. Met. 159, (2009) 177]. Because of their high porosity and associated high specific surface area, controlled surface cleaning studies are important for fabricating electronic devices from these films. In this study, quantification of surface composition and surface cleaning studies on ns-C films synthesized by carbonization of di-block copolymers of polyacrylonitrile-b-poly(n-butyl acrylate) (PAN-b-PBA) at two different temperatures were carried out. X-ray photoelectron spectroscopy was used for elemental analysis and to determine the efficacy of various surface cleaning methods for ns-C films and to examine the polymer residues in the films. The in-situ surface cleaning methods included: HF vapor treatment, vacuum annealing, and exposure to UV-ozone. Quantitative analysis of high-resolution XPS scans showed 11 at. % of nitrogen present in the films pyrolyzed at 600 °C, suggesting incomplete denitrogenation of the copolymer films. The nitrogen atomic concentration reduced significantly for films pyrolyzed at 900 °C confirming extensive denitrogenation at that temperature. Furthermore, quantitative analysis of nitrogen sub-peaks indicated higher loss of nitrogen atoms residing at the edge of graphitic clusters relative to that of nitrogen atoms within the graphitic cluster, suggesting higher graphitization with increasing pyrolysis temperature. Of the surface cleaning methods investigated, in-situ annealing of the films at 300 °C for 40 min was found to be the most efficacious in removing adventitious carbon and oxygen impurities from the surface.

  9. Study of surface cleaning methods and pyrolysis temperatures on nanostructured carbon films using x-ray photoelectron spectroscopy

    SciTech Connect

    Kerber, Pranita; Porter, Lisa M.; McCullough, Lynne A.; Kowalewski, Tomasz; Engelhard, Mark; Baer, Donald

    2012-11-15

    Nanostructured carbon (ns-C) films fabricated by stabilization and pyrolysis of diblock copolymers are of interest for a variety of electrical/electronic applications due to their chemical inertness, high-temperature insensitivity, very high surface area, and tunable electrical resistivity over a wide range [Kulkarni et al., Synth. Met. 159, 177 (2009)]. Because of their high porosity and associated high specific surface area, controlled surface cleaning studies are important for fabricating electronic devices from these films. In this study, quantification of surface composition and surface cleaning studies on ns-C films synthesized by carbonization of diblock copolymers of polyacrylonitrile-b-poly(n-butyl acrylate) at two different temperatures were carried out. X-ray photoelectron spectroscopy was used for elemental analysis and to determine the efficacy of various surface cleaning methods for ns-C films and to examine the polymer residues in the films. The in-situ surface cleaning methods included HF vapor treatment, vacuum annealing, and exposure to UV-ozone. Quantitative analysis of high-resolution XPS scans showed 11 at. % nitrogen was present in the films pyrolyzed at 600 Degree-Sign C, suggesting incomplete denitrogenation of the copolymer films. The nitrogen atomic concentration decreased significantly for films pyrolyzed at 900 Degree-Sign C confirming extensive denitrogenation at that temperature. Furthermore, quantitative analysis of nitrogen subpeaks indicated higher loss of nitrogen atoms residing at the edge of graphitic clusters relative to that of nitrogen atoms within the graphitic clusters, suggesting higher graphitization with increasing pyrolysis temperature. Of the surface cleaning methods investigated, in-situ annealing of the films at 300 Degree-Sign C for 40 min was found to be the most efficacious in removing adventitious carbon and oxygen impurities from the surface.

  10. Probing ultrathin film continuity and interface abruptness with x-ray photoelectron spectroscopy and low-energy ion scattering

    SciTech Connect

    Zhang, Wenyu; Nahm, Rambert K.; Engstrom, James R.; Ma, Paul F.

    2013-11-15

    The authors have examined ultrathin (≤10 Å) tantalum nitride (TaN{sub x}) thin films deposited by atomic layer deposition (ALD) on three surfaces relevant to interconnect layers in microelectronic devices: thermally grown SiO{sub 2}; a Cu thin film grown by physical vapor deposition, and a carbon-doped SiO{sub 2} porous low-κ thin film. The authors have employed ex situ angle-resolved x-ray photoelectron spectroscopy (ARXPS), low-energy ion scattering spectroscopy (LEISS), and atomic force microscopy (AFM) to determine the continuity of these thin films, and by implication, the abruptness of the thin film/substrate interface. On SiO{sub 2} and low-κ, the authors find similar results: both ARXPS and AFM indicate that smooth, uniform thin films are deposited, consistent with nearly layer-by-layer growth of TaN{sub x} on these surfaces. Examination of these films using LEISS reveals that while the 10 Å TaN{sub x} thin films are continuous, the 5 Å TaN{sub x} thin films are not continuous and may possess on the order of ∼10% exposed substrate in the form of small subnanometer inclusions. On Cu, the situation is quite different. The TaN{sub x} thin films on these surfaces are not continuous, and our results point to a mixed layer of TaN{sub x} and Cu forming during ALD. In all cases, if one were to rely solely on results from ARXPS, the picture would be incomplete as the results from LEISS are ultimately decisive concerning thin film continuity.

  11. Angle resolved x-ray photoelectron spectroscopy (ARXPS) analysis of lanthanum oxide for micro-flexography printing

    NASA Astrophysics Data System (ADS)

    Hassan, S.; Yusof, M. S.; Embong, Z.; Maksud, M. I.

    2016-01-01

    Micro-flexography printing was developed in patterning technique from micron to nano scale range to be used for graphic, electronic and bio-medical device on variable substrates. In this work, lanthanum oxide (La2O3) has been used as a rare earth metal candidate as depositing agent. This metal deposit was embedded on Carbon (C) and Silica (Si) wafer substrate using Magnetron Sputtering technique. The choose of Lanthanum as a target is due to its wide application in producing electronic devices such as thin film battery and printed circuit board. The La2O3 deposited on the surface of Si wafer substrate was then analyzed using Angle Resolve X-Ray Photoelectron Spectroscopy (ARXPS). The position for each synthetic component in the narrow scan of Lanthanum (La) 3d and O 1s are referred to the electron binding energy (eV). The La 3d narrow scan revealed that the oxide species of this particular metal is mainly contributed by La2O3 and La(OH)3. The information of oxygen species, O2- component from O 1s narrow scan indicated that there are four types of species which are contributed from the bulk (O2-), two chemisorb component (La2O3) and La(OH)3 and physisorp component (OH). Here, it is proposed that from the adhesive and surface chemical properties of La, it is suitable as an alternative medium for micro-flexography printing technique in printing multiple fine solid lines at nano scale. Hence, this paper will describe the capability of this particular metal as rare earth metal for use in of micro-flexography printing practice. The review of other parameters contributing to print fine lines will also be described later.

  12. Quantitative X-ray photoelectron spectroscopy-based depth profiling of bioleached arsenopyrite surface by Acidithiobacillus ferrooxidans

    NASA Astrophysics Data System (ADS)

    Zhu, Tingting; Lu, Xiancai; Liu, Huan; Li, Juan; Zhu, Xiangyu; Lu, Jianjun; Wang, Rucheng

    2014-02-01

    In supergene environments, microbial activities significantly enhance sulfide oxidation and result in the release of heavy metals, causing serious contamination of soils and waters. As the most commonly encountered arsenic mineral in nature, arsenopyrite (FeAsS) accounts for arsenic contaminants in various environments. In order to investigate the geochemical behavior of arsenic during microbial oxidation of arsenopyrite, (2 3 0) surfaces of arsenopyrite slices were characterized after acidic (pH 2.00) and oxidative decomposition with or without an acidophilic microorganism Acidithiobacillus ferrooxidans. The morphology as well as chemical and elemental depth profiles of the oxidized arsenopyrite surface were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. With the mediation of bacteria, cell-shaped and acicular pits were observed on the reacted arsenopyrite surface, and the concentration of released arsenic species in solution was 50 times as high as that of the abiotic reaction after 10 days reaction. Fine-scale XPS depth profiles of the reacted arsenopyrite surfaces after both microbial and abiotic oxidation provided insights into the changes in chemical states of the elements in arsenopyrite surface layers. Within the 450 nm surface layer of abiotically oxidized arsenopyrite, Fe(III)-oxides appeared and gradually increased towards the surface, and detectable sulfite and monovalent arsenic appeared above 50 nm. In comparison, higher contents of ferric sulfate, sulfite, and arsenite were found in the surface layer of approximately 3 μm of the microbially oxidized arsenopyrite. Intermediates, such as Fe(III)-AsS and S0, were detectable in the presence of bacteria. Changes of oxidative species derived from XPS depth profiles show the oxidation sequence is Fe > As = S in abiotic oxidation, and Fe > S > As in microbial oxidation. Based on these results, a possible reaction path of microbial oxidation was proposed in a concept model.

  13. X-Ray Absorption Studies of Silica-Supported Platinum Catalysts.

    NASA Astrophysics Data System (ADS)

    Mansour, Azzam Nouman

    X-ray absorption spectroscopy (near-edge structure and EXAFS) was used to characterize Pt/SiO(,2) catalysts both electronically and structurally. Two major developments have been made to characterize this system. A technique to quantitatively extract the number of d-band holes in a material utilizing measurements of the L(,2) and L(,3) x-ray absorption edge spectra is presented. The quantity determined is called "the d-electron character" and is defined as the fractional change in the number of d-band holes relative to a reference material. Next, EXAFS analysis procedures were extended to the higher shells (second, third, and fourth) by using the appropriate model shells from EXAFS data of a 2.5-(mu)m-thick platinum foil taken at liquid nitrogen temperature. Four samples were prepared: three by the ion-exchange technique with Pt loadings of 2 wt.%, 1 wt.%, and 0.5 wt.%, and one by the impregnation (incipient wetness) technique with Pt loading of 2 wt.%. The samples were subjected to different pretreatment conditions and were characterized by atomic absorption spectroscopy, electron microscopy, and hydrogen chemisorption. The conclusions made by x-ray absorption spectroscopy were as follows. All samples consist of highly dispersed spherical Pt particles with an average size in the range of 8-28 (ANGSTROM) and are electron deficient relative to bulk Pt. No significant changes on the structural and electronic properties are observed for Pt loadings in the range 1-2 wt.% and H('2)-reduction temperatures in the range 473-723 K for samples prepared by the ion-exchange technique. Slightly smaller Pt particles, which are more electron deficient, are formed when the Pt loading is decreased to 0.5 wt.%. The ion-exchange technique produces smaller Pt particles, which are more electron deficient relative to the impregnation technique. Samples prepared without the O('2)-calcination consist of smaller Pt particles, which are more electron deficient relative to samples prepared

  14. Saturable absorption of an x-ray free-electron-laser heated solid-density aluminum plasma.

    PubMed

    Rackstraw, D S; Ciricosta, O; Vinko, S M; Barbrel, B; Burian, T; Chalupský, J; Cho, B I; Chung, H-K; Dakovski, G L; Engelhorn, K; Hájková, V; Heimann, P; Holmes, M; Juha, L; Krzywinski, J; Lee, R W; Toleikis, S; Turner, J J; Zastrau, U; Wark, J S

    2015-01-01

    High-intensity x-ray pulses from an x-ray free-electron laser are used to heat and probe a solid-density aluminum sample. The photon-energy-dependent transmission of the heating beam is studied through the use of a photodiode. Saturable absorption is observed, with the resulting transmission differing significantly from the cold case, in good agreement with atomic-kinetics simulations.

  15. Synchrotron soft X-ray absorption spectroscopy study of carbon and silicon nanostructures for energy applications.

    PubMed

    Zhong, Jun; Zhang, Hui; Sun, Xuhui; Lee, Shuit-Tong

    2014-12-10

    Carbon and silicon materials are two of the most important materials involved in the history of the science and technology development. In the last two decades, C and Si nanoscale materials, e.g., carbon nanotubes, graphene, and silicon nanowires, and quantum dots, have also emerged as the most interesting nanomaterials in nanoscience and nanotechnology for their myriad promising applications such as for electronics, sensors, biotechnology, etc. In particular, carbon and silicon nanostructures are being utilized in energy-related applications such as catalysis, batteries, solar cells, etc., with significant advances. Understanding of the nature of surface and electronic structures of nanostructures plays a key role in the development and improvement of energy conversion and storage nanosystems. Synchrotron soft X-ray absorption spectroscopy (XAS) and related techniques, such as X-ray emission spectroscopy (XES) and scanning transmission X-ray microscopy (STXM), show unique capability in revealing the surface and electronic structures of C and Si nanomaterials. In this review, XAS is demonstrated as a powerful technique for probing chemical bonding, the electronic structure, and the surface chemistry of carbon and silicon nanomaterials, which can greatly enhance the fundamental understanding and also applicability of these nanomaterials in energy applications. The focus is on the unique advantages of XAS as a complementary tool to conventional microscopy and spectroscopy for effectively providing chemical and structural information about carbon and silicon nanostructures. The employment of XAS for in situ, real-time study of property evolution of C and Si nanostructures to elucidate the mechanisms in energy conversion or storage processes is also discussed.

  16. Following the molecular motion of near-resonant excited CO on Pt(111): A simulated x-ray photoelectron diffraction study based on molecular dynamics calculations

    PubMed Central

    Greif, Michael; Nagy, Tibor; Soloviov, Maksym; Castiglioni, Luca; Hengsberger, Matthias; Meuwly, Markus; Osterwalder, Jürg

    2015-01-01

    A THz-pump and x-ray-probe experiment is simulated where x-ray photoelectron diffraction (XPD) patterns record the coherent vibrational motion of carbon monoxide molecules adsorbed on a Pt(111) surface. Using molecular dynamics simulations, the excitation of frustrated wagging-type motion of the CO molecules by a few-cycle pulse of 2 THz radiation is calculated. From the atomic coordinates, the time-resolved XPD patterns of the C 1s core level photoelectrons are generated. Due to the direct structural information in these data provided by the forward scattering maximum along the carbon-oxygen direction, the sequence of these patterns represents the equivalent of a molecular movie. PMID:26798798

  17. Characterization of interfacially electronic structures of gold-magnetite heterostructures using X-ray absorption spectroscopy.

    PubMed

    Lin, Fang-hsin; Doong, Ruey-an

    2014-03-01

    Gold-magnetite heterostructures are novel nanomaterials which can rapidly catalyze the reduction reaction of nitroaromatics. In this study, the interfacially structural and electronic properties of various morphologies of Au-Fe3O4 heterostructures were systematically investigated using X-ray absorbance spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The effect of change in electronic structure and charge transfer on electrochemically catalytic activity of Au-Fe3O4 heterostructures was further evaluated by oxygen reduction reaction (ORR). The shifts in binding energy of Au4f and Fe2p peaks in XPS spectra indicate the charge transfer between the Au and Fe3O4 nanoparticles. The increase in d-hole population of Au seeds after the conjugation with iron oxides follows the order flower-like Au-Fe3O4 (FLNPs)>dumbbell-like Au-Fe3O4 (DBNPs)>Au seeds. In addition, the Fe(2+) valence state increases in Au-Fe3O4 heterostructures, which provides evidence to support the hypothesis of charge transfer between Au and Fe3O4 nanoparticles. The theoretical simulation of Au L3-edge XAS further confirms the production of Au-Fe and Au-O bonds at the interface of Au/Fe3O4 and the epitaxial linkage relationship between Au and Fe3O4 nanoparticles. In addition, the electron deficient of Au seeds increases upon increasing Fe3O4 nanoparticles on a single Au seed, and subsequently decreases the catalytic activity of Au in the Au-Fe3O4 heterostructures. The catalytic activity of Au-Fe3O4 toward ORR follows the order Au seeds>Au-Fe3O4 DBNPs>Au-Fe3O4 FLNPs, which is positively correlated to the extent of electronic deficiency of Au in Au-Fe3O4 heterostructures.

  18. In situ synchrotron based x-ray techniques as monitoring tools for atomic layer deposition

    SciTech Connect

    Devloo-Casier, Kilian Detavernier, Christophe; Dendooven, Jolien

    2014-01-15

    Atomic layer deposition (ALD) is a thin film deposition technique that has been studied with a variety of in situ techniques. By exploiting the high photon flux and energy tunability of synchrotron based x-rays, a variety of new in situ techniques become available. X-ray reflectivity, grazing incidence small angle x-ray scattering, x-ray diffraction, x-ray fluorescence, x-ray absorption spectroscopy, and x-ray photoelectron spectroscopy are reviewed as possible in situ techniques during ALD. All these techniques are especially sensitive to changes on the (sub-)nanometer scale, allowing a unique insight into different aspects of the ALD growth mechanisms.

  19. Unveiling the X-ray/UV properties of AGN winds using Broad and mini-Broad Absorption Line Quasars

    NASA Astrophysics Data System (ADS)

    Giustini, M.

    2015-07-01

    BAL/mini-BALs are observed in the UV spectra of ˜ 20-30% of optically selected AGN as broad absorption troughs blueshifted by several thousands km/s, indicative of powerful nuclear winds. They could be representative of the average AGN if their winds cover only 20-30% of the continuum source, and/or represent an evolutionary state analogous to the high-soft state of BHB, when the jet emission is quenched and strong X-ray absorbing equatorial disk winds are virtually ubiquitous. High-quality, possibly time-resolved X-ray/UV studies are crucial to assess the global amount and 'character' of absorption in BAL/mini-BAL QSOs and to constrain the physical mechanism responsible for the launch and acceleration of their winds, therefore placing them in the broader context of AGN geometry and evolution. I will review here the known X-ray properties of BAL/mini-BAL QSOs, and present new results from a comprehensive X-ray spectral analysis of all the Palomar-Green BAL/mini-BAL QSOs with available XMM-Newton observations, for a total of 51 pointings of 14 different sources. These will include the most recent results from a high-quality simultaneous XMM/HST observational campaign on the mini-BAL QSO PG 1126-041, that unveiled with stunning details the X-ray/UV connection in action in an AGN disk wind through correlated X-ray/UV absorption variability.

  20. Diagnosis of a two wire X-pinch by X-ray absorption spectroscopy utilizing a doubly curved ellipsoidal crystal

    SciTech Connect

    Cahill, A. D. Hoyt, C. L. Shelkovenko, T. A. Pikuz, S. A. Hammer, D. A.

    2014-12-15

    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 initial absorption spectra obtained from an aluminum x-pinch plasma.

  1. The search for absorption of 1 keV X-rays by the Small Magellanic Cloud

    NASA Technical Reports Server (NTRS)

    Marazas, Brad

    1989-01-01

    The contribution of the extragalactic component of the diffuse background to the 1 keV energy band remains unknown. An effective way to ascertain this contribution is to measure the absorption of the extragalactic component by the neutral hydrogen in the Small Magellanic Cloud (SMC) with an instrument capable of eliminating point sources from the X-ray data that compensate for absorption. The image proportional counter data from the Einstein observatory can be used for this purpose. Additionally, any extended emission must also be eliminated. The resulting source free data can be compared to the neutral hydrogen and the amount of absorption can then be obtained when compared to the diffuse flux away from the SMC. However, due to other types of radiation contaminating the X-ray data, a true measure of the X-ray absorption was not obtained.

  2. An in situ x-ray photoelectron spectroscopy study of the initial stages of rf magnetron sputter deposition of indium tin oxide on p-type Si substrate

    SciTech Connect

    Rein, M. H.; Holt, A. O.; Hohmann, M. V.; Klein, A.; Thogersen, A.; Mayandi, J.; Monakhov, E. V.

    2013-01-14

    The interface between indium tin oxide and p-type silicon is studied by in situ X-ray photoelectron spectroscopy (XPS). This is done by performing XPS without breaking vacuum after deposition of ultrathin layers in sequences. Elemental tin and indium are shown to be present at the interface, both after 2 and 10 s of deposition. In addition, the silicon oxide layer at the interface is shown to be composed of mainly silicon suboxides rather than silicon dioxide.

  3. Physical constraints on X-ray absorption and emission regions of NGC 4151

    NASA Astrophysics Data System (ADS)

    Armentrout, Bryan Keith

    2009-06-01

    I present the results of spectral analysis and modeling of nine Chandra and XMM-Newton X-ray observations of NGC 4151, spanning the period 2000-2007. The complex and highly variable spectrum is characterized by attenuation of the intrinsic power-law continuum by nested absorption components, which contribute both broadband curvature in the 1-5 keV continuum, and individual line absorption. Significant and variable narrow line emission and radiative recombination continua dominate energies below ~1.5 keV. The modeling process made extensive use of absorption tables produced by a newly-available Cloudy- XSPEC interface. Observed spectral evolution could not be explained entirely by simple changes in absorber ionization states in response to variations in the level of incident continuum, but required additional variations in absorber column densities. This fact implies transverse motion of the absorbers across the line of sight. The transverse velocity, coupled with observed absorber outflow determined from line energies, suggest a possible helical motion for the absorbers. Scattered incident continuum flux was also indicated. Model results predict that the absorbers may also serve as substantial emitters of observed soft X-ray narrow line emission. However, additional emission components, not represented by absorbers, were required. Narrow emission line modeling of a single observation required three separate components, two of which may be represented by model absorbers. A strong Fe Ka fluorescent line was present in all observations, with highly-variable equivalent width. While photoionization model results predicted contributions to Fe Ka line flux by all absorbers, the absorber contributions to emission were minor. High-energy feature analysis revealed the presence of an additional, highly-ionized absorber in at least one observation.

  4. X-ray absorption spectroscopy of lithium sulfur battery reaction intermediates

    NASA Astrophysics Data System (ADS)

    Wujcik, Kevin; Pascal, Tod; Prendergast, David; Balsara, Nitash

    2015-03-01

    Lithium sulfur batteries have a theoretical energy density nearly five times greater than current lithium ion battery standards, but questions still remain regarding the reaction pathways through which soluble lithium polysulfide (Li2Sx, ``x'' ranging from 2 to 8) reaction intermediates are formed. Complicating spectroelectrochemical approaches to elucidate redox pathways is the challenge of obtaining spectral standards for individual Li2Sx species. Lithium polysulfides cannot be isolated as individual component and exist only in solution as a distribution of different Li2Sx molecules formed via disproportionation reactions (e.g. 2Li2S4 goes to Li2S3 + Li2S5). X-ray absorption spectroscopy (XAS) at the sulfur K-edge has recently been employed as a technique to study Li-S chemistry. We have recently obtained XAS standards for individual Li2Sx species via first principles DFT simulations and the excited electron and core hole approach. Here, experimental sulfur K-edge XAS of Li2Sx species dissolved in poly(ethylene oxide) are compared to spectra obtained from analogous theoretical calculations. The impact that polysulfide solution concentration and the presence of other lithium salts (e.g. LiNO3) have on X-ray spectra of Li2Sx species is explored via experiment and theory.

  5. Predicting X-ray absorption spectra of semiconducting polymers for electronic structure and morphology characterization

    NASA Astrophysics Data System (ADS)

    Su, Gregory; Patel, Shrayesh; Pemmaraju, C. Das; Kramer, Edward; Prendergast, David; Chabinyc, Michael

    2015-03-01

    Core-level X-ray absorption spectroscopy (XAS) reveals important information on the electronic structure of materials and plays a key role in morphology characterization. Semiconducting polymers are the active component in many organic electronics. Their electronic properties are critically linked to device performance, and a proper understanding of semiconducting polymer XAS is crucial. Techniques such as resonant X-ray scattering rely on core-level transitions to gain materials contrast and probe orientational order. However, it is difficult to identify these transitions based on experiments alone, and complementary simulations are required. We show that first-principles calculations can capture the essential features of experimental XAS of semiconducting polymers, and provide insight into which molecular model, such as oligomers or periodic boundary conditions, are best suited for XAS calculations. Simulated XAS can reveal contributions from individual atoms and be used to visualize molecular orbitals. This allows for improved characterization of molecular orientation and scattering analysis. These predictions lay the groundwork for understanding how chemical makeup is linked to electronic structure, and to properly utilize experiments to characterize semiconducting polymers.

  6. High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue

    SciTech Connect

    Collingwood, J.F.; Mikhaylova, A.; Davidson, M.R.; Batich, C.; Streit, W.J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R.S.; Dobson, J.

    2008-06-16

    Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (< 5 microns). Recent progress in developing the technique is reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterize anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution {approx} 5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

  7. High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue

    NASA Astrophysics Data System (ADS)

    Collingwood, J. F.; Mikhaylova, A.; Davidson, M. R.; Batich, C.; Streit, W. J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R. S.; Dobson, J.

    2005-01-01

    Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (<5 microns). Recent progress in developing the technique is reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterise anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution ~5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

  8. Segmented Monolithic Germanium Detector Arrays for X-ray Absorption Spectroscopy

    SciTech Connect

    Dr. Ethan L. Hull

    2011-03-27

    The experimental results from the Phase I effort were extremely encouraging. During Phase I PHDs Co. made the first strides toward a new detector technology that could have great impact on synchrotron x-ray absorption (XAS) measurements, and x-ray detector technology in general. Detector hardware that allowed critical demonstration measurements of our technology was designed and fabricated. This new technology allows good charge collection from many pixels on a single side of a multi-element monolithic germanium planar detector. The detector technology provides “dot-like” collection electrodes having very low capacitance. The detector technology appears to perform as anticipated in the Phase I proposal. In particular, the 7-pixel detector studied showed remarkable properties; making it an interesting example of detector physics. The technology is enabled by the use of amorphous germanium contact technology on germanium planar detectors. Because of the scalability associated with the fabrication of these technologies at PHDs Co., we anticipate being able to supply larger detector systems at significantly lower cost than systems made in the conventional manner.

  9. X-ray absorption spectroscopy of iron at multimegabar pressures in laser shock experiments

    NASA Astrophysics Data System (ADS)

    Harmand, M.; Ravasio, A.; Mazevet, S.; Bouchet, J.; Denoeud, A.; Dorchies, F.; Feng, Y.; Fourment, C.; Galtier, E.; Gaudin, J.; Guyot, F.; Kodama, R.; Koenig, M.; Lee, H. J.; Miyanishi, K.; Morard, G.; Musella, R.; Nagler, B.; Nakatsutsumi, M.; Ozaki, N.; Recoules, V.; Toleikis, S.; Vinci, T.; Zastrau, U.; Zhu, D.; Benuzzi-Mounaix, A.

    2015-07-01

    Taking advantage of the new opportunities provided by x-ray free electron laser (FEL) sources when coupled to a long laser pulse as available at the Linear Coherent Light Source (LCLS), we have performed x-ray absorption near-edge spectroscopy (XANES) of laser shock compressed iron up to 420 GPa (±50 ) and 10 800 K (±1390 ). Visible diagnostics coupled with hydrodynamic simulations were used to infer the thermodynamical conditions along the Hugoniot and the release adiabat. A modification of the pre-edge feature at 7.12 keV in the XANES spectra is observed above pressures of 260 GPa along the Hugoniot. Comparing with ab initio calculations and with previous laser-heated diamond cell data, we propose that such changes in the XANES pre-edge could be a signature of molten iron. This interpretation then suggests that iron is molten at pressures and temperatures higher than 260 GPa (±29 ) and 5680 K (±700 ) along the principal Fe Hugoniot.

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

    SciTech Connect

    Vaverka, April Susan Montoya

    2008-01-01

    Resolving open questions regarding transport in nanostructures can have a huge impact on a broad range of future technologies such as light harvesting for energy. Silicon has potential to be used in many of these applications. Understanding how the band edges of nanostructures move as a function of size, surface termination and assembly is of fundamental importance in understanding the transport properties of these materials. In this thesis work I have investigated the change in the electronic structure of silicon nanoparticle assemblies as the surface termination is changed. Nanoparticles are synthesized using a thermal evaporation technique and sizes are determined using atomic force microscopy (AFM). By passivating the particles with molecules containing alcohol groups we are able to modify the size dependent band edge shifts. Both the valence and conduction bands are measured using synchrotron based x-ray absorption spectroscopy (XAS) and soft x-ray fluorescence (SXF) techniques. Particles synthesized via recrystallization of amorphous silicon/SiO2 multilayers of thicknesses below 10 nm are also investigated using the synchrotron techniques. These samples also show quantum confinement effects but the electronic structure is different from those synthesized via evaporation methods. The total bandgap is determined for all samples measured. The origins of these differences in the electronic structures are discussed.

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

    USGS Publications Warehouse

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

    2006-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  13. The Chemistry os Spent Nuclear Fuel From X-Ray Absorption Spectroscopy

    SciTech Connect

    F.A. Fortner; A.J. Kropf; J.C. Cunnane

    2006-09-21

    Present and future nuclear fuel cycles will require an understanding of the complex chemistry of trace fission products and transuranium actinides in spent nuclear fuel (SNF). Because of the unique analytical challenges presented by SNF to the materials scientist, many of its fundamental physical and chemical properties remain poorly understood, especially on the microscopic scale. Such an understanding of the chemical states of radionuclides in SNF would benefit development of technologies for fuel monitoring, fuel performance improvement and modeling, fuel reprocessing, and spent fuel storage and disposal. We have recently demonstrated the use of synchrotron x-ray absorption spectroscopy (XAS) to examine crystal chemical properties of actinides and fission products in extracted specimens of SNF. Information obtained includes oxidation state, chemical bond coordination, and quantitative elemental concentration and distribution. We have also used XAS in a scanning mode to obtain x-ray spectral micrographs with resolution approaching 1 micron. A brief overview of the technique will be presented, along with findings on uranium, plutonium, neptunium, technetium, and molybdenum in commercial PWR SNF specimens.

  14. Characterising legacy spent nuclear fuel pond materials using microfocus X-ray absorption spectroscopy.

    PubMed

    Bower, W R; Morris, K; Mosselmans, J F W; Thompson, O R; Banford, A W; Law, K; Pattrick, R A D

    2016-11-01

    Analysis of a radioactive, coated concrete core from the decommissioned, spent nuclear fuel cooling pond at the Hunterston-A nuclear site (UK) has provided a unique opportunity to study radionuclides within a real-world system. The core, obtained from a dividing wall and sampled at the fill level of the pond, exhibited radioactivity (dominantly (137)Cs and (90)Sr) heterogeneously distributed across both painted faces. Chemical analysis of the core was undertaken using microfocus spectroscopy at Diamond Light Source, UK. Mapping of Sr across the surface coatings using microfocus X-ray fluorescence (μXRF) combined with X-ray absorption spectroscopy showed that Sr was bound to TiO2 particles in the paint layers, suggesting an association between TiO2 and radiostrontium. Stable Sr and Cs sorption experiments using concrete coupons were also undertaken to assess their interactions with the bulk concrete in case of a breach in the coating layers. μXRF and scanning electron microscopy showed that Sr was immobilized by the cement phases, whilst at the elevated experimental concentrations, Cs was associated with clay minerals in the aggregates. This study provides a crucial insight into poorly understood infrastructural contamination in complex systems and is directly applicable to the UK's nuclear decommissioning efforts. PMID:27262277

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

    SciTech Connect

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

    1993-05-19

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

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

    SciTech Connect

    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.

  17. Effects of Spatially Heterogeneous Porosity on Matrix-Diffusion as Investigated by X ray Absorption Imaging

    SciTech Connect

    Boney, C.; Christian-Frear, T.; Meigs, L.C.; Tidwell, V.C.

    1998-10-20

    Laboratory experiments were performed to investigate the effects of spatial variation in porosity on matrix-diffusion processes. Four centimeter-scale slabs of Culebra dolomite taken from the Waste Isolation Pilot Plant site were used in the tests. Experiments involved the simple diffusion of iodine into a single edge of each rock slab while X ray absorption imaging was used to measure the resulting two-dmensional solute concentration field as a function of time. X ray imaging was also used to quantify the two-dimensional porosity field of each rock slab. Image analysis provided a unique opportunity to both visuake and quantifj the effects of the spatially variable porosi~ on matrixdMusion. Four key results were obtained. First, significant variation in rates of diffusion were realized over the relatively small length (centimeter) and time scales (months) investigated. Second, clear evidence of diffusion preferentially following zones of relatively higher porosity was noted. Third, rate of difhion was found to vary as tracer diffused into the rock slabs encountering changing porosity conditions. Fourth, strong correlation between porosi~ and the calculated diffusion coefficients was found. In fact, the nature of the correlation can be related to the geometry, position, and orientation of the heterogeneous porosity features populating each rock slab.

  18. Surface oxidation of pyrite under ambient atmospheric and aqueous (pH = 2 to 10) conditions: electronic structure and mineralogy from X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Todd, E. C.; Sherman, D. M.; Purton, J. A.

    2003-03-01

    The nature of the surface oxidation phase on pyrite, FeS 2, reacted in aqueous electrolytes at pH = 2 to 10 and with air under ambient atmospheric conditions was studied using synchrotron-based oxygen K edge, sulfur L III edge, and iron L II,III edge X-ray absorption spectroscopy. We demonstrate that O K edge X-ray absorption spectra provide a sensitive probe of sulfide surface oxidation that is complementary to X-ray photoelectron spectroscopy. Using total electron yield detection, the top 20 to 50 Å of the pyrite surface is characterized. In air, pyrite oxidizes to form predominantly ferric sulfate. In aqueous air-saturated solutions, the surface oxidation products of pyrite vary with pH, with a marked transition occurring around pH 4. Below pH = 4, a ferric (hydroxy)sulfate is the main oxidation product on the pyrite surface. At higher pH, we find iron(III) oxyhydroxide in addition to ferric (hydroxy)sulfate on the surface. Under the most alkaline conditions, the O K edge spectrum closely resembles that of goethite, FeOOH, and the surface is oxidized to the extent that no FeS 2 can be detected in the X-ray absorption spectra. In a 1.667 × 10 -3 mol/L Fe 3+ solution with ferric iron present as FeCl 3 in NaCl, the oxidation of pyrite is autocatalyzed, and formation of the surface iron(III) oxyhydroxide phase is promoted at low pH.

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

    NASA Astrophysics Data System (ADS)

    Liu, Shanshan

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

  20. Characterizing Quasar Outflows IV: Regulating Outflows Through X-ray and EUV Absorption

    NASA Astrophysics Data System (ADS)

    Derseweh, Jeffrey; Ganguly, R.; Richmond, J. M.; Stark, M. A.; Christenson, D. H.; Robbins, J. M.; Townsend, S. L.

    2012-05-01

    Galaxy evolution models have shown that quasars are a crucial ingredient in the evolution of massive galaxies. Outflows play a key role in the story of quasars and their host galaxies, by helping regulate the accretion process, the star-formation rate and mass of the host galaxy (i.e., feedback). The prescription for modeling outflows as a contributor to feedback requires knowledge of the outflow velocity, geometry, and column density. In particular, we need to understand how these depend on physical parameters and how much is determined stochastically (and with what distribution). For this purpose, we are examining a sample of 11000 z=1.7-2.0 quasars from the Sloan Digital Sky Survey. This redshift range permits the following from the SDSS spectra: (1) separation of objects that do and do not exhibit outflows; (2) classification/measurement of outflow properties (ionization, velocity, velocity width); and (3) measurements of UV emission line and continuum parameters. In this poster, we add photometry from the GALEX All-sky imaging survey, as well as the Chandra and ROSAT archives. These provide coverage of the rest-frame extreme ultraviolet, and soft X-ray bands. In an accompanying poster, we have subjectively divided these quasars into four categories: broad absorption-line quasars (2700 objects), associated absorption-line quasars (1700 objects), reddened quasars (160 objects), and unabsorbed/unreddened quasars (6300 objects). We are interested in testing the radiative-driving hypothesis that requires a suppression of X-ray flux in order to transfer momentum efficiently to the UV-absorbing gas. Hence, we explore how absorption in both the extreme ultraviolet and the soft X-ray bands correlate with properties of the UV outflows, quasar property, and changes in SED shape. This material is based upon work supported by the National Aeronautics and Space Administration under Grant No. 09-ADP09-0016 issued through the Astrophysics Data Analysis Program and by Chandra

  1. Microbeam x-ray absorption spectroscopy study of chromium in large-grain uranium dioxide fuel

    NASA Astrophysics Data System (ADS)

    Mieszczynski, C.; Kuri, G.; Bertsch, J.; Martin, M.; Borca, C. N.; Delafoy, Ch; Simoni, E.

    2014-09-01

    Synchrotron-based microprobe x-ray absorption spectroscopy (XAS) has been used to study the local atomic structure of chromium in chromia-doped uranium dioxide (UO2) grains. The specimens investigated were a commercial grade chromia-doped UO2 fresh fuel pellet, and materials from a spent fuel pellet of the same batch, irradiated with an average burnup of ~40 MW d kg-1. Uranium L3-edge and chromium K-edge XAS have been measured, and the structural environments of central uranium and chromium atoms have been elucidated. The Fourier transform of uranium L3-edge extended x-ray absorption fine structure shows two well-defined peaks of U-O and U-U bonds at average distances of 2.36 and 3.83 Å. Their coordination numbers are determined as 8 and 11, respectively. The chromium Fourier transform extended x-ray absorption fine structure of the pristine UO2 matrix shows similar structural features with the corresponding spectrum of the irradiated spent fuel, indicative of analogous chromium environments in the two samples studied. From the chromium XAS experimental data, detectable next neighbor atoms are oxygen and uranium of the cation-substituted UO2 lattice, and two distinct subshells of chromium and oxygen neighbors, possibly because of undissolved chromia particles present in the doped fuels. Curve-fitting analyses using theoretical amplitude and phase-shift functions of the closest Cr-O shell and calculations with ab initio computer code FEFF and atomic clusters generated from the chromium-dissolved UO2 structure have been carried out. There is a prominent reduction in the length of the adjacent Cr-O bond of about 0.3 Å in chromia-doped UO2 compared with the ideal U-O bond length in standard UO2 that would be expected because of the change in effective Coulomb interactions resulting from replacing U4+ with Cr3+ and their ionic size differences. The contraction of shortest Cr-U bond is ~0.1 Å relative to the U-U bond length in bulk UO2. The difference in the

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  3. Distribution and speciation of bromine in mammalian tissue and fluids by X-ray fluorescence imaging and X-ray absorption spectroscopy.

    PubMed

    Ceko, Melanie J; Hummitzsch, Katja; Hatzirodos, Nicholas; Bonner, Wendy; James, Simon A; Kirby, Jason K; Rodgers, Raymond J; Harris, Hugh H

    2015-05-01

    Bromine is one of the most abundant and ubiquitous trace elements in the biosphere and until recently had not been shown to perform any essential biological function in animals. A recent study demonstrated that bromine is required as a cofactor for peroxidasin-catalysed formation of sulfilimine crosslinks in Drosophila. In addition, bromine dietary deficiency is lethal in Drosophila, whereas bromine replenishment restores viability. The aim of this study was to examine the distribution and speciation of bromine in mammalian tissues and fluids to provide further insights into the role and function of this element in biological systems. In this study we used X-ray fluorescence (XRF) imaging and inductively coupled plasma-mass spectrometry (ICP-MS) to examine the distribution of bromine in bovine ovarian tissue samples, follicular fluid and aortic serum, as well as human whole blood and serum and X-ray absorption spectroscopy (XAS) to identify the chemical species of bromine in a range of mammalian tissue (bovine, ovine, porcine and murine), whole blood and serum samples (bovine, ovine, porcine, murine and human), and marine samples (salmon (Salmo salar), kingfish (Seriola lalandi) and Scleractinian coral). Bromine was found to be widely distributed across all tissues and fluids examined. In the bovine ovary in particular it was more concentrated in the sub-endothelial regions of arterioles. Statistical comparison of the near-edge region of the X-ray absorption spectra with a library of bromine standards led to the conclusion that the major form of bromine in all samples analysed was bromide.

  4. Distribution and speciation of bromine in mammalian tissue and fluids by X-ray fluorescence imaging and X-ray absorption spectroscopy.

    PubMed

    Ceko, Melanie J; Hummitzsch, Katja; Hatzirodos, Nicholas; Bonner, Wendy; James, Simon A; Kirby, Jason K; Rodgers, Raymond J; Harris, Hugh H

    2015-05-01

    Bromine is one of the most abundant and ubiquitous trace elements in the biosphere and until recently had not been shown to perform any essential biological function in animals. A recent study demonstrated that bromine is required as a cofactor for peroxidasin-catalysed formation of sulfilimine crosslinks in Drosophila. In addition, bromine dietary deficiency is lethal in Drosophila, whereas bromine replenishment restores viability. The aim of this study was to examine the distribution and speciation of bromine in mammalian tissues and fluids to provide further insights into the role and function of this element in biological systems. In this study we used X-ray fluorescence (XRF) imaging and inductively coupled plasma-mass spectrometry (ICP-MS) to examine the distribution of bromine in bovine ovarian tissue samples, follicular fluid and aortic serum, as well as human whole blood and serum and X-ray absorption spectroscopy (XAS) to identify the chemical species of bromine in a range of mammalian tissue (bovine, ovine, porcine and murine), whole blood and serum samples (bovine, ovine, porcine, murine and human), and marine samples (salmon (Salmo salar), kingfish (Seriola lalandi) and Scleractinian coral). Bromine was found to be widely distributed across all tissues and fluids examined. In the bovine ovary in particular it was more concentrated in the sub-endothelial regions of arterioles. Statistical comparison of the near-edge region of the X-ray absorption spectra with a library of bromine standards led to the conclusion that the major form of bromine in all samples analysed was bromide. PMID:25675086

  5. (De)lithiation mechanism of Li/SeS(x) (x = 0-7) batteries determined by in situ synchrotron X-ray diffraction and X-ray absorption spectroscopy.

    PubMed

    Cui, Yanjie; Abouimrane, Ali; Lu, Jun; Bolin, Trudy; Ren, Yang; Weng, Wei; Sun, Chengjun; Maroni, Victor A; Heald, Steve M; Amine, Khalil

    2013-05-29

    Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge.

  6. (De)lithiation mechanism of Li/SeS(x) (x = 0-7) batteries determined by in situ synchrotron X-ray diffraction and X-ray absorption spectroscopy.

    PubMed

    Cui, Yanjie; Abouimrane, Ali; Lu, Jun; Bolin, Trudy; Ren, Yang; Weng, Wei; Sun, Chengjun; Maroni, Victor A; Heald, Steve M; Amine, Khalil

    2013-05-29

    Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge. PMID:23631402

  7. On Different Absorption Components in the X-ray Spectra of the Intermediate Polar Systems

    NASA Astrophysics Data System (ADS)

    Balman, S.; Okcu, B.

    2014-07-01

    We present orbital phase-resolved spectroscopy of the Intermediate polars (IP) AO Psc, HT Cam, V1223 Sgr and XSS J0056+4548 using the XMM-Newton EPIC pn data. We detect increase of absorption by neutral hydrogen column density N_{H} during the phases corresponding to the orbital minima in a range ˜ (1.0-2.0)× 10^{22} cm^{-2}. AO Psc indicates spectral hardening in the soft plasma emission component. HT Cam, reveals an increase of N_{H} at the orbital minimum from 0.05× 10^{22} cm^{-2} to 0.13× 10^{22} cm^{-2}. These high N_{H} values are most likely a result of absorption by the bulge material at the accretion impact zone. We discuss implications of this interms of warmabsorbers in IPs and bulge temperatures. The four IPs reveal a second high absorption component that is constant over the orbital phase in a range (5.0-11.0)× 10^{22} cm^{-2}. We attribute this component to the accretion column/curtain. These results are in accordance with the orbital phase-resolved analysis presented in Pekon & Balman (2011) for EX Hya and (2012) for FO Aqr. We strongly suggest that absorption by the bulge at the accretion impact zone is a distinct component in the IP X-ray spectra.

  8. Soft X-Ray Absorption by High-Redshift Intergalactic Helium.

    PubMed

    Miralda-Escudé

    2000-01-01

    The Lyalpha absorption from intergalactic, once-ionized helium (He ii) has been measured with the Hubble Space Telescope in four quasars over the last few years in the redshift range 2.4absorption can be observed becomes increasingly difficult at higher redshift owing to the large abundance of hydrogen Lyman limit systems. It is pointed out here that He ii in the IGM should also cause detectable continuum absorption in the soft X-rays. The spectrum of a high-redshift source seen behind the IGM when most of the helium was He ii should recover from the He ii Lyman continuum absorption at an observed energy of approximately 0.1 keV. Galactic absorption will generally be stronger, but not by a large factor; the intergalactic He ii absorption can be detected as an excess over the expected Galactic absorption from the 21 cm H i column density. In principle, this method allows a direct determination of the fraction of helium that was singly ionized as a function of redshift if the measurement is done on a large sample of high-redshift sources over a range of redshifts. PMID:10587481

  9. Negative thermal expansion in CuCl: An extended x-ray absorption fine structure study

    SciTech Connect

    Vaccari, M.; Grisenti, R.; Fornasini, P.; Rocca, F.; Sanson, A.

    2007-05-01

    Extended x-ray absorption fine structure (EXAFS) has been measured from liquid helium to ambient temperature at the Cu K edge of copper chloride (CuCl) to investigate the local origin of negative thermal expansion. A quantitative analysis of the first coordination shell, performed by the cumulant method, reveals that the nearest-neighbor Cu-Cl interatomic distance undergoes a strong positive expansion, contrasting with the much weaker negative expansion of the crystallographic distance between average atomic positions below 100 K. The anisotropy of relative thermal vibrations, monitored by the ratio {gamma} between perpendicular and parallel mean square relative displacements, is considerably high, while the diffraction thermal factors are isotropic. The relative perpendicular vibrations measured by EXAFS are related to the tension mechanism and to the transverse acoustic modes, which are considered responsible for negative thermal expansion in zinc-blende structures.

  10. X-ray absorption spectroscopy study in the BaFe2As2 family

    NASA Astrophysics Data System (ADS)

    Koh, Yoonyoung; Kim, Yeongkwan; Yang, Wanli; Kim, Changyoung

    2012-02-01

    One of the representative Fe-based superconductor families, BaFe2As2 (Tc =38K) is a semimetal with the same number of hole and electron carriers, and is in a spin density wave state below 139K. It has been reported that various types of ``doped'' BaFe2As2 systems can obtained by substitution of Ba, Fe, and As atoms. However, an important issue has been recently raised regarding whether each type of substitution indeed induces effective charge doping or not. It is essential to clarify whether each type of substitution indeed induce an effective doping in BaFe2As2 system. To clarify the carrier doping issue, we performed high resolution X-ray absorption spectroscopy experiment on Ba(Fe,Co)2As2, Ba(Fe,Ru)2As2, BaFe2(As,P)2 which are representative ``doped'' BaFe2As2 systems.

  11. X-ray Absorption Improvement of Single Wall Carbon Nanotube through Gadolinium Encapsulation

    NASA Astrophysics Data System (ADS)

    Alimin; Narsito, I.; Kartini; Santosa, S. J.

    2016-02-01

    X-ray absorption improvement of single-wall carbon nanotube (SWCNT) through gadolinium (Gd) encapsulation has been studied. The liquid phase adsorption using ethanol has been performed for the doping treatment. The Gd-doped SWCNT (Gd@SWCNT) was characterized by nitrogen adsorption isotherms, Raman spectroscopy, Transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA) techniques. A relatively high residual weight of Gd@SWCNT compared to non-doped SWCNT (n-SWCNT) indicated that Gd has been doped in the nanotube. Even though Gd nanoparticles could not be observed clearly by TEM image, however, a significant decrease of nitrogen uptakes at low pressure and RBM (Radial Breathing Mode) upshift of Raman spectra of Gd@SWCNT specimen suggest that the metal nanoparticles might be encapsulated in the internal tube spaces of the nanotube. It was found that Gd-doped in the SWCNT increased significantly mass attenuation coefficient of the nanotube.

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

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

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

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

    SciTech Connect

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

    2003-03-01

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

  14. Zinc ligands in the metal hyperaccumulator Thlaspi caerulescens as determined using X-ray absorption spectroscopy

    SciTech Connect

    Salt, D.E.; Prince, R.C.; Baker, A.J.M.; Raskin, I.; Pickering, I.J.

    1999-03-01

    Using the noninvasive technique of X-ray absorption spectroscopy (XAS), the authors have been able to determine the ligand environment of Zn in different tissues of the Zn-hyperaccumulator Thlaspi caerulescens. The majority of intracellular Zn in roots of T. caerulescens was found to be coordinated with histidine. In the xylem sap Zn was found to be transported mainly as the free hydrated Zn{sup 2+} cation with a smaller proportion coordinated with organic acids. In the shoots, Zn coordination occurred mainly via organic acids, with a smaller proportion present as the hydrated cation and coordinated with histidine and the cell wall. Their data suggest that histidine plays an important role in Zn homeostasis in the roots, whereas organic acids are involved in xylem transport and Zn storage in shoots.

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

    PubMed Central

    Derricotte, Wallace D.; Evangelista, Francesco A.

    2015-01-01

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

  16. Studies of Y-Ba-Cu-O single crystals by x-ray absorption spectroscopy

    SciTech Connect

    Krol, A.; Ming, Z.H.; Kao, Y.H.; Nuecker, N.; Roth, G.; Fink, J.; Smith, G.C.; Erband, A.; Mueller-Vogt, G.; Karpinski, J.; Kaldis, E.; Schoenmann, K.

    1992-02-01

    The symmetry and density of unoccupied states of YBa{sub 2}Cu{sub 3}O{sub 7} YBa{sub 2}Cu{sub 4}O{sub 8} have been investigated by orientation dependent x-ray absorption spectroscopy on the O 1s edge using a bulk-sensitive fluorescence-yield-detection method. It has been found that the O 2p holes are distributed equally between the CuO{sub 2} planes and CuO chains and that the partial density of unoccupied O 2p states in the CuO{sub 2} planes are identical in both systems investigated. The upper Hubbard band has been observed in the planes but not in the chains in both systems. 18 refs.

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

    SciTech Connect

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

    2015-06-24

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

  18. X-ray absorption studies of Ti/polymer and Cr/polymer interfaces

    SciTech Connect

    Opila, R.L.; Konstadinidis, K.; Ibidunni, A.O; Davenport, A.J.; Isaacs, H.S.

    1993-11-01

    The interface formed between metals, Ti and Cr, and polymers, epoxy, and triazine, have been studied, non-destructively, using x-ray absorption spectroscopy. The metals were sputtered onto the polymer surfaces. Titanium reacts extensively, up to Ti thickness of 100 {Angstrom} while Cr remains primarily metallic. In situ heating at 200{degree}C increases the extent of reaction for both metals. Heating has a greater effect on metal/epoxy interfaces than metal/triazine. Titanium and Cr were ion implanted into the polymer in order to determine the interactions of isolated metal atoms with the polymer. Titanium and Cr appear to form oxides as the final reaction product, and the Ti is tetrahedrally coordinated.

  19. Studies of fluorine in catalysts with ultrasoft X-ray absorption spectroscopy

    SciTech Connect

    Davis, S.M. ); Meitzner, G.D. ); Fischer, D.A. ); Gland, J. )

    1993-08-01

    The structures of fluorine-doped alumina catalyst powders have been studied by fluorescence yield ultrasoft X-ray absorption spectroscopy. The results presented here demonstrate that important local structural information can be obtained by the technique. It is established that fluoride ions are substituted for oxygen in alumina at low concentration of adsorbed fluorine. For doping levels larger than those required for saturation of the monolayer, the authors observed AlF[sub 3]-like features in the radial structure function. These results are in agreement with previous observations of bulk AlF[sub 3] in aluminas with high levels of fluorine doping. The fluorescence yield method is well suited for determining structures of a wide range of ceramic materials. 22 refs., 4 figs.

  20. X-Ray absorption spectroscopy investigation of 1-alkyl-3-methylimidazolium bromide salts

    SciTech Connect

    D'Angelo, Paola; Zitolo, Andrea; Migliorati, Valentina; Bodo, Enrico; Caminiti, Ruggero; Aquilanti, Giuliana; Hazemann, Jean Louis; Testemale, Denis; Mancini, Giordano

    2011-08-21

    X-ray absorption spectroscopy (XAS) has been used to unveil the bromide ion local coordination structure in 1-alkyl-3-methylimidazolium bromide [C{sub n}mim]Br ionic liquids (ILs) with different alkyl chains. The XAS spectrum of 1-ethyl-3-methylimidazolium bromide has been found to be different from those of the other members of the series, from the butyl to the decyl derivatives, that have all identical XAS spectra. This result indicates that starting from 1-buthyl-3-methylimidazolium bromide the local molecular arrangement around the bromide anion is the same independently from the length of the alkyl chain, and that the imidazolium head groups in the liquid ILs with long alkyl chains assume locally the same orientation as in the [C{sub 4}mim]Br crystal. With this study we show that the XAS technique is an effective direct tool for unveiling the local structural arrangements around selected atoms in ILs.