First-Principles Fe L 2,3 -Edge and O K-Edge XANES and XMCD Spectra for Iron Oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sassi, Michel; Pearce, Carolyn I.; Bagus, Paul S.

X-ray absorption near-edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) spectroscopies are tools in widespread use for providing detailed local atomic structure, oxidation state, and magnetic structure information for materials and organometallic complexes. The analysis of these spectra for transition-metal L-edges is routinely performed on the basis of ligand-field multiplet theory because one- and two-particle mean-field ab initio methods typically cannot describe the multiplet structure. Here we show that multireference configuration interaction (MRCI) calculations can satisfactorily reproduce measured XANES spectra for a range of complex iron oxide materials including hematite and magnetite. MRCI Fe L2,3-edge XANES and XMCD spectramore » of Fe(II)O6, Fe(III)O6, and Fe(III)O4 in magnetite are found to be in very good qualitative agreement with experiment and multiplet calculations. Point-charge embedding and small distortions of the first-shell oxygen ligands have only small effects. Oxygen K-edge XANES/XMCD spectra for magnetite investigated by a real-space Green’s function approach complete the very good qualitative agreement with experiment. Material-specific differences in local coordination and site symmetry are well reproduced, making the approach useful for assigning spectral features to specific oxidation states and coordination environments.« less

Assignment of Pre-edge Features in the Ru K-edge X-ray Absorption Spectra of Organometallic Ruthenium Complexes

PubMed Central

Getty, Kendra; Delgado-Jaime, Mario Ulises

2010-01-01

The nature of the lowest energy bound-state transition in the Ru K-edge X-ray Absorption Spectra for a series of Grubbs-type ruthenium complexes was investigated. The pre-edge feature was unambiguously assigned as resulting from formally electric dipole forbidden Ru 4d←1s transitions. The intensities of these transitions are extremely sensitive to the ligand environment and the symmetry of the metal centre. In centrosymmetric complexes the pre-edge is very weak since it is limited by the weak electric quadrupole intensity mechanism. By contrast, upon breaking centrosymmetry, Ru 5p-4d mixing allows for introduction of electric dipole allowed character resulting in a dramatic increase in the pre-edge intensity. The information content of this approach is explored as it relates to complexes of importance in olefin metathesis and its relevance as a tool for the study of reactive intermediates. PMID:20151030

Reference spectra of important adsorbed organic and inorganic phosphate binding forms for soil P speciation using synchrotron-based K-edge XANES spectroscopy.

PubMed

Prietzel, Jörg; Harrington, Gertraud; Häusler, Werner; Heister, Katja; Werner, Florian; Klysubun, Wantana

2016-03-01

Direct speciation of soil phosphorus (P) by linear combination fitting (LCF) of P K-edge XANES spectra requires a standard set of spectra representing all major P species supposed to be present in the investigated soil. Here, available spectra of free- and cation-bound inositol hexakisphosphate (IHP), representing organic P, and of Fe, Al and Ca phosphate minerals are supplemented with spectra of adsorbed P binding forms. First, various soil constituents assumed to be potentially relevant for P sorption were compared with respect to their retention efficiency for orthophosphate and IHP at P levels typical for soils. Then, P K-edge XANES spectra for orthophosphate and IHP retained by the most relevant constituents were acquired. The spectra were compared with each other as well as with spectra of Ca, Al or Fe orthophosphate and IHP precipitates. Orthophosphate and IHP were retained particularly efficiently by ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated soil organic matter (SOM), but far less efficiently by hematite, Ca-saturated montmorillonite and Ca-saturated SOM. P retention by dolomite was negligible. Calcite retained a large portion of the applied IHP, but no orthophosphate. The respective P K-edge XANES spectra of orthophosphate and IHP adsorbed to ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated SOM differ from each other. They also are different from the spectra of amorphous FePO4, amorphous or crystalline AlPO4, Ca phosphates and free IHP. Inclusion of reference spectra of orthophosphate as well as IHP adsorbed to P-retaining soil minerals in addition to spectra of free or cation-bound IHP, AlPO4, FePO4 and Ca phosphate minerals in linear combination fitting exercises results in improved fit quality and a more realistic soil P speciation. A standard set of P K-edge XANES spectra of the most relevant adsorbed P binding forms in soils is presented.

Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

NASA Astrophysics Data System (ADS)

van Aken, P. A.; Sharp, T. G.; Seifert, F.

The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si-O bond distances, coordination numbers and Debye-Waller factors). The mean Si-O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R 0.172 nm and N 5) to R 0.167 nm and N 4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by

Retention Mechanisms of Citric Acid in Ternary Kaolinite-Fe(III)-Citrate Acid Systems Using Fe K-edge EXAFS and L3,2-edge XANES Spectroscopy

PubMed Central

Yang, Jianjun; Wang, Jian; Pan, Weinan; Regier, Tom; Hu, Yongfeng; Rumpel, Cornelia; Bolan, Nanthi; Sparks, Donald

2016-01-01

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. These findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils. PMID:27212680

Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L 3,2-edge XANES spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jianjun; Wang, Jian; Pan, Weinan

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L- 3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorptionmore » and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.« less

Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L 3,2-edge XANES spectroscopy

DOE PAGES

Yang, Jianjun; Wang, Jian; Pan, Weinan; ...

2016-05-23

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L- 3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorptionmore » and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.« less

Long-Range Chemical Sensitivity in the Sulfur K-Edge X-ray Absorption Spectra of Substituted Thiophenes

PubMed Central

2015-01-01

Thiophenes are the simplest aromatic sulfur-containing compounds and are stable and widespread in fossil fuels. Regulation of sulfur levels in fuels and emissions has become and continues to be ever more stringent as part of governments’ efforts to address negative environmental impacts of sulfur dioxide. In turn, more effective removal methods are continually being sought. In a chemical sense, thiophenes are somewhat obdurate and hence their removal from fossil fuels poses problems for the industrial chemist. Sulfur K-edge X-ray absorption spectroscopy provides key information on thiophenic components in fuels. Here we present a systematic study of the spectroscopic sensitivity to chemical modifications of the thiophene system. We conclude that while the utility of sulfur K-edge X-ray absorption spectra in understanding the chemical composition of sulfur-containing fossil fuels has already been demonstrated, care must be exercised in interpreting these spectra because the assumption of an invariant spectrum for thiophenic forms may not always be valid. PMID:25116792

Calcium EXAFS Establishes the Mn-Ca Cluster in the Oxygen-Evolving Complex of Photosystem II†

PubMed Central

Cinco, Roehl M.; Holman, Karen L. McFarlane; Robblee, John H.; Yano, Junko; Pizarro, Shelly A.; Bellacchio, Emanuele; Sauer, Kenneth; Yachandra, Vittal K.

2014-01-01

The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared subsequent to Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 Å, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is ~ 3.5 Å distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster. PMID:12390018

Edge profiles in K shell photoabsorption spectra of gaseous hydrides of 3p elements and homologues

NASA Astrophysics Data System (ADS)

Hauko, R.; Gomilšek, J. Padežnik; Kodre, A.; Arčon, I.; Aquilanti, G.

2017-10-01

Photoabsorption spectra of gaseous hydrides of 3p elements (PH3, H2S, HCl) are measured in the energy region of photoexcitations pertaining to K edge. The analysis of the edge profile is extended to hydrides of 4p series (GeH4, AsH3, H2Se, HBr) from an earlier experiment, and to published spectra of 2p hydrides (CH4, NH3, H2O, HF) and noble gases Ar, Kr and Ne and SiH4. The edge profiles are modelled with a linear combination of lorentzian components, describing excitations to individual bound states and to continuum. Transition energies and probabilities are also calculated in the non-relativistic molecular model of the ORCA code, in good agreement with the experiment. Edge profiles in the heavier homologues are closely similar, the symmetry of the molecule governs the transitions to the lowest unoccupied orbitals. In 2p series the effect of the strong nuclear potential prevails. Transitions to higher, atomic-like levels remain very much the same as in free atoms.

EXAFS and XANES investigation of the ETS-10 microporous titanosilicate.

PubMed

Prestipino, C; Solari, P L; Lamberti, C

2005-07-14

In this work, we report state-of-the-art analysis of both Ti K-edge high-resolution XANES and EXAFS data collected on the ETS-10 molecular sieve at the GILDA BM8 beamline of the ESRF facility. The interatomic distances and the angles obtained in our EXAFS study are in fair agreement with the single-crystal XRD data of Wang and Jacobson (Chem. Commun. 1999, 973) and with the recent ab initio periodic study of Damin et al. (J. Phys. Chem. B 2004, 108, 1328) Differently from previous EXAFS work (J. Phys. Chem. 1996, 100, 449), our study supports a model of ETS-10 where the Ti atoms are bonded with two equivalent axial oxygen atoms. This model is also able to reproduce the edge and the post-edge region of the XANES spectrum. Conversely, the weak but well-defined pre-edge peak at 4971.3 eV can be explained only by assuming that a fraction of Ti atoms are in a local geometry similar to that of the pentacoordinated Ti sites in the ETS-4 structure. These Ti atoms in ETS-10 should be the terminal of the -Ti-O-Ti-O-Ti- chains, of which the actual number is strongly increased by the high crystal defectivity (Ti vacancies).

Calculation of optical and K pre-edge absorption spectra for ferrous iron of distorted sites in oxide crystals

NASA Astrophysics Data System (ADS)

Vercamer, Vincent; Hunault, Myrtille O. J. Y.; Lelong, Gérald; Haverkort, Maurits W.; Calas, Georges; Arai, Yusuke; Hijiya, Hiroyuki; Paulatto, Lorenzo; Brouder, Christian; Arrio, Marie-Anne; Juhin, Amélie

2016-12-01

Advanced semiempirical calculations have been performed to compute simultaneously optical absorption and K pre-edge x-ray absorption spectra of Fe2 + in four distinct site symmetries found in minerals. The four symmetries, i.e., a distorted octahedron, a distorted tetrahedron, a square planar site, and a trigonal bipyramidal site, are representative of the Fe2 + sites found in crystals and glasses. A particular attention has been paid to the definition of the p -d hybridization Hamiltonian which occurs for noncentrosymmetric symmetries in order to account for electric dipole transitions. For the different sites under study, an excellent agreement between calculations and experiments was found for both optical and x-ray absorption spectra, in particular in terms of relative intensities and energy positions of electronic transitions. To our knowledge, these are the first calculations of optical absorption spectra on Fe2 + placed in such diverse site symmetries, including centrosymmetric sites. The proposed theoretical model should help to interpret the features of both the optical absorption and the K pre-edge absorption spectra of 3 d transition metal ions and to go beyond the usual fingerprint interpretation.

A pre-edge analysis of Mn K-edge XANES spectra to help determine the speciation of manganese in minerals and glasses

NASA Astrophysics Data System (ADS)

Chalmin, E.; Farges, F.; Brown, G. E.

2009-01-01

High-resolution manganese K-edge X-ray absorption near edge structure spectra were collected on a set of 40 Mn-bearing minerals. The pre-edge feature information (position, area) was investigated to extract as much as possible quantitative valence and symmetry information for manganese in various “test” and “unknown” minerals and glasses. The samples present a range of manganese symmetry environments (tetrahedral, square planar, octahedral, and cubic) and valences (II to VII). The extraction of the pre-edge information is based on a previous multiple scattering and multiplet calculations for model compounds. Using the method described in this study, a robust estimation of the manganese valence could be obtained from the pre-edge region at 5% accuracy level. This method applied to 20 “test” compounds (such as hausmannite and rancieite) and to 15 “unknown” compounds (such as axinite and birnessite) provides a quantitative estimate of the average valence of manganese in complex minerals and silicate glasses.

Simulations of iron K pre-edge X-ray absorption spectra using the restricted active space method.

PubMed

Guo, Meiyuan; Sørensen, Lasse Kragh; Delcey, Mickaël G; Pinjari, Rahul V; Lundberg, Marcus

2016-01-28

The intensities and relative energies of metal K pre-edge features are sensitive to both geometric and electronic structures. With the possibility to collect high-resolution spectral data it is important to find theoretical methods that include all important spectral effects: ligand-field splitting, multiplet structures, 3d-4p orbital hybridization, and charge-transfer excitations. Here the restricted active space (RAS) method is used for the first time to calculate metal K pre-edge spectra of open-shell systems, and its performance is tested against on six iron complexes: [FeCl6](n-), [FeCl4](n-), and [Fe(CN)6](n-) in ferrous and ferric oxidation states. The method gives good descriptions of the spectral shapes for all six systems. The mean absolute deviation for the relative energies of different peaks is only 0.1 eV. For the two systems that lack centrosymmetry [FeCl4](2-/1-), the ratios between dipole and quadrupole intensity contributions are reproduced with an error of 10%, which leads to good descriptions of the integrated pre-edge intensities. To gain further chemical insight, the origins of the pre-edge features have been analyzed with a chemically intuitive molecular orbital picture that serves as a bridge between the spectra and the electronic structures. The pre-edges contain information about both ligand-field strengths and orbital covalencies, which can be understood by analyzing the RAS wavefunction. The RAS method can thus be used to predict and rationalize the effects of changes in both the oxidation state and ligand environment in a number of hard X-ray studies of small and medium-sized molecular systems.

Kα X-Ray Emission Spectra and K X-Ray Absorption-Edge Structures of Fluorine in 3d Transition-Metal Difluorides

NASA Astrophysics Data System (ADS)

Sugiura, Chikara

1991-08-01

The fluorine Kα emission spectra in fluorescence from a series of 3d transition-metal difluorides MF2 (M=Mn, Fe, Co, Ni, Cu and Zn) have been measured with a high-resolution two-crystal vacuum spectrometer. It is shown that the observed FWHM of the Kα1,2 emission band is closely related to the difference in the electronegativity between the metal and fluorine atoms. The measured emission spectra are presented along with the UPS or XPS spectra of the valence bands and the fluorine K absorption spectra of the metal difluorides, reported previously. The structures at the fluorine K absorption edges are interpreted in terms of a molecular orbital (MO) model.

The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds

NASA Astrophysics Data System (ADS)

Pantelouris, A.; Modrow, H.; Pantelouris, M.; Hormes, J.; Reinen, D.

2004-05-01

X-ray absorption spectra at the chromium K-edge are reported for a number of selected chromium compounds of known chemical structure. The spectra were obtained with use of synchrotron radiation available at the ELectron Stretcher Accelerator ELSA in Bonn. The compounds studied include the tetrahedrally coordinated compounds Ca 2Ge 0.8Cr 0.2O 4, Ba 2Ge 0.1Cr 0.9O 4, Sr 2CrO 4, Ca 2(PO 4) x(CrO 4) 1- xCl ( x=0.25,0.5), Ca 5(CrO 4) 3Cl, CrO 3, the octahedrally coordinated compounds Cr(II)-acetate, CrCl 3, CrF 3, Cr 2O 3, KCr(SO 4) 2 · 12H 2O, CrO 2 and cubic coordinated metallic chromium. In these compounds chromium exhibits a wide range of formal oxidation states (0 to VI). The absorption features in the near edge region are shown to be characteristic of the spatial environment of the absorbing atom. The occurrence of a single pre-edge line easily allows one to distinguish between tetrahedral and octahedral coordination geometry, whereas the energy position of the absorption edge is found to be very sensitive to the valency of the excited chromium atom. Calculations of the ionisation potential of Cr in different oxidation states using the non-relativistic Hartree-Fock method (Froese-Fischer) confirm that the ionisation limit shifts to higher energy with increasing Cr valency. More detailed information on the electronic structure of the different compounds is gained by real-space full multiple scattering calculations using the FEFF8 code.

A high pressure La K-edge X-ray absorption fine structure spectroscopy investigation of La1/3NbO3

NASA Astrophysics Data System (ADS)

Marini, C.; Joseph, B.; Noked, O.; Shuker, R.; Kennedy, B. J.; Mathon, O.; Pascarelli, S.; Sterer, E.

2018-01-01

La K-edge X-ray absorption spectroscopy has been used to elucidate the changes in the local electronic and lattice structure that occur in the A-site deficient double perovskite La?NbO? up to 6 GPa. The pressure evolution of the oxygen dodecahedrum around the A-site has been examined. XANES (X-ray absorption near edge structure) data show modifications ascribed to the increase of bands overlapping as a consequence of the bond distance contraction, which has been directly probed by EXAFS (extended x-ray absorption fine structure) spectra. The La-O Debye Waller factors (DWFs) tend to increase whereas the La-Nb bond DWFs show only a tendency to decrease indicating the robustness of the crystal lattice structure, even in presence of the oxygen disordering. This permits the system to reverse back to its original conditions in this pressure range as evident from the measurements upon pressure release. The present results have been interpreted in the light of charge transfer related to the two-step reduction mechanism acting at the Nb site (with niobium ions passing from Nb? to Nb?) which also results in the elongation of the Nb-O bond distances in the octahedra, in agreement with the Nb K-edge results reported earlier.

Augmentation of Quick-EXAFS measurement facility at the energy scanning EXAFS beamline at INDUS-2 SRS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poswal, A. K., E-mail: poswalashwini@gmail.com; Agrawal, Ankur; Bhattachryya, D.

2015-06-24

In this paper implementation of Quick-EXAFS data acquisition facility at the Energy Scanning EXAFS beamline(BL-09) at INDUS-2 synchrotron source, Indore is presented. By adopting a continuous-scan mode in the Double Crystal monochromator (DCM), a high signal-to-noise ratio is maintained and the acquisition time is reduced to few seconds. The quality of spectra and repeatability is checked by measuring standards. The present mode of data acquisition would enable EXAFS measurement for in-situ studies even in fluorescence mode.

Fischer–Tropsch Synthesis: XANES Spectra of Potassium in Promoted Precipitated Iron Catalysts as a Function of Time On-stream

DOE PAGES

Jacobs, Gary; Pendyala, Venkat Ramana Rao; Martinelli, Michela; ...

2017-06-06

XANES K-edge spectra of potassium promoter in precipitated Fe catalysts were acquired following activation by carburization in CO and as a function of time on-stream during the course of a Fischer–Tropsch synthesis run for a 100Fe:2K catalyst by withdrawing catalysts, sealed in wax product, for analysis. CO-activated and end-of-run spectra of the catalyst were also obtained for a 100Fe:5K catalyst. Peaks representing electronic transitions and multiple scattering were observed and resembled reference spectra for potassium carbonate or potassium formate. The shift in the multiple scattering peak to higher energy was consistent with sintering of potassium promoter during the course ofmore » the reaction test. The catalyst, however, retained its carbidic state, as demonstrated by XANES and EXAFS spectra at the iron K-edge, suggesting that sintering of potassium did not adversely affect the carburization rate, which is important for preventing iron carbides from oxidizing. This method serves as a starting point for developing better understanding of the chemical state and changes in structure occurring with alkali promoter.« less

Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, S.DeBeer; Petrenko, T.; Neese, F.

2009-05-14

Iron K-edge X-ray absorption pre-edge features have been calculated using a time-dependent density functional approach. The influence of functional, solvation, and relativistic effects on the calculated energies and intensities has been examined by correlation of the calculated parameters to experimental data on a series of 10 iron model complexes, which span a range of high-spin and low-spin ferrous and ferric complexes in O{sub h} to T{sub d} geometries. Both quadrupole and dipole contributions to the spectra have been calculated. We find that good agreement between theory and experiment is obtained by using the BP86 functional with the CP(PPP) basis setmore » on the Fe and TZVP one of the remaining atoms. Inclusion of solvation yields a small improvement in the calculated energies. However, the inclusion of scalar relativistic effects did not yield any improved correlation with experiment. The use of these methods to uniquely assign individual spectral transitions and to examine experimental contributions to backbonding is discussed.« less

Weathering and precipitation after meteorite impact of Ni, Cr, Fe, Ca and Mn in K-T boundary clays from Stevns Klint

NASA Astrophysics Data System (ADS)

Miyano, Yumiko; Yoshiasa, Akira; Tobase, Tsubasa; Isobe, Hiroshi; Hongu, Hidetomo; Okube, Maki; Nakatsuka, Akihiko; Sugiyama, Kazumasa

2016-05-01

Ni, Cr, Fe, Ca and Mn K-edge XANES and EXAFS spectra were measured on K-T boundary clays from Stevns Klint in Denmark. According to XANES spectra and EXAFS analyses, the local structures of Ni, Cr and Fe in K-T boundary clays is similar to Ni(OH)2, Cr2O3 and FeOOH, respectively. It is assumed that the Ni, Cr and Fe elements in impact related glasses is changing into stable hydrate and oxide by the weathering and diagenesis at the surface of the Earth. Ca in K-T boundary clays maintains the diopside-like structure. Local structure of Ca in K-T clays seems to keep information on the condition at meteorite impact. Mn has a local structure like MnCO3 with divalent state. It is assumed that the origin on low abundant of Mn in the Fe-group element in K-T clays was the consumption by life activity and the diffusion to other parts.

Background subtraction for fluorescence EXAFS data of a very dilute dopant Z in Z + 1 host.

PubMed

Medling, Scott; Bridges, Frank

2011-07-01

When conducting EXAFS at the Cu K-edge for ZnS:Cu with very low Cu concentration (<0.04% Cu), a large background was present that increased with energy. This background arises from a Zn X-ray Raman peak, which moves through the Cu fluorescence window, plus the tail of the Zn fluorescence peak. This large background distorts the EXAFS and must be removed separately before reducing the data. A simple means to remove this background is described.

X-ray absorption spectroscopy: EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge Structure)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alp, E.E.; Mini, S.M.; Ramanathan, M.

1990-04-01

The x-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. It has also played an important role in the discovery and systematization of rare-earth elements. The discovery of synchrotron radiation in 1952, and later the availability of broadly tunable synchrotron based x-ray sources have revitalized this technique since the 1970's. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge by Sayers et. al. has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-raymore » Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. An excellent description of the principles and data analysis techniques of EXAFS is given by Teo. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, we will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and samples limitations.« less

Effect of aluminum on the local structure of silicon in zeolites as studied by Si K edge X-ray absorption near-edge fine structure: spectra simulation with a non-muffin tin atomic background.

PubMed

Bugaev, Lusegen A; Bokhoven, Jeroen A van; Khrapko, Valerii V

2009-04-09

Experimental Si K edge X-ray absorption near-edge fine structure (XANES) of zeolite faujasite, mordenite, and beta are interpreted by means of the FEFF8 code, replacing the theoretical atomic background mu(0) by a background that was extracted from an experimental spectrum. To some extent, this diminished the effect of the inaccuracy introduced by the MT potential and accounted for the intrinsic loss of photoelectrons. The agreement of the theoretical and experimental spectra at energies above the white lines enabled us to identify structural distortion around silicon, which occurs with increasing aluminum content. The Si K edge XANES spectra are very sensitive to slight distortions in the silicon coordination. Placing an aluminum atom on a nearest neighboring T site causes a distortion in the silicon tetrahedron, shortening one of the silicon-oxygen bonds relative to the other three.

Experimental and theoretical comparison of the O K-edge nonresonant inelastic X-ray scattering and X-ray absorption spectra of NaReO4.

PubMed

Bradley, Joseph A; Yang, Ping; Batista, Enrique R; Boland, Kevin S; Burns, Carol J; Clark, David L; Conradson, Steven D; Kozimor, Stosh A; Martin, Richard L; Seidler, Gerald T; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Wolfsberg, Laura E

2010-10-06

Accurate X-ray absorption spectra (XAS) of first row atoms, e.g., O, are notoriously difficult to obtain due to the extreme sensitivity of the measurement to surface contamination, self-absorption, and saturation affects. Herein, we describe a comprehensive approach for determining reliable O K-edge XAS data for ReO(4)(1-) and provide methodology for obtaining trustworthy and quantitative data on nonconducting molecular systems, even in the presence of surface contamination. This involves comparing spectra measured by nonresonant inelastic X-ray scattering (NRIXS), a bulk-sensitive technique that is not prone to X-ray self-absorption and provides exact peak intensities, with XAS spectra obtained by three different detection modes, namely total electron yield (TEY), fluorescence yield (FY), and scanning transmission X-ray microscopy (STXM). For ReO(4)(1-), TEY measurements were heavily influenced by surface contamination, while the FY and STXM data agree well with the bulk NRIXS analysis. These spectra all showed two intense pre-edge features indicative of the covalent interaction between the Re 5d and O 2p orbitals. Density functional theory calculations were used to assign these two peaks as O 1s excitations to the e and t(2) molecular orbitals that result from Re 5d and O 2p covalent mixing in T(d) symmetry. Electronic structure calculations were used to determine the amount of O 2p character (%) in these molecular orbitals. Time dependent-density functional theory (TD-DFT) was also used to calculate the energies and intensities of the pre-edge transitions. Overall, under these experimental conditions, this analysis suggests that NRIXS, STXM, and FY operate cooperatively, providing a sound basis for validation of bulk-like excitation spectra and, in combination with electronic structure calculations, suggest that NaReO(4) may serve as a well-defined O K-edge energy and intensity standard for future O K-edge XAS studies.

Vanadium K-edge XAS studies on the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis.

PubMed

Renirie, Rokus; Charnock, John M; Garner, C David; Wever, Ron

2010-06-01

Vanadium K-edge X-ray Absorption Spectra have been recorded for the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis at pH 6.0. The Extended X-ray Absorption Fine Structure (EXAFS) regions provide a refinement of previously reported crystallographic data; one short V=O bond (1.54A) is present in both forms. For the native enzyme, the vanadium is coordinated to two other oxygen atoms at 1.69A, another oxygen atom at 1.93A and the nitrogen of an imidazole group at 2.02A. In the peroxo-form, the vanadium is coordinated to two other oxygen atoms at 1.67A, another oxygen atom at 1.88A and the nitrogen of an imidazole group at 1.93A. When combined with the available crystallographic and kinetic data, a likely interpretation of the EXAFS distances is a side-on bound peroxide involving V-O bonds of 1.67 and 1.88A; thus, the latter oxygen would be 'activated' for transfer. The shorter V-N bond observed in the peroxo-form is in line with the previously reported stronger binding of the cofactor in this form of the enzyme. Reduction of the enzyme with dithionite has a clear influence on the spectrum, showing a change from vanadium(V) to vanadium(IV).

Temperature dependence of pre-edge features in Ti K-edge XANES spectra for ATiO₃ (A = Ca and Sr), A₂TiO₄ (A = Mg and Fe), TiO₂ rutile and TiO₂ anatase.

PubMed

Hiratoko, Tatsuya; Yoshiasa, Akira; Nakatani, Tomotaka; Okube, Maki; Nakatsuka, Akihiko; Sugiyama, Kazumasa

2013-07-01

XANES (X-ray absorption near-edge structure) spectra of the Ti K-edges of ATiO3 (A = Ca and Sr), A2TiO4 (A = Mg and Fe), TiO2 rutile and TiO2 anatase were measured in the temperature range 20-900 K. Ti atoms for all samples were located in TiO6 octahedral sites. The absorption intensity invariant point (AIIP) was found to be between the pre-edge and post-edge. After the AIIP, amplitudes damped due to Debye-Waller factor effects with temperature. Amplitudes in the pre-edge region increased with temperature normally by thermal vibration. Use of the AIIP peak intensity as a standard point enables a quantitative comparison of the intensity of the pre-edge peaks in various titanium compounds over a wide temperature range.

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

USGS Publications Warehouse

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

1996-01-01

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

Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

DOE PAGES

Martin-Diaconescu, Vlad; Gennari, Marcello; Gerey, Bertrand; ...

2014-12-10

Calcium K-edge pre-edges coupled with TD-DFT theoretical calculation of spectra provide a powerful approach for the characterization of complex calcium centers in inorganic and bioinorganic chemistry. Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodologymore » to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.« less

Photoabsorption study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

NASA Technical Reports Server (NTRS)

Frigo, Sean P.; McNulty,Ian; Richmond, Robert C.; Ehret, Charles F.

2003-01-01

We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include red phosphorus, hydrated sodium phosphate (Na3PO4 12 H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position, where each is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B.meguterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition, the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

Photoabsorption Study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

NASA Technical Reports Server (NTRS)

Frigo, Sean P.; McNulty, Ian; Richmond, Robert C.; Ehret, Charles F.

2002-01-01

We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include elemental red phosphorus, hydrated sodium phosphate (Na3PO4.12H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Elemental red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position. Each spectrum for these substances is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for elemental red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B. megaterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition,the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

Transition metal atomic multiplets in the ligand K-edge x-ray absorption spectra and multiple oxidation states in the L2,3 emission of strongly correlated compounds

NASA Astrophysics Data System (ADS)

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

2014-07-01

We present results that show that atomic multiplet ligand field calculations are in very good agreement with experimental x-ray absorption spectra at the L2,3 edge of transition metal (TM) di-fluorides (MF2, MCrCu). For chromium more than one TM oxidation state is needed to achieve such an agreement. We also show that signature of the TM atomic multiplet can be found at the pre-edge of the fluorine K-edge x-ray absorption spectra. TM atomic multiplet ligand field calculations with a structureless core hole show good agreement with the observed pre-edges in the experimental fluorine absorption spectra. Preliminary results for the comparison between calculated and experimental resonant x-ray emission spectra for nominal CrF2 with more than one oxidation state indicate the presence of three chromium oxidation states in the bulk.

Magnesium K-edge XANES spectroscopy of geological standards.

PubMed

Yoshimura, Toshihiro; Tamenori, Yusuke; Iwasaki, Nozomu; Hasegawa, Hiroshi; Suzuki, Atsushi; Kawahata, Hodaka

2013-09-01

Magnesium K-edge X-ray absorption near-edge structure (XANES) spectra have been investigated to develop a systematic understanding of a suite of Mg-bearing geological materials such as silicate and carbonate minerals, sediments, rocks and chemical reagents. For the model compounds the Mg XANES was found to vary widely between compounds and to provide a fingerprint for the form of Mg involved in geologic materials. The energy positions and resonance features obtained from these spectra can be used to specify the dominant molecular host site of Mg, thus shedding light on Mg partitioning and isotope fractionation in geologic materials and providing a valuable complement to existing knowledge of Mg geochemistry.

Combined Mössbauer spectroscopic, multi-edge X-ray absorption spectroscopic, and density functional theoretical study of the radical SAM enzyme spore photoproduct lyase.

PubMed

Silver, Sunshine C; Gardenghi, David J; Naik, Sunil G; Shepard, Eric M; Huynh, Boi Hanh; Szilagyi, Robert K; Broderick, Joan B

2014-03-01

Spore photoproduct lyase (SPL), a member of the radical S-adenosyl-L-methionine (SAM) superfamily, catalyzes the direct reversal of the spore photoproduct, a thymine dimer specific to bacterial spores, to two thymines. SPL requires SAM and a redox-active [4Fe-4S] cluster for catalysis. Mössbauer analysis of anaerobically purified SPL indicates the presence of a mixture of cluster states with the majority (40 %) as [2Fe-2S](2+) clusters and a smaller amount (15 %) as [4Fe-4S](2+) clusters. On reduction, the cluster content changes to primarily (60 %) [4Fe-4S](+). The speciation information from Mössbauer data allowed us to deconvolute iron and sulfur K-edge X-ray absorption spectra to uncover electronic (X-ray absorption near-edge structure, XANES) and geometric (extended X-ray absorption fine structure, EXAFS) structural features of the Fe-S clusters, and their interactions with SAM. The iron K-edge EXAFS data provide evidence for elongation of a [2Fe-2S] rhomb of the [4Fe-4S] cluster on binding SAM on the basis of an Fe···Fe scatterer at 3.0 Å. The XANES spectra of reduced SPL in the absence and presence of SAM overlay one another, indicating that SAM is not undergoing reductive cleavage. The X-ray absorption spectroscopy data for SPL samples and data for model complexes from the literature allowed the deconvolution of contributions from [2Fe-2S] and [4Fe-4S] clusters to the sulfur K-edge XANES spectra. The analysis of pre-edge features revealed electronic changes in the Fe-S clusters as a function of the presence of SAM. The spectroscopic findings were further corroborated by density functional theory calculations that provided insights into structural and electronic perturbations that can be correlated by considering the role of SAM as a catalyst or substrate.

EXAFS study of some coordination polymers of copper

NASA Astrophysics Data System (ADS)

Deshpande, A. P.

1995-02-01

The EXAFS spectra for (1) azelaic acid bis phenyl hydrazide, (2) azelaic acid bis 2,4 dinitro phenyl hydrazide and (3) sebacic acid bis phenyl hydrazide coordination polymers of copper were obtained using the EXAFS facility of the Daresbury Laboratory. The EXAFS analysis revealed that copper is surrounded by four nitrogen and two oxygen atoms in the first coordination shell, while the second coordination shell consists of two carbon atoms. This information suggests the octahedral geometry for the repeating units of polymeric complexes, in contrast to the square planar geometry previously proposed.

Fermi edge singularities in the mesoscopic regime: Photoabsorption spectra

NASA Astrophysics Data System (ADS)

Hentschel, Martina; Ullmo, Denis; Baranger, Harold U.

2007-12-01

We study Fermi edge singularities in photoabsorption spectra of generic mesoscopic systems such as quantum dots or nanoparticles. We predict deviations from macroscopic-metallic behavior and propose experimental setups for the observation of these effects. The theory is based on the model of a localized, or rank one, perturbation caused by the (core) hole left behind after the photoexcitation of an electron into the conduction band. The photoabsorption spectra result from the competition between two many-body responses, Anderson’s orthogonality catastrophe and the Mahan-Nozières-DeDominicis contribution. Both mechanisms depend on the system size through the number of particles and, more importantly, fluctuations produced by the coherence characteristic of mesoscopic samples. The latter lead to a modification of the dipole matrix element and trigger one of our key results: a rounded K -edge typically found in metals will turn into a (slightly) peaked edge on average in the mesoscopic regime. We consider in detail the effect of the “bound state” produced by the core hole.

Two-peak structure in the K-edge RIXS spectra of a spatially frustrated Heisenberg antiferromagnet

NASA Astrophysics Data System (ADS)

Datta, Trinanjan; Luo, Cheng; Yao, Dao-Xin

2014-03-01

Quantum fluctuations due to spatial anisotropy and strong magnetic frustration lead to the formation of a two-peak structure in the K-edge bimagnon RIXS intensity spectra of a Jx-Jy-J2 Heisenberg model on a square lattice. We compute the RIXS intensity, including up to first order 1/S spin wave expansion correction, using the Bethe-Salpeter equation within the ladder approximation scheme. The two-peak feature occurs in both the antiferromagnetic phase and the collinear antiferromagnetic phase. A knowledge of the peak splitting energy from both magnetically ordered regime can provide experimentalists with an alternative means to measure and study the effects of local microscopic exchange constants. Cottrell Research Corporation, NSFC-11074310, NSFC-11275279, Specialized Research Fund for the Doctoral Program of Higher Education.

Combined EXAFS Spectroscopic and Quantum Chemical Study on the Complex Formation of Am(III) with Formate.

PubMed

Fröhlich, Daniel R; Kremleva, Alena; Rossberg, André; Skerencak-Frech, Andrej; Koke, Carsten; Krüger, Sven; Rösch, Notker; Panak, Petra J

2017-06-19

The complexation of Am(III) with formate in aqueous solution is studied as a function of the pH value using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy, iterative transformation factor analysis (ITFA), and quantum chemical calculations. The Am L III -edge EXAFS spectra are analyzed to determine the molecular structure (coordination numbers; Am-O and Am-C distances) of the formed Am(III)-formate species and to track the shift of the Am(III) speciation with increasing pH. The experimental data are compared to predictions from density functional calculations. The results indicate that formate binds to Am(III) in a monodentate fashion, in agreement with crystal structures of lanthanide formates. Furthermore, the investigations are complemented by thermodynamic speciation calculations to verify further the results obtained.

Atomic multiplets at the L2,3 edge of 3d transition metals and the ligand K edge in x-ray absorption spectroscopy of ionic systems

NASA Astrophysics Data System (ADS)

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

2013-06-01

Experimental X-ray absorption spectra at the fluorine K and transition metal L2,3 absorption edges of the MF2 (M=Cr-Ni) family are presented. Ligand field calculations in D4h symmetry show very good agreement with the transition metal L2,3 XAS spectra. To successfully explain nominal Cr2+ L2,3 XAS spectrum in CrF2, the inclusion of Cr+ and Cr3+ was needed implying the presence of a disproportionation reaction. The multiplet calculations were then modified to remove the structure of the 2p hole in the calculated M 2p→3d absorption spectra. These results for the 3dn+1 states are in one to one correspondence with the leading edge structures found at the fluorine K edge. A direct comparison with the metal L2,3 edges also indicates that there is evidence of the metal multiplet at the fluorine K pre-edge structures.

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

NASA Astrophysics Data System (ADS)

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

2010-06-01

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

Effects of phonon broadening on x-ray near-edge spectra in molecular crystals

NASA Astrophysics Data System (ADS)

Vinson, John; Jach, Terrence; Elam, Tim; Denlinger, Jonathon

2014-03-01

Calculations of near-edge x-ray spectra are often carried out using the average atomic coordinates from x-ray or neutron scattering experiments or from density functional theory (DFT) energy minimization. This neglects disorder from thermal and zero-point vibrations. Here we look at the nitrogen K-edge of ammonium chloride and ammonium nitrate, comparing Bethe-Salpeter calculations of absorption and fluorescence to experiment. We find that intra-molecular vibrational effects lead to significant, non-uniform broadening of the spectra, and that for some features zero-point motion is the primary source of the observed shape.

Core level electron energy-loss spectra of minerals: pre-edge fine structures at the oxygen K-edge . Comment on ``Water in minerals detectable by electron energy-loss spectroscopy EELS'' by R. Wirth, Phys Chem Minerals (1997) 24:561-568

NASA Astrophysics Data System (ADS)

van Aken, P. A.; Liebscher, B.; Styrsa, V. J.

In a recent paper entitled ``Water in minerals detectable by electron energy-loss spectroscopy EELS'' by R. Wirth, it has been claimed that OH-- and H2O-bearing minerals exhibit a characteristic peak in the ELNES spectra at about 528 eV prior to the onset of the O K-edge at 532 eV, which could be used for (semi-)quantitative determination of water- or OH-contents on a nanometer scale. It is shown here by parallel electron energy-loss spectroscopy (PEELS) recorded in a transmission electron microscope (TEM) that O K-pre-edge peaks with very high intensities may also exist in water-free compounds and minerals, in particular when they contain transition metals. These spectral features arise from covalent mixing of the metal and oxygen states, which introduces oxygen p character in unoccupied states of mainly metal character. The point is illustrated by the comparison of hematite (α-Fe2O3) and lepidocrocite (γ-FeOOH) O K-edge PEELS spectra which exhibit similar intensities of the pre-edge peak, despite of their grossly different OH- contents. As a consequence, the general validity of the method proposed by Wirth is questioned.

A new detector for sub-millisecond EXAFS spectroscopy at the European Synchrotron Radiation Facility.

PubMed

Kantor, Innokenty; Labiche, Jean-Claude; Collet, Emmanuel; Siron, Laurent; Thevenin, Jean-Jacques; Ponchut, Cyril; Borrel, Jacques; Mairs, Trevor; Marini, Carlo; Strohm, Cornelius; Mathon, Olivier; Pascarelli, Sakura

2014-11-01

A new FReLoN (Fast-Readout Low-Noise) high-frame-rate detector adopted for the fast continuous collection of X-ray absorption spectra is presented. The detector is installed on the energy-dispersive X-ray absorption beamline ID24 at the ESRF and is capable of full time-resolved EXAFS spectra collection with over 4 kHz repetition rate and 0.2 ms exposure time. An example of the in situ kinetic study of the high-temperature oxidation of metallic iron is presented.

Sequestration of Sr(II) By Calcium Oxalate - a Batch Uptake Study And EXAFS Analysis of Model Compounds And Reaction Products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singer, D.M.; Johnson, S.B.; Catalano, J.G.

Calcium oxalate monohydrate (CaC{sub 2}O{sub 4}{center_dot}H{sub 2}O -- abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II){sub aq} following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4--10, with initial Sr solution concentrations, [Sr]{sub aq}, ranging from 1 x 10{sup -4} to 1 x 10{sup -3} M and ionic strengths ranging of 0.001--0.1more » M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sr{sub aq} for two days, the solution Ca concentration, [Ca]{sup aq}, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sr{sub aq} removed from solution was nearly equal to the total [Ca]{sup aq} after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric

Mn K-Edge XANES and Kβ XES Studies of Two Mn–Oxo Binuclear Complexes: Investigation of Three Different Oxidation States Relevant to the Oxygen-Evolving Complex of Photosystem II

PubMed Central

Visser, Hendrik; Anxolabéhère-Mallart, Elodie; Bergmann, Uwe; Glatzel, Pieter; Robblee, John H.; Cramer, Stephen P.; Girerd, Jean-Jacques; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

2014-01-01

Two structurally homologous Mn compounds in different oxidation states were studied to investigate the relative influence of oxidation state and ligand environment on Mn K-edge X-ray absorption near-edge structure (XANES) and Mn Kβ X-ray emission spectroscopy (Kβ XES). The two manganese compounds are the di-μ-oxo compound [L′2MnIIIO2MnIVL′2](ClO4)3, where L′ is 1,10-phenanthroline (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623–6630) and the linear mono-μ-oxo compound [LMnIIIOMnIIIL](ClO4)2, where L− is the monoanionic N,N-bis(2-pyridylmethyl)-N′-salicylidene-1,2-diaminoethane ligand (Horner, O.; Anxolabéhère-Mallart, E.; Charlot, M. F.; Tchertanov, L.; Guilhem, J.; Mattioli, T. A.; Boussac, A.; Girerd, J.-J. Inorg. Chem. 1999, 38, 1222–1232). Preparative bulk electrolysis in acetonitrile was used to obtain higher oxidation states of the compounds: the MnIVMnIV species for the di-μ-oxo compound and the MnIIIMnIV and MnIVMnIV species for the mono-μ-oxo compound. IR, UV/vis, EPR, and EXAFS spectra were used to determine the purity and integrity of the various sample solutions. The Mn K-edge XANES spectra shift to higher energy upon oxidation when the ligand environment remains similar. However, shifts in energy are also observed when only the ligand environment is altered. This is achieved by comparing the di-μ-oxo and linear mono-μ-oxo Mn–Mn moieties in equivalent oxidation states, which represent major structural changes. The magnitude of an energy shift due to major changes in ligand environment can be as large as that of an oxidation-state change. Therefore, care must be exercised when correlating the Mn K-edge energies to manganese oxidation states without taking into account the nature of the ligand environment and the overall structure of the compound. In contrast to Mn K-edge XANES, Kβ XES spectra show less dependence on ligand environment. The Kβ1,3 peak energies are comparable for the di-μ-oxo and mono

Mn K-Edge X-ray Absorption Studies of Oxo- and Hydroxo-manganese(IV) Complexes: Experimental and Theoretical Insights into Pre-Edge Properties

PubMed Central

2015-01-01

Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [MnII(Cl)2(Me2EBC)], [MnIV(OH)2(Me2EBC)]2+, and [MnIV(O)(OH)(Me2EBC)]+, which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [MnIV(O)(OH)(Me2EBC)]+ revealed Mn–O scatterers at 1.71 and 1.84 Å and Mn–N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [MnII(Cl)2(Me2EBC)] and [MnIV(OH)2(Me2EBC)]2+ are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn–O(H) distances and pre-edge peak areas of MnIV=O and MnIV–OH complexes, but this trend was strongly modulated by the MnIV coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn–O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal MnIV=O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn=O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn=O σ* molecular orbital (MO) but also show intense transitions to 3dx2–y2 and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal MnIV=O adducts. These results underscore the importance of reporting experimental pre-edge areas

Mn K-edge X-ray absorption studies of oxo- and hydroxo-manganese(IV) complexes: experimental and theoretical insights into pre-edge properties.

PubMed

Leto, Domenick F; Jackson, Timothy A

2014-06-16

Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [Mn(II)(Cl)2(Me2EBC)], [Mn(IV)(OH)2(Me2EBC)](2+), and [Mn(IV)(O)(OH)(Me2EBC)](+), which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [Mn(IV)(O)(OH)(Me2EBC)](+) revealed Mn-O scatterers at 1.71 and 1.84 Å and Mn-N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [Mn(II)(Cl)2(Me2EBC)] and [Mn(IV)(OH)2(Me2EBC)](2+) are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn-O(H) distances and pre-edge peak areas of Mn(IV)═O and Mn(IV)-OH complexes, but this trend was strongly modulated by the Mn(IV) coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn-O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal Mn(IV)═O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn═O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn═O σ* molecular orbital (MO) but also show intense transitions to 3dx(2)-y(2) and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal Mn(IV)═O adducts. These results underscore the importance of

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

NASA Astrophysics Data System (ADS)

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

2015-05-01

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

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2004-06-01

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe 2O 3) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH) 6 polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe 2(OH) 2(H 2O) 8Cu(OH) 4and Fe 3(OH) 4(H 2O) 10Cu 2(OH) 6 clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO 4H n) n-6 and Fe(O,OH) 6 polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH) 2. Having identified the bidentate (FeOH) 2Cu(OH) 20 and tridentate (Fe 3O(OH) 2)Cu 2(OH) 30 surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions 3( FeOH)+2 Cu2++3 H2O=( Fe3O( OH) 2) Cu2( OH) 30+4 H+ and 2( FeOH)+ Cu2++2 H2O=( FeOH) 2Cu( OH) 20+2 H+. The two stability constants are similar for the three iron (hydr)oxide phases investigated.

Mammographic x-ray unit kilovoltage test tool based on k-edge absorption effect.

PubMed

Napolitano, Mary E; Trueblood, Jon H; Hertel, Nolan E; David, George

2002-09-01

A simple tool to determine the peak kilovoltage (kVp) of a mammographic x-ray unit has been designed. Tool design is based on comparing the effect of k-edge discontinuity of the attenuation coefficient for a series of element filters. Compatibility with the mammography accreditation phantom (MAP) to obtain a single quality control film is a second design objective. When the attenuation of a series of sequential elements is studied simultaneously, differences in the absorption characteristics due to the k-edge discontinuities are more evident. Specifically, when the incident photon energy is higher than the k-edge energy of a number of the elements and lower than the remainder, an inflection may be seen in the resulting attenuation data. The maximum energy of the incident photon spectra may be determined based on this inflection point for a series of element filters. Monte Carlo photon transport analysis was used to estimate the photon transmission probabilities for each of the sequential k-edge filter elements. The photon transmission corresponds directly to optical density recorded on mammographic x-ray film. To observe the inflection, the element filters chosen must have k-edge energies that span a range greater than the expected range of the end point energies to be determined. For the design, incident x-ray spectra ranging from 25 to 40 kVp were assumed to be from a molybdenum target. Over this range, the k-edge energy changes by approximately 1.5 keV between sequential elements. For this design 21 elements spanning an energy range from 20 to 50 keV were chosen. Optimum filter element thicknesses were calculated to maximize attenuation differences at the k-edge while maintaining optical densities between 0.10 and 3.00. Calculated relative transmission data show that the kVp could be determined to within +/-1 kV. To obtain experimental data, a phantom was constructed containing 21 different elements placed in an acrylic holder. MAP images were used to determine

XAS study of TiO2-based nanomaterials

NASA Astrophysics Data System (ADS)

Schneider, K.; Zajac, D.; Sikora, M.; Kapusta, Cz.; Michalow-Mauke, K.; Graule, Th.; Rekas, M.

2015-07-01

X-Ray Absorption Spectroscopy studies of the W (0-1 at% W) and Mo-doped TiO2 (0-1 at% Mo) nanoparticle specimens at the K edges of titanium and molybdenum as well as at the L2 L3 edges of tungsten are presented. The materials were prepared with Flame Spray Synthesis process by oxidation of metal-organic precursors. The Ti:K edge spectra in the XANES range show pre-edge and post-edge features characteristic for anatase. A decrease of the amplitude of the EXAFS function with doping is observed and attributed to a softening of the crystal lattice. The Mo EXAFS functions show a considerable decrease of the second-neighbour-shell peak with increasing Mo content, which is attributed to an increased number of cation vacancies. For tungsten a less pronounced effect is observed. The Mo and W XANES spectra do not show noticeable changes with doping level, which indicates their unchanged oxidation states.

Multifunctional synchrotron spectrometer of the National Research Center "Kurchatov Institute": I. EXAFS in dispersive mode

NASA Astrophysics Data System (ADS)

Aksenov, V. L.; Tyutyunnikov, S. I.; Shalyapin, V. N.; Belyaev, A. D.; Artemiev, A. N.; Artemiev, N. A.; Kirillov, B. F.; Kovalchiuk, M. V.; Demkiv, A. A.; Knyazev, G. A.

2017-01-01

The improved X-ray optical scheme, the system of registration, and the measurement procedure of the multifunctional synchrotron radiation spectrometer in the dispersive EXAFS mode are described. The results of the spectrometer energy resolution measurements are given. The advantages and disadvantages of traditional and dispersive EXAFS spectrometers are analyzed. Examples of EXAFS spectra measured in the dispersive mode are given.

Temperature and radiation effects at the fluorine K-edge in LiF

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwartz, Craig P.; Ponce, Francisco; Friedrich, Stephan

Here, the fluorine K-edge of LiF is studied both experimentally and theoretically as a function of temperature. Instantaneous thermal fluctuations in atomic positions are shown in molecular dynamics simulations to increase in amplitude from 0.029 to 0.064 nm in the temperature range from 40 to 298 K. This is sufficient to cause instantaneous deviations from local octahedral atomic symmetry in this rock-salt crystal, resulting in altered electronic structure. The lowered symmetry of the lowest core-excited states of fluorine atoms is evident in X-ray absorption spectra at the F K-edge. In addition, sufficient radiation exposure produces a new X-ray absorption peak,more » below the F K-edge of LiF, which is assigned to defects in LiF based on both calculations and comparison to previous experiments.« less

Temperature and radiation effects at the fluorine K-edge in LiF

DOE PAGES

Schwartz, Craig P.; Ponce, Francisco; Friedrich, Stephan; ...

2017-05-30

Here, the fluorine K-edge of LiF is studied both experimentally and theoretically as a function of temperature. Instantaneous thermal fluctuations in atomic positions are shown in molecular dynamics simulations to increase in amplitude from 0.029 to 0.064 nm in the temperature range from 40 to 298 K. This is sufficient to cause instantaneous deviations from local octahedral atomic symmetry in this rock-salt crystal, resulting in altered electronic structure. The lowered symmetry of the lowest core-excited states of fluorine atoms is evident in X-ray absorption spectra at the F K-edge. In addition, sufficient radiation exposure produces a new X-ray absorption peak,more » below the F K-edge of LiF, which is assigned to defects in LiF based on both calculations and comparison to previous experiments.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shimada, Hiroyuki, E-mail: hshimada@cc.tuat.ac.jp; Minami, Hirotake; Okuizumi, Naoto

2015-05-07

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

Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3.

PubMed

Marini, C; Noked, O; Kantor, I; Joseph, B; Mathon, O; Shuker, R; Kennedy, B J; Pascarelli, S; Sterer, E

2016-02-03

Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb(5+) towards Nb(4+) above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ∼14.5 GPa.

Absorption-Edge-Modulated Transmission Spectra for Water Contaminant Monitoring

DTIC Science & Technology

2016-03-31

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9675 Absorption-Edge-Modulated Transmission Spectra for Water Contaminant ...ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Absorption-Edge-Modulated Transmission Spectra for Water Contaminant Monitoring...Unlimited Unclassified Unlimited 35 Samuel G. Lambrakos (202) 767-2601 Monitoring of contaminants associated with specific water resources using

EXAFS Study on LiFePO4 Powders Produced From Two Sol-Gel Routes

NASA Astrophysics Data System (ADS)

Negara, V. S. I.; Latif, C.; Wongtepa, W.; Pratapa, S.

2018-04-01

The local structure of LiFePO4 powders has been investigated using Fe K-edge Extended X-Ray Absorption Fine Structure (EXAFS) Spectroscopy data. The synthesis of LFP powders was carried out using two different sol-gel methods. The raw materials for Fe source were ironstone and commercial precursor of FeCl2·4H2O. Synthesis using natural materials produced two phases, namely LiFePO4 olivine and Li3Fe2(PO4)3 nasicon, whereas that using a commercial product produced a single phase of LiFePO4 olivine. The EXAFS data for both samples were collected at Synchrotron Light Research Institute (SLRI), Thailand. Fitting of the model on the experimental curve provided parameters that can be interpreted as the distance between Fe as the absorber and the nearest atoms on the LFP materials. The EXAFS data analysis has shown that synthesis of LFPs using different Fe sources gives slightly different nearest-neighbor distances, namely Fe-O of 0.21% -0.23%, Fe-P of 0.14% - 0.16%, Fe-Fe of 0.12% for both samples, respectively.

Phosphorus K-edge XANES spectroscopy of mineral standards

PubMed Central

Ingall, Ellery D.; Brandes, Jay A.; Diaz, Julia M.; de Jonge, Martin D.; Paterson, David; McNulty, Ian; Elliott, W. Crawford; Northrup, Paul

2011-01-01

Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was performed on phosphate mineral specimens including (a) twelve specimens from the apatite group covering a range of compositional variation and crystallinity; (b) six non-apatite calcium-rich phosphate minerals; (c) 15 aluminium-rich phosphate minerals; (d) ten phosphate minerals rich in either reduced iron or manganese; (e) four phosphate minerals rich in either oxidized iron or manganese; (f) eight phosphate minerals rich in either magnesium, copper, lead, zinc or rare-earth elements; and (g) four uranium phosphate minerals. The identity of all minerals examined in this study was independently confirmed using X-ray powder diffraction. Minerals were distinguished using XANES spectra with a combination of pre-edge features, edge position, peak shapes and post-edge features. Shared spectral features were observed in minerals with compositions dominated by the same specific cation. Analyses of apatite-group minerals indicate that XANES spectral patterns are not strongly affected by variations in composition and crystallinity typical of natural mineral specimens. PMID:21335905

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer.

PubMed

Frank, Patrick; Szilagyi, Robert K; Gramlich, Volker; Hsu, Hua-Fen; Hedman, Britt; Hodgson, Keith O

2017-02-06

Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M II (itao)(SO 4 )(H 2 O) 0,1 ] (M = Co, Ni, Cu) and [Cu(Me 6 tren)(SO 4 )] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal-sulfur bond, while the XAS preedge of [Zn(itao)(SO 4 )] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO 4 )] but not of [Cu(Me 6 tren)(SO 4 )] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M II (SO 4 )(H 2 O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5-2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal-absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

DOE PAGES

Frank, Patrick; Szilagyi, Robert K.; Gramlich, Volker; ...

2017-01-09

Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M II(itao)(SO 4)(H 2O) 0,1] (M = Co, Ni, Cu) and [Cu(Me 6tren)(SO 4)] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal–sulfur bond, while the XAS preedge of [Zn(itao)(SO 4)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO 4)] but not of [Cu(Me 6tren)(SO 4)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M II(SO 4)(Hmore » 2O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5–2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal–absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which

The irreversible formation of palladium carbide during hydrogenation of 1-pentyne over silica-supported palladium nanoparticles: in situ Pd K and L3 edge XAS.

PubMed

Tew, Min Wei; Nachtegaal, Maarten; Janousch, Markus; Huthwelker, Thomas; van Bokhoven, Jeroen A

2012-04-28

The catalytically active phase of silica-supported palladium catalysts in the selective and non-selective hydrogenation of 1-pentyne was determined using in situ X-ray absorption spectroscopy at the Pd K and L(3) edges. Upon exposure to alkyne, a palladium carbide-like phase rapidly forms, which prevents hydrogen to diffuse into the bulk of the nano-sized particles. Both selective and non-selective hydrogenation occur over carbided particles. The palladium carbide-like phase is stable under reaction conditions and only partially decomposes under high hydrogen partial pressure. Non-selective hydrogenation to pentane is not indicative of hydride formation. The palladium carbide phase was detected in the EXAFS analysis and the K edge XANES showed representative features. This journal is © the Owner Societies 2012

Aqueous solubility diagrams for cementitious waste stabilization systems. 3. Mechanism of zinc immobilizaton by calcium silicate hydrate.

PubMed

Tommaseo, C E; Kersten, M

2002-07-01

Zinc oxide was added during hydration of alite (C3S) as an analogue for solidification/stabilization by cement of metal-bearing hazardous waste. Curing of samples was stopped at various intervals between 8 h and 100 d, and the reaction products were analyzed by both X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS at Zn, Ca, and Si K-edges). Calcium zincate hydrate (CaZn2(OH)6 x 2H2O) initially formed together with calcium silicate hydrate (CSH) vanishes from X-ray diffractograms after 14 d, and no other crystalline Zn-bearing phase could be detected thereafter. EXAFS Zn K-edge data analysis reveals that Zn(O,OH)4 tetrahedra continue to determine the first shell coordination. However, a new Zn-Si bond appears in the second coordination shell as indicated by both Zn K-edge and Si K-edge EXAFS. Together with the Ca-Zn and Ca-Ca shells derived from the Ca K-edge EXAFS spectra, a structural model for the site occupation of Zn in CSH is proposed, whereby the Zn(O,OH)4 tetrahedra are bound in layer rather than interlayer positions substituting for the silicate bridging tetrahedra and/or at terminal silicate chain sites. This structural model enables ultimately the formulation of a thermodyamic Lippmann model to predict the aqueous solubility of Zn in solid solution with a CSH phase of a Ca/Si ratio fixed to unity.

Nanoparticulate mackinawite formation; a stopped and continuous flow XANES and EXAFS investigation

NASA Astrophysics Data System (ADS)

Butler, I. B.; Bell, A. M.; Charnock, J. M.; Rickard, D.; Vaughan, D. J.; Oldroyd, A.

2009-12-01

The sequestration of sulfur and iron within sedimentary iron sulfides, and ultimately as pyrite, is a major sink in global biogeochemical cycles of those elements and has impacts on global carbon and oxygen cycles. The formation of the metastable black iron (II) monosulfide mackinawite is a key process because mackinawite forms in aqueous solutions where the Fe(II) and S(-II) IAP exceeds mackinawite’s Ksp. Mackinawite is the first formed iron sulfide phase, a consequence of Ostwald’s step rule and is a reactant phase during the formation of thermodynamically stable sedimentary iron sulfide minerals such as pyrite. The reaction of dissolved Fe(II) and sulfide is extremely fast and reactions in the environmentally significant near-neutral pH range tend to completion in <1 second. We have combined stopped and continuous flow techniques with X-ray absorption spectroscopy to evaluate the products of the fast precipitation kinetics of mackinawite over millisecond timescales. EXAFS spectra and data collected during flow experiments were compared with those from a well characterised freeze-dried nanoparticulate mackinawite standard and with published data. Published work has used Rietveld crystal structure refinement to determine bond distances of 2.2558 and 2.5976Å for Fe-S and Fe-Fe respectively. In our experiments Fe K edge XANES is consistent with tetrahedrally coordinated Fe in the precipitated sulfide phase. EXAFS data show that local Fe-S and Fe-Fe coordination and interatomic distances (Fe-S = 2.24Å; Fe-Fe = 2.57Å) are consistent with those determined for the standard mackinawite and published data. The coordination and spacing are developed in the precipitated phase after <10ms reaction at pH5, and considerably faster in experiments at near neutral to alkaline pH. No evidence for phases structurally intermediate between hexaqua Fe(II) and precipitated mackinawite was observed. Aqueous FeS° cluster complexes previously identified as intermediates during

XANES and EXAFS study of Au-substituted YBa2Cu3O(7-delta)

NASA Technical Reports Server (NTRS)

Ruckman, Mark W.; Hepp, Aloysius F.

1990-01-01

The near-edge structure (XANES) of the Au L3 and Cu K edges of YBa2Au(0.3)Cu(2.7)O(7-delta) was studied. X ray diffraction suggests that Au goes on the Cu(1) site and XANES shows that this has little effect on the oxidation state of the remaining copper. The gold L3 edge develops a white line feature whose position lies between that of trivalent gold oxide (Au2O3) and monovalent potassium gold cyanide (KAu(CN)2) and whose intensity relative to the edge step is smaller than in the two reference compounds. The L3 EXAFS for Au in the superconductor resembles that of Au2O3. However, differences in the envelope of the Fourier filtered component for the first shell suggest that the local structure of the Au in the superconductor is not equivalent to Au2O3.

Characterization of extracellular polymeric substances in the biofilms of typical bacteria by the sulfur K-edge XANES spectroscopy.

PubMed

Lin, Huirong; Ye, Chengsong; Lv, Lu; Zheng, Clark Renjun; Zhang, Shenghua; Zheng, Lei; Zhao, Yidong; Yu, Xin

2014-08-01

A combined approach of physicochemical extraction and sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy was applied to characterize the extracellular polymeric substances (EPS) of typical bacterial biofilms in this study. Physicochemical analysis showed variation of the contents of DNA, polysaccharide and protein in different fractions of EPS in different mediums. The sulfur K-edge XANES analysis yielded a variety of spectra. Spectral fitting of the XANES spectra utilizing a large set of model compounds showed that there was more reduced sulfur in both LB-EPS (loosely bound EPS) and TB-EPS (tightly bound EPS) of all the biofilms in LB medium than in R2A medium. More oxidized sulfur was identified in LB-EPS than that in TB-EPS, suggesting different niches and physiological heterogeneity in the biofilms. Our results suggested that the sulfur K-edge XANES can be a useful tool to analyze the sulfur speciation in EPS of biofilms. Copyright © 2014. Published by Elsevier B.V.

Bimagnon studies in cuprates with resonant inelastic x-ray scattering at the O K edge. I. Assessment on La2CuO4 and comparison with the excitation at Cu L3 and Cu K edges

NASA Astrophysics Data System (ADS)

Bisogni, V.; Simonelli, L.; Ament, L. J. P.; Forte, F.; Moretti Sala, M.; Minola, M.; Huotari, S.; van den Brink, J.; Ghiringhelli, G.; Brookes, N. B.; Braicovich, L.

2012-06-01

We assess the capabilities of magnetic resonant inelastic x-ray scattering (RIXS) at the O K edge in undoped cuprates by taking La2CuO4 as a benchmark case, based on a series of RIXS measurements that we present here. By combining the experimental results with basic theory we point out the fingerprints of bimagnon excitation in the O K edge RIXS spectra. These are a dominant peak around 450 meV, the almost complete absence of dispersion both with π and σ polarization, and the almost constant intensity vs the transferred momentum with σ polarization. This behavior is quite different from Cu L3 edge RIXS giving a strongly dispersing bimagnon tending to zero at the center of the Brillouin zone. This is clearly shown by RIXS measurements at the Cu L3 edge that we present. The Cu L3 bimagnon spectra and those at the Cu K edge—both from the literature and from our data—however, have the same shape. These similarities and differences are understood in terms of different sampling of the bimagnon continuum. This panorama points out the unique possibilities offered by O K RIXS in the study of magnetic excitations in cuprates near the center of the BZ.

Borosilicate glass structure: An investigation of high resolution B K-edge XANES

NASA Astrophysics Data System (ADS)

Dong, S.; Henderson, G. S.; Galoisy, L.; Calas, G.

2009-05-01

The Alkali-borosilicate glasses in the systems Na2O-B2O3-SiO2 and K2O- B2O3-SiO2 have been prepared by melting/quenching in air and studied using synchrotron radiation B K-edge XANES to estimate the evolution of boron coordination as a function of composition. The ratio of alkali/B2O3 (R) and SiO2/B2O3 (K) in the glasses are respectively between 0.5 to 2.0 and 0.5 to 7.0. The edge features of trigonal B ([3]B) and tetrahedral B ([4]B) in B K-edge XANES spectra have been interpreted carefully from B standards such as (B2O3 and BPO4), as well as, a wide range of borate minerals. We find that the proportion of tetrahedral B in glass is increasing as a function of both R and K, similar to previous studies. Contributions of the [3]B and [4]B features to the B K-edge XANES is complex with 6-7 individual transitions contributing to the overall spectral envelope. Many of these transitions are common to both B coordination states making extraction of quantitative [4]B numbers difficult. However, we can calculate the proportion of tetrahedral B accurately by appropriate curve- fitting.

Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang; Cui, Shengsheng; Sun, Zijun

Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onsetmore » potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.« less

Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

USGS Publications Warehouse

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

1993-01-01

EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, ?? (goethite), ?? (akaganeite), and ?? (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface (3.28 ??0.01 A ??) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces (3.25 ?? 0.02 A ??). Mono-dentate arsenate linkages (3.60 ?? 0.03 A ??) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ?? 0.01 A ??. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As Fe ratio is increased. Coherent crystallite size is probably no more than 10 A?? in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As Fe) indicates ferrihydrite units consisting mainly

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.

Geometry of sorbed arsenate on ferrihydrite and crystalline FeOOH: Re-evaluation of EXAFS results and topological factors in predicting sorbate geometry, and evidence for monodentate complexes

USGS Publications Warehouse

Waychunas , Glenn A.; Davis, James A.; Fuller, Christopher C.

1995-01-01

Manceau's (1995) reinterpretation of some of our EXAFS results (Waychunas et al., 1993) has been analyzed using both old and newly collected data in an attempt to clarify the nature of proposed monodentate and edge-sharing bidentate arsenate complexes on the ferrihydrite surface. It is shown that EXAFS analysis utilizing data with sufficient k-range does indicate the presence of relatively short AsFe bonds, suggestive of an edge-sharing complex as indicated by Manceau (1995). However, a variety of data analysis factors and crystal chemical considerations create doubt in this assignment. Most significantly, X-ray scattering data collected on a sample of ferrihydrite with a large density of sorbed arsenate, which should show a substantial fraction of the edge-sharing complex, does not show any such correlation within fitting uncertainty. We also suggest that it is unnecessary to invoke the presence of edge-sharing bidentate arsenate to explain the surface growth poisoning of ferrihydrite with increasing sorbed arsenate, as Manceau (1995) claims.Further, we show that a model based on the topology of close packed oxygen ions offers a clear explanation why monodentate arsenate should appear on some surfaces and not on others, and why differing AsFe distances might be observed on a single surface with a single type of complex. This model also explains why bidentate sorbed arsenate can occupy positions with consistent “tilt” angles. Without such consistency, the sorbed arsenate would be highly positionally disordered, and difficult to detect accurately via EXAFS methods.

Time-Resolved K-shell Photoabsorption Edge Measurement in a Strongly Coupled Matter Driven by Laser-converted Radiation

NASA Astrophysics Data System (ADS)

Zhao, Yang; Yang, Jia-Min; Zhang, Ji-Yan; Yang, Guo-Hong; Xiong, Gang; Wei, Min-Xi; Song, Tian-Ming; Zhang, Zhi-Yu

2013-06-01

A time-resolved K edge absorption measurement of warm dense KCl was performed on Shenguang II laser facility. The x-ray radiation driven shocks were adopted to take colliding shocks compression. By using Dog bone hohlraum the CH/KCl/CH sample was shielded from the laser hitting point to suppress the M band preheating and enhance the compressibility. Thus, an unexplored and extreme region of the plasma state with the maximum 5 times solid density and temperature lower than 3 eV (with coupling constant Γii around 100) was first obtained. The photoabsorption spectra of chlorine near the K-shell edge have been measured with a crystal spectrometer using a short x-ray backlighter. The K edge red shift up to 11.7 eV and broadening of 15.2 eV were obtained for the maximum compression. The electron temperature, inferred by Fermi-Dirac fit of the measured K-edge broadening, was consistent with the hydrodynamic predictions. The comparison of the K edge shift with a plasma model, in which the ionization effect, continuum lowering and partial degeneracy are considered, shows that more improvements are desired to describe in details the variation of K edge shift. This work might extend future study of WDM in extreme conditions of high compression.

Analysis of the detailed configuration of hydrated lanthanoid(III) ions in aqueous solution and crystalline salts by using K- and L(3)-edge XANES spectroscopy.

PubMed

D'Angelo, Paola; Zitolo, Andrea; Migliorati, Valentina; Persson, Ingmar

2010-01-11

The structural properties of the hydrated lanthanoid(III) ions in aqueous solution and in the isostructural trifluoromethanesulfonate salts have been investigated by a quantitative analysis of the X-ray absorption near-edge structure (XANES) spectra at the K- and L(3)-edges. The XANES analysis has provided a clear description of the variation of lanthanoid(III) hydration properties across the series. It was found that all of the lanthanoid(III) hydration complexes retain a tricapped trigonal prism (TTP) geometry, and along the series two of the capping water molecules become less and less strongly bound, before finally, on average, one of them leaves the hydration cluster. This gives rise to an eight-coordinated distorted bicapped trigonal prism with two different Ln--O capping distances for the smallest lanthanoid(III) ions. This systematic study has shown that for lanthanoid compounds more accurate structural information is obtained from the analysis of the L(3)-edge than from K-edge XANES data. Moreover, whereas the second hydration shells provide a detectable contribution to the L(3)-edge XANES spectra of the lighter lanthanoid ions, the K-edge spectra are insensitive to the more distant coordination spheres.

K-Shell Photoabsorption Edge of Strongly Coupled Matter Driven by Laser-Converted Radiation

NASA Astrophysics Data System (ADS)

Zhao, Yang; Yang, Jiamin; Zhang, Jiyan; Yang, Guohong; Wei, Minxi; Xiong, Gang; Song, Tianming; Zhang, Zhiyu; Bao, Lihua; Deng, Bo; Li, Yukun; He, Xiaoan; Li, Chaoguang; Mei, Yu; Yu, Ruizhen; Jiang, Shaoen; Liu, Shenye; Ding, Yongkun; Zhang, Baohan

2013-10-01

The first observation of the K-shell photoabsorption edge of strongly coupled matter with an ion-ion coupling parameter of about 65 generated by intense x-ray radiation-driven shocks is reported. The soft x-ray radiation generated by laser interaction with a “dog bone” high-Z hohlraum is used to ablate two thick CH layers, which cover a KCl sample, to create symmetrical inward shocks. While the two shocks impact at the central KCl sample, a highly compressed KCl is obtained with a density of 3-5 times solid density and a temperature of about 2-4 eV. The photoabsorption spectra of chlorine near the K-shell edge are measured with a crystal spectrometer using a short x-ray backlighter. The redshift of the K edge up to 11.7 eV and broadening of 15.2 eV are obtained for the maximum compression. A comparison of the measured redshifts and broadenings with dense plasma calculations are made, and it indicates potential improvements in the theoretical description.

Solid energy calibration standards for P K-edge XANES: electronic structure analysis of PPh4Br.

PubMed

Blake, Anastasia V; Wei, Haochuan; Donahue, Courtney M; Lee, Kyounghoon; Keith, Jason M; Daly, Scott R

2018-03-01

P K-edge X-ray absorption near-edge structure (XANES) spectroscopy is a powerful method for analyzing the electronic structure of organic and inorganic phosphorus compounds. Like all XANES experiments, P K-edge XANES requires well defined and readily accessible calibration standards for energy referencing so that spectra collected at different beamlines or under different conditions can be compared. This is especially true for ligand K-edge X-ray absorption spectroscopy, which has well established energy calibration standards for Cl (Cs 2 CuCl 4 ) and S (Na 2 S 2 O 3 ·5H 2 O), but not neighboring P. This paper presents a review of common P K-edge XANES energy calibration standards and analysis of PPh 4 Br as a potential alternative. The P K-edge XANES region of commercially available PPh 4 Br revealed a single, highly resolved pre-edge feature with a maximum at 2146.96 eV. PPh 4 Br also showed no evidence of photodecomposition when repeatedly scanned over the course of several days. In contrast, we found that PPh 3 rapidly decomposes under identical conditions. Density functional theory calculations performed on PPh 3 and PPh 4 + revealed large differences in the molecular orbital energies that were ascribed to differences in the phosphorus oxidation state (III versus V) and molecular charge (neutral versus +1). Time-dependent density functional theory calculations corroborated the experimental data and allowed the spectral features to be assigned. The first pre-edge feature in the P K-edge XANES spectrum of PPh 4 Br was assigned to P 1s → P-C π* transitions, whereas those at higher energy were P 1s → P-C σ*. Overall, the analysis suggests that PPh 4 Br is an excellent alternative to other solid energy calibration standards commonly used in P K-edge XANES experiments.

Oxidant K edge x-ray emission spectroscopy of UF 4 and UO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tobin, J. G.; Yu, S. -W.; Qiao, R.

The K-Edge (1s) x-ray emission spectroscopy of uranium tetrafluoride and uranium dioxide were compared to each other and to the results of a pair of earlier cluster calculations. Here, using a very simplified approach, it is possible to qualitatively reconstruct the main features of the x-ray emission spectra from the cluster calculation state energies and 2p percentages.

Oxidant K edge x-ray emission spectroscopy of UF 4 and UO 2

DOE PAGES

Tobin, J. G.; Yu, S. -W.; Qiao, R.; ...

2018-01-31

The K-Edge (1s) x-ray emission spectroscopy of uranium tetrafluoride and uranium dioxide were compared to each other and to the results of a pair of earlier cluster calculations. Here, using a very simplified approach, it is possible to qualitatively reconstruct the main features of the x-ray emission spectra from the cluster calculation state energies and 2p percentages.

Long- and Short-Range Structure of Ferrimagnetic Iron-Chromium Maghemites.

PubMed

García-Guaderrama, Marco; Montero-Cabrera, María E; Morán, Emilio; Alario-Franco, Miguel A; Fuentes-Cobas, Luis E; Macías-Ríos, Edgar; Esparza-Ponce, Hilda E; Fuentes-Montero, María E

2015-12-07

Maghemite-like materials containing Fe(3+) and Cr(3+) in comparable amounts have been prepared by solution-combustion synthesis. The conditions of synthesis and the magnetic properties are described. These materials are ferrimagnetic and are much more stable than pure iron maghemite since their maghemite-hematite transformation takes place at about ∼ 700 °C instead of ∼ 300 °C, as usually reported. These materials were studied by synchrotron radiation X-ray diffraction (XRD) and by X-ray absorption fine structure (XAFS) of the K-absorption edge of two elements. High-resolution XRD patterns were processed by means of the Rietveld method. Thus, maghemites were studied by XAFS in both Fe and Cr K-edges to clarify the short-range structure of the investigated systems. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure transitions were performed. The extended X-ray absorption fine structure (EXAFS) spectra were fitted considering the facts that the central atom of Fe is able to occupy octahedral and tetrahedral sites, each with a weight adjustment, while Cr occupies only octahedral sites. Interatomic distances were determined for x = 1, by fitting simultaneously both Fe and Cr K-edges average EXAFS spectra. The results showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO3).

EXAFS studies on the reaction of gold (III) chloride complex ions with sodium hydroxide and glucose.

PubMed

Pacławski, K; Zajac, D A; Borowiec, M; Kapusta, Cz; Fitzner, K

2010-11-11

EXAFS and QEXAFS experiments were carried out at Hasylab laboratory in DESY center (X1 beamline, Hamburg, Germany) to monitor the course of the hydrolysis reactions of [AuCl(4)](-) complex ions as well as their reduction using glucose. As a result, changes in the spectra of [AuCl(4)](-) ions and disappearance of absorption Au-L(3) edge were registered. From the results of the experiments we have carried out, the changes in bond lengths between Au(3+) central ion and Cl(-) ligands as well as the reduction of Au(3+) to metallic form (colloidal gold was formed in the system) are evident. Good quality spectra obtained before and after the reactions gave a chance to determine the bond length characteristic of Au-Cl, Au-OH and Au-Au pairs. Additionally, the obtained results were compared with the simulated spectra of different gold (III) complex ions, possibly present in the solution. Finally, the mechanism of these reactions was suggested. Unfortunately, it was not possible to detect the changes in the structure of gold (III) complex ions within the time of reaction, because of too high rates of both processes (hydrolysis and reduction) as compared with the detection time.

X-ray absorption near-edge spectroscopy in bioinorganic chemistry: Application to M–O2 systems

PubMed Central

Sarangi, Ritimukta

2012-01-01

Metal K-edge X-ray absorption spectroscopy (XAS) has been extensively applied to bioinorganic chemistry to obtain geometric structure information on metalloprotein and biomimetic model complex active sites by analyzing the higher energy extended X-ray absorption fine structure (EXAFS) region of the spectrum. In recent years, focus has been on developing methodologies to interpret the lower energy K-pre-edge and rising-edge regions (XANES) and using it for electronic structure determination in complex bioinorganic systems. In this review, the evolution and progress of 3d-transition metal K-pre-edge and rising-edge methodology development is presented with particular focus on applications to bioinorganic systems. Applications to biomimetic transition metal–O2 intermediates (M = Fe, Co, Ni and Cu) are reviewed, which demonstrate the power of the method as an electronic structure determination technique and its impact in understanding the role of supporting ligands in tuning the electronic configuration of transition metal–O2 systems. PMID:23525635

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Tetrahedrally Coordinated Fe3+ in Silicate Glasses: A Mossbauer, Iron K-edge XANES and Raman Spectroscopies Study

NASA Astrophysics Data System (ADS)

Cochain, B.; Neuville, D. R.; McCammon, C.; Henderson, G. S.; de Ligny, D.; Pinet, O.; Richet, P.

2009-05-01

In natural or industrial glasses, iron is the most abundant transition metal. A good knowledge of its redox equilibrium is important to better understand the chemical and structural evolution of magmas (crystallization, viscosity), and also to optimize vitrification processes and properties of iron-bearing glasses. To study the role of iron in silicate glasses and melts, we have used in a consistent manner the Mössbauer, iron K-edge XANES and Raman spectroscopies to investigate several series of silicate glasses as a function of redox state. The samples were selected to cover a wide composition range and to investigate the interactions of iron with two network forming cations, namely, Al3+ and B3+. The glasses investigated were synthesized at high temperature under various conditions of oxygen fugacity to achieve different redox ratios for each composition. Therefore, the iron redox state was varied from the most oxidized to the most reduced. Iron redox ratios were first determined by wet chemical analysis and in some cases by room temperature Mossbauer spectroscopy. This experimental method was also used to determine the local structure of iron of some of the investigated glasses. These results where compared to iron K-edge XANES/EXAFS spectroscopy results, which lead to the iron redox state and indicate that Fe2+ is in octahedral coordination whereas Fe3+ is in tetrahedral coordination. In addition, Raman spectroscopy gave us information on the network polymerization of glasses. Clearly changes in Raman spectra are visible with the evolution of iron redox ratio. For a given composition, we observed systematically, in the 800-1200 cm-1 envelope, which is sensitive to the environment of tetrahedrally coordinated cations, the growth of a band with the iron content and the oxidation state of the sample. The peak area of this band, which we attribute to vibrational modes involving tetrahedrally coordinated Fe3+, increases with the oxidation of the sample. This

EXAFS analysis of a human Cu,Zn SOD isoform focused using non-denaturing gel electrophoresis

NASA Astrophysics Data System (ADS)

Chevreux, Sylviane; Solari, Pier Lorenzo; Roudeau, Stéphane; Deves, Guillaume; Alliot, Isabelle; Testemale, Denis; Hazemann, Jean Louis; Ortega, Richard

2009-11-01

Isoelectric point isoforms of a metalloprotein, copper-zinc superoxide dismutase (CuZnSOD), separated on electrophoresis gels were analyzed using X-ray Absorption Spectroscopy. Mutations of this protein are involved in familial cases of amyotrophic lateral sclerosis. The toxicity of mutants could be relied to defects in the metallation state. Our purpose is to establish analytical protocols to study metallation state of protein isoforms such as those from CuZnSOD. We previously highlighted differences in the copper oxidation state between CuZnSOD isoforms using XANES. Here, we present the first results for EXAFS analyses performed at Cu and Zn K-edge on the majoritary expressed isoform of human CuZnSOD separated on electrophoresis gels.

Identification of Uranyl Minerals Using Oxygen K-Edge X Ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.

2016-03-01

Uranium analysis is consistently needed throughout the fuel cycle, from mining to fuel fabrication to environmental monitoring. Although most of the world’s uranium is immobilized as pitchblende or uraninite, there exists a plethora of secondary uranium minerals, nearly all of which contain the uranyl cation. Analysis of uranyl compounds can provide clues as to a sample’s facility of origin and chemical history. X-ray absorption spectroscopy is one technique that could enhance our ability to identify uranium minerals. Although there is limited chemical information to be gained from the uranium X-ray absorption edges, recent studies have successfully used ligand NEXAFS tomore » study the physical chemistry of various uranium compounds. This study extends the use of ligand NEXAFS to analyze a suite of uranium minerals. We find that major classes of uranyl compounds (carbonate, oxyhydroxide, silicate, and phosphate) exhibit characteristic lineshapes in the oxygen K-edge absorption spectra. As a result, this work establishes a library of reference spectra that can be used to classify unknown uranyl minerals.« less

Development of high resolution x-ray spectrometers for the investigation of bioinorganic chemistry in metalloproteins

NASA Astrophysics Data System (ADS)

Drury, Owen Byron

We have built an X-ray spectrometer for synchrotron-based high-resolution soft X-ray spectroscopy. The spectrometer uses four 9-pixel arrays of superconducting tunnel junctions (STJs) as sensors. They infer the energy of an absorbed X-ray from a temporary increase in tunneling current. The STJs are operated in a two-stage adiabatic demagnetization refrigerator (ADR) that uses liquid nitrogen and helium for precooling to 77 K and 4.2 K, and gallium gadolinium garnet and iron ammonium sulfate to attain a base temperature below 0.1 K. The sensors are held at the end of a 40-cm-long cold finger within ˜1 cm of a sample located inside the vacuum chamber of a synchrotron beam line end station. The spectrometer has an energy resolution between 10 eV and 20 eV FWHM below 1 keV, can be operated at rates up to ˜106 counts/s. STJ spectrometers are suited for chemical analysis of dilute samples by fluorescence-detected X-ray absorption spectroscopy (XAS) in cases where conventional germanium detectors do not have enough energy resolution. We have used this STJ spectrometer at the Advanced Light Source synchrotron for spectroscopy on the lower energy X-ray absorption edges of the elements Mo, S, Fe and N. These elements play an important role in biological nitrogen fixation at the metalloprotein nitrogenase, and we have examined if STJ spectrometers can be used to provide new insights into some of the open questions regarding the reaction mechanism of this protein. We have taken X-ray absorption near-edge spectra (XANES) and extended fine structure spectra (EXAFS) of an Fe 6N(CO)15-compound containing a single N atom inside a cluster of six Fe atoms, as postulated to exist inside the Fe-S cluster of the FeMo-cofactor (FeMo-co) in nitrogenase. The STJ detector has enabled the first-ever extended range EXAFS scans on nitrogen through the oxygen K-edge, enabling a comparison with N EXAFS on FeMo-co. We have taken iron L23-edge spectra of the Fe-S cluster in FeMo-co, which can be

Application of x-ray absorption fine structure (XAFS) to local-order analysis in Fe-Cr maghemite-like materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montero-Cabrera, M. E., E-mail: elena.montero@cimav.edu.mx; Fuentes-Cobas, L. E.; Macías-Ríos, E.

2015-07-23

The maghemite-like oxide system γ-Fe{sub 2-x}Cr{sub x}O{sub 3} (x=0.75, 1 and 1.25) was studied by X-ray absorption fine structure (XAFS) and by synchrotron radiation X-ray diffraction (XRD). Measurements were performed at the Stanford Synchrotron Radiation Lightsource at room temperature, at beamlines 2-1, 2-3 and 4-3. High-resolution XRD patterns were processed by means of the Rietveld method. In cases of atoms being neighbors in the Periodic Table, the order/disorder degree of the considered solutions is indiscernible by “normal” (absence of “anomalous scattering”) diffraction experiments. Thus, maghemite-like materials were investigated by XAFS in both Fe and Cr K-edges to clarify, via short-rangemore » structure characterization, the local ordering of the investigated system. Athena and Artemis graphic user interfaces for IFEFFIT and FEFF8.4 codes were employed for XAFS spectra interpretation. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure (XANES) transitions were performed. By analysis of the Cr K-edge XANES, it has been confirmed that Cr is located in an octahedral environment. Fitting of the extended X-ray absorption fine structure (EXAFS) spectra was performed under the consideration that the central atom of Fe is allowed to occupy octa- and tetrahedral positions, while Cr occupies only octahedral ones. Coordination number of neighboring atoms, interatomic distances and their quadratic deviation average were determined for x=1, by fitting simultaneously the EXAFS spectra of both Fe and Cr K-edges. The results of fitting the experimental spectra with theoretical standards showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO{sub 3})« less

Photoionization of the Fe lons: Structure of the K-Edge

NASA Technical Reports Server (NTRS)

Palmeri, P.; Mendoza, C.; Kallman, T.; Bautista, M.; White, Nicholas E. (Technical Monitor)

2002-01-01

X-ray absorption and emission features arising from the inner-shell transitions in iron are of practical importance in astrophysics due to the Fe cosmic abundance and to the absence of traits from other elements in the nearby spectrum. As a result, the strengths and energies of such features can constrain the ionization stage, elemental abundance, and column density of the gas in the vicinity of the exotic cosmic objects, e.g. active galactic nuclei (AGN) and galactic black hole candidates. Although the observational technology in X-ray astronomy is still evolving and currently lacks high spectroscopic resolution, the astrophysical models have been based on atomic calculations that predict a sudden and high step-like increase of the cross section at the K-shell threshold (see for instance. New Breit-Pauli R-matrix calculations of the photoionization cross section of the ground states of Fe XVII in the region near the K threshold are presented. They strongly support the view that the previously assumed sharp edge behaviour is not correct. The latter has been caused by the neglect of spectator Auger channels in the decay of the resonances converging to the K threshold. These decay channels include the dominant KLL channels and give rise to constant widths (independent of n). As a consequence, these series display damped Lorentzian components that rapidly blend to impose continuity at threshold, thus reformatting the previously held picture of the edge. Apparent broadened iron edges detected in the spectra of AGN and galactic black hole candidates seem to indicate that these quantum effects may be at least partially responsible for the observed broadening.

Bayes-Turchin analysis of x-ray absorption data above the Fe L{sub 2,3}-edges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rossner, H. H.; Schmitz, D.; Imperia, P.

2006-10-01

Extended x-ray absorption fine structure (EXAFS) data and magnetic EXAFS (MEXAFS) data were measured at two temperatures (180 and 296 K) in the energy region of the overlapping L-edges of bcc Fe grown on a V(110) crystal surface. In combination with a Bayes-Turchin data analysis procedure these measurements enable the exploration of local crystallographic and magnetic structures. The analysis determined the atomic-like background together with the EXAFS parameters which consisted of ten shell radii, the Debye-Waller parameters, separated into structural and vibrational components, and the third cumulant of the first scattering path. The vibrational components for 97 different scattering pathsmore » were determined by a two parameter force-field model using a priori values adjusted to Born-von Karman parameters of inelastic neutron scattering data. The investigations of the system Fe/V(110) demonstrate that the simultaneous fitting of atomic background parameters and EXAFS parameters can be performed reliably. Using the L{sub 2}- and L{sub 3}-components extracted from the EXAFS analysis and the rigid-band model, the MEXAFS oscillations can only be described when the sign of the exchange energy is changed compared to the predictions of the Hedin Lundquist exchange and correlation functional.« less

Coupling CP-MD simulations and X-ray absorption spectroscopy: exploring the structure of oxaliplatin in aqueous solution.

PubMed

Beret, Elizabeth C; Provost, Karine; Müller, Diane; Marcos, Enrique Sánchez

2009-09-10

A combined experimental-theoretical approach applying X-ray absorption spectroscopy and ab initio molecular dynamics (CP-MD) simulations is used to get insight into the structural determination of oxaliplatin, a third-generation anticancer drug of the cisplatin family, in aqueous solution. Experimental Pt L(III)-edge EXAFS and XANES spectra of oxaliplatin in water are compared with theoretical XAS spectra. The latter are obtained as statistically averaged spectra computed for a set of selected snapshots extracted from the MD trajectory of ethyldiamineoxalatoplatinum(II) (EDO-Pt) in liquid water. This compound is a simplified structure of oxaliplatin, where the outer part of the cyclohexane ring contained in the cyclohexanediamine ligand of oxaliplatin has been removed. We show that EDO-Pt is an appropriate model to simulate the spectroscopical properties of oxaliplatin given that the cyclohexane ring does not generate particular features in neither the EXAFS nor the XANES spectra. The computation of average EXAFS spectra using structures from the MD simulation in which atoms are selected according to different cutoff radii around the Pt center allows the assignment of spectral features to particular structural motifs, both in k and R-spaces. The outer oxygen atoms of the oxalate ligand (R(Pt-O(II)) = 3.97 +/- 0.03 A) are responsible for a well-defined hump at around 6.5 A(-1) in the k(2)-weighted EXAFS spectrum. The conventional EXAFS analysis data procedure is reexamined by its application to the simulated average EXAFS spectra. The structural parameters resulting from the fit may then be compared with those obtained from the simulation, providing an estimation of the methodological error associated with the global fitting procedure. A thorough discussion on the synergy between the experimental and theoretical XAS approaches is presented, and evidence for the detection of a slight hydration structure around the Pt complex is shown, leading to the suggestion of a

Effect of Fe-substitution on the structure and magnetism of single crystals Mn2-xFexBO4

NASA Astrophysics Data System (ADS)

Platunov, M. S.; Kazak, N. V.; Knyazev, Yu. V.; Bezmaternykh, L. N.; Moshkina, E. M.; Trigub, A. L.; Veligzhanin, A. A.; Zubavichus, Y. V.; Solovyov, L. A.; Velikanov, D. A.; Ovchinnikov, S. G.

2017-10-01

Single crystalline Mn2-xFexBO4 with x = 0.3, 0.5, 0.7 grown by the flux method have been studied by means of X-ray diffraction and X-ray absorption spectroscopy at both Mn and Fe K edges. The compounds were found to crystallize in an orthorhombic warwickite structure (sp. gr. Pnam). The lattice parameters change linearly with x thus obeying the Vegard's law. The Fe3+ substitution for Mn3+ has been deduced from the X-ray absorption near-edge structure (XANES) spectra. Two energy positions of the absorption edges have been observed in Mn K-edge XANES spectra indicating the presence of manganese in two different oxidation states. Extended X-ray absorption fine structure (EXAFS) analysis has shown the reduction of local structural distortions upon Fe substitution. The magnetization data have revealed a spin-glass transition at TSG = 11, 14 and 18 K for x = 0.3, 0.5 and 0.7, respectively.

Complex polarization propagator approach in the restricted open-shell, self-consistent field approximation: the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine.

PubMed

Linares, Mathieu; Stafström, Sven; Rinkevicius, Zilvinas; Ågren, Hans; Norman, Patrick

2011-05-12

A presentation of the complex polarization propagator in the restricted open-shell self-consistent field approximation is given. It rests on a formulation of a resonant-convergent, first-order polarization propagator approach that makes it possible to directly calculate the X-ray absorption cross section at a particular frequency without explicitly addressing the excited states. The quality of the predicted X-ray spectra relates only to the type of density functional applied without any separate treatment of dynamical relaxation effects. The method is applied to the calculation of the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine. Comparison is made between the spectra of the radicals and those of the corresponding cations and anions to assess the effect of the increase of electron charge in the frontier orbital. The method offers the possibility for unique assignment of symmetry-independent atoms. The overall excellent spectral agreement motivates the application of the method as a routine precise tool for analyzing X-ray absorption of large systems of technological interest.

High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory.

PubMed

Lima, Frederico A; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena

2013-12-28

X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core-hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas-Kroll-Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.

An x-ray absorption spectroscopy study of Ni-Mn-Ga shape memory alloys.

PubMed

Sathe, V G; Dubey, Aditi; Banik, Soma; Barman, S R; Olivi, L

2013-01-30

The austenite to martensite phase transition in Ni-Mn-Ga ferromagnetic shape memory alloys was studied by extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectroscopy. The spectra at all the three elements', namely, Mn, Ga and Ni, K-edges in several Ni-Mn-Ga samples (with both Ni and Mn excess) were analyzed at room temperature and low temperatures. The EXAFS analysis suggested a displacement of Mn and Ga atoms in opposite direction with respect to the Ni atoms when the compound transforms from the austenite phase to the martensite phase. The first coordination distances around the Mn and Ga atoms remained undisturbed on transition, while the second and subsequent shells showed dramatic changes indicating the presence of a modulated structure. The Mn rich compounds showed the presence of antisite disorder of Mn and Ga. The XANES results showed remarkable changes in the unoccupied partial density of states corresponding to Mn and Ni, while the electronic structure of Ga remained unperturbed across the martensite transition. The post-edge features in the Mn K-edge XANES spectra changed from a double peak like structure to a flat peak like structure upon phase transition. The study establishes strong correlation between the crystal structure and the unoccupied electronic structure in these shape memory alloys.

A wavelet analysis for the X-ray absorption spectra of molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Penfold, T. J.; Ecole polytechnique Federale de Lausanne, Laboratoire de chimie et biochimie computationnelles, ISIC, FSB-BCH, CH-1015 Lausanne; SwissFEL, Paul Scherrer Inst, CH-5232 Villigen

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 rheniummore » 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.« less

Assignment of polarization-dependent peaks in carbon K-edge spectra from biogenic and geologic aragonite.

PubMed

Zhou, Dong; Metzler, Rebecca A; Tyliszczak, Tolek; Guo, Jinghua; Abrecht, Mike; Coppersmith, Susan N; Gilbert, P U P A

2008-10-16

Many biominerals, including mollusk and echinoderm shells, avian eggshells, modern and fossil bacterial sediments, planktonic coccolithophores, and foraminifera, contain carbonates in the form of biogenic aragonite or calcite. Here we analyze biogenic and geologic aragonite using different kinds of surface- and bulk-sensitive X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge, as well as high-resolution scanning transmission X-ray microscopy (STXM). Besides the well-known main pi* and sigma* carbonate peaks, we observed and fully characterized four minor peaks, at energies between the main pi* and sigma* peaks. As expected, the main peaks are similar in geologic and biogenic aragonite, while the minor peaks differ in relative intensity. In this and previous work, the minor peaks appear to be the ones most affected in biomineralization processes, hence the interest in characterizing them. Peak assignment was achieved by correlation of polarization-dependent behavior of the minor peaks with that of the main pi* and sigma* peaks. The present characterization provides the background for future studies of aragonitic biominerals.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parsons, J.G.; Dokken, K.; Peralta-Videa, J.R.

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

Strong excitonic interactions in the oxygen K-edge of perovskite oxides.

PubMed

Tomita, Kota; Miyata, Tomohiro; Olovsson, Weine; Mizoguchi, Teruyasu

2017-07-01

Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO 3 , SrTiO 3 , and BaTiO 3 , together with reference oxides, MgO, CaO, SrO, BaO, and TiO 2 , were investigated using a first-principles Bethe-Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti-O-Ti bonds. Copyright © 2016 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobs, Gary; Pendyala, Venkat Ramana Rao; Martinelli, Michela

XANES K-edge spectra of potassium promoter in precipitated Fe catalysts were acquired following activation by carburization in CO and as a function of time on-stream during the course of a Fischer–Tropsch synthesis run for a 100Fe:2K catalyst by withdrawing catalysts, sealed in wax product, for analysis. CO-activated and end-of-run spectra of the catalyst were also obtained for a 100Fe:5K catalyst. Peaks representing electronic transitions and multiple scattering were observed and resembled reference spectra for potassium carbonate or potassium formate. The shift in the multiple scattering peak to higher energy was consistent with sintering of potassium promoter during the course ofmore » the reaction test. The catalyst, however, retained its carbidic state, as demonstrated by XANES and EXAFS spectra at the iron K-edge, suggesting that sintering of potassium did not adversely affect the carburization rate, which is important for preventing iron carbides from oxidizing. This method serves as a starting point for developing better understanding of the chemical state and changes in structure occurring with alkali promoter.« less

Resonant inelastic x-ray scattering on iso-C₂H₂Cl₂ around the chlorine K-edge: structural and dynamical aspects.

PubMed

Kawerk, Elie; Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Piancastelli, Maria Novella; Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok; Kavčič, Matjaž; Céolin, Denis; Khoury, Antonio; Simon, Marc

2014-10-14

We report a theoretical and experimental study of the high resolution resonant K(α) X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K(α) emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

On the Structure of the Iron K-Edge

NASA Technical Reports Server (NTRS)

Palmeri, P.; Mendoza, C.; Kallman, T. R.; Bautista, M. A.; White, Nicholas E. (Technical Monitor)

2002-01-01

It is shown that the commonly held view of a sharp Fe K edge must be modified if the decay pathways of the series of resonances converging to the K thresholds are adequately taken into account. These resonances display damped Lorentzian profiles of nearly constant widths that are smeared to impose continuity across the threshold. By modeling the effects of K damping on opacities, it is found that the broadening of the K edge grows with the ionization level of the plasma, and the appearance at high ionization of a localized absorption feature at 7.2 keV is identified as the Kbeta unresolved transition array.

Temperature dependence of Ti 1s near-edge spectra in Ti-based perovskites: theory and experiment

NASA Astrophysics Data System (ADS)

Shirley, Eric; Cockayne, Eric; Ravel, Bruce; Woicik, Joseph

Ti 1s near-edge spectra (around 4970 eV) in SrTiO3 and PbTiO3 reveal electric-dipole and quadrupole transitions to Ti 3d, 4p and mixed 3d-4p states. Crystal field-split pre-edge features attributed to 1s ->3d transitions are small compared to the main edge jump at the onset of the Ti 4s/4p continuum. Pre-edge and subsequent near-edge features are predicted to be weaker than what is observed, unless one accounts for ferroelectric polarization in PbTiO3 and thermal motion in both compounds. Using density-functional theory molecular dynamics simulations at various temperatures (including sampling two phases of PbTiO3), we capture the statistically averaged root-mean-square deviations of Ti4+ ions from the centers of their oxygen cages. By sampling appropriate snapshots of atomic configurations and averaging Ti 1s absorption spectra computed within a Bethe-Salpeter Equation framework, we obtain absorption spectra that agree well with experiment, including details related to ferroelectric polarization, phase transitions, and fluctuations of atomic coordinates.

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

PubMed

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

2013-09-25

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

Sulfur K-edge X-ray absorption spectroscopy and time-dependent density functional theory of arsenic dithiocarbamates.

PubMed

Donahue, Courtney M; Pacheco, Juan S Lezama; Keith, Jason M; Daly, Scott R

2014-06-28

S K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT) calculations were performed on a series of As[S2CNR2]3 complexes, where R2 = Et2, (CH2)5 and Ph2, to determine how dithiocarbamate substituents attached to N affect As[S2CNR2]3 electronic structure. Complimentary [PPh4][S2CNR2] salts were also studied to compare dithiocarbamate bonding in the absence of As. The XAS results indicate that changing the orientation of the alkyl substituents from trans to cis (R2 = Et2vs. (CH2)5) yields subtle variations whereas differences associated with a change from alkyl to aryl are much more pronounced. For example, despite the differences in As 4p mixing, the first features in the S K-edge XAS spectra of [PPh4][S2CNPh2] and As[S2CNPh2]3 were both shifted by 0.3 eV compared to their alkyl-substituted derivatives. DFT calculations revealed that the unique shift observed for [PPh4][S2CNPh2] is due to phenyl-induced splitting of the π* orbitals delocalized over N, C and S. A similar phenomenon accounts for the shift observed for As[S2CNPh2]3, but the presence of two unique S environments (As-S and As···S) prevented reliable analysis of As-S covalency from the XAS data. In the absence of experimental values, DFT calculations revealed a decrease in As-S orbital mixing in As[S2CNPh2]3 that stems from a redistribution of electron density to S atoms participating in weaker As···S interactions. Simulated spectra obtained from TDDFT calculations reproduce the experimental differences in the S K-edge XAS data, which suggests that the theory is accurately modeling the experimental differences in As-S orbital mixing. The results highlight how S K-edge XAS and DFT can be used cooperatively to understand the electronic structure of low symmetry coordination complexes containing S atoms in different chemical environments.

Use of X-ray absorption near edge structure (XANES) to identify physisorption and chemisorption of phosphate onto ferrihydrite-modified diatomite.

PubMed

Xiong, Wenhui; Peng, Jian; Hu, Yongfeng

2012-02-15

This paper presents a novel technique integrating bulk-sensitive and surface-sensitive XANES methods to distinguish between physisorption and chemisorption for phosphate adsorption onto ferrihydrite-modified diatomite (FHMD). XANES P K-edge, L-edge, and Fe M-edge spectra were obtained for reference samples (K(2)HPO(4) and FePO(4)·2H(2)O) and test samples (phosphate adsorbed onto FHMD (FHMD-Ps) and Si-containing ferrihydrite (FHYD-Ps)). A resolvable pre-edge peak in the P K-edge spectra of FHMD-Ps and FHYD-Ps provided direct evidence for the formation of P-O-Fe(III) coordination and the occurrence of chemisorption. The resemblance between the P L-edge spectra of K(2)HPO(4) and FHMD-Ps and the marked difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O indicated the intact existence of the adsorbate and the adsorbent. The similarity between Fe M-edge spectra of FHMD and FHMD-Ps and the difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O confirmed the findings from P L-edge analyses. Therefore, chemisorption and physisorption coexisted during phosphate adsorption onto FHMD. Phosphate chemisorption occurred in the deeper zone of FHMD (from 50 nm to 5 μm); whereas physisorption occurred in the zone of FHMD shallower than 50 nm since the probing depth of XANES P K-edge method is 5 μm and that of P L-edge and Fe M-edge methods is 50 nm. Copyright © 2011 Elsevier Inc. All rights reserved.

Spectral K-edge subtraction imaging

NASA Astrophysics Data System (ADS)

Zhu, Y.; Samadi, N.; Martinson, M.; Bassey, B.; Wei, Z.; Belev, G.; Chapman, D.

2014-05-01

We describe a spectral x-ray transmission method to provide images of independent material components of an object using a synchrotron x-ray source. The imaging system and process is similar to K-edge subtraction (KES) imaging where two imaging energies are prepared above and below the K-absorption edge of a contrast element and a quantifiable image of the contrast element and a water equivalent image are obtained. The spectral method, termed ‘spectral-KES’ employs a continuous spectrum encompassing an absorption edge of an element within the object. The spectrum is prepared by a bent Laue monochromator with good focal and energy dispersive properties. The monochromator focuses the spectral beam at the object location, which then diverges onto an area detector such that one dimension in the detector is an energy axis. A least-squares method is used to interpret the transmitted spectral data with fits to either measured and/or calculated absorption of the contrast and matrix material-water. The spectral-KES system is very simple to implement and is comprised of a bent Laue monochromator, a stage for sample manipulation for projection and computed tomography imaging, and a pixelated area detector. The imaging system and examples of its applications to biological imaging are presented. The system is particularly well suited for a synchrotron bend magnet beamline with white beam access.

Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

PubMed

Schreck, Simon; Wernet, Philippe

2016-09-14

The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

A X-Ray Absorption Study of Transition Metal Oxides

NASA Astrophysics Data System (ADS)

Bunker, Grant Byrd

This work is an experimental and theoretical study of the x-ray absorption near-edge structure of selected 3d transition metal compounds. The goal is to understand the physical mechanisms of XANES, using the competing multiple scattering (MS) and single scattering formalisms of Durham et al, and of Muller and Schaich, respectively. Careful experimental measurements of the K edge absorption of Mn oxides and KMnO(,4) at 300(DEGREES)K, 140(DEGREES)K and 80(DEGREES)K were made. These materials were chosen because they exhibit a variety of structures and oxidation states. Computer simulations of the XANES using the formalisms above were also performed. The experimental results show that atoms beyond the first coordination shell significantly affect the XANES near and above the edge; in particular the temperature dependent XANES and the "white line" in MnO establish this. We conclude that XANES, like EXAFS, is primarily sensitive to geometrical structure, except within about 1 Rydberg of the Fermi level. Two types of MS are distinguished: type 1 (forward scattering) is important in both XANES and EXAFS regions; type 2 (large angle scattering) is important only at and below the edge. MS of the photoelectron among the first shell Oxygen atoms in KMnO(,4) is observed experimentally, and found to become negligible above (DBLTURN) 1 Rydberg past the edge. The sharp features in XANES are primarily due to scattering from distant atoms, rather than localized states, except below the edge. This is supported by the observation that (alpha)-Mn(,2)O(,3) and Mn(,3)O(,4) spectra are nearly identical; their structures are the same, but the average oxidation states are different. We find the bond length strongly affects the edge position and the intensity of the 3d absorption in tetrahedrally coordinated transition metals. Other new results are the first shell EXAFS amplitude in MnO shows an anomalous energy dependence, which apparently cannot be explained by current theory. A new

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.; Eiden, Gregory C.; Pemmaraju, C. D.; Prendergast, David; Duffin, Andrew M.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Chemical analyses of these compounds are important for process and environmental monitoring. X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride, and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. The effect of hydration state on the sample, a potential complication in interpreting oxygen K-edge spectra, is discussed. These compounds have unique spectral signatures that can be used to identify unknown samples.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xin

1996-12-01

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

The protonation states of oxo-bridged Mn(IV) dimers resolved by experimental and computational Mn K pre-edge X-ray absorption spectroscopy.

PubMed

Krewald, Vera; Lassalle-Kaiser, Benedikt; Boron, Thaddeus T; Pollock, Christopher J; Kern, Jan; Beckwith, Martha A; Yachandra, Vittal K; Pecoraro, Vincent L; Yano, Junko; Neese, Frank; DeBeer, Serena

2013-11-18

In nature, the protonation of oxo bridges is a commonly encountered mechanism for fine-tuning chemical properties and reaction pathways. Often, however, the protonation states are difficult to establish experimentally. This is of particular importance in the oxygen evolving complex of photosystem II, where identification of the bridging oxo protonation states is one of the essential requirements toward unraveling the mechanism. In order to establish a combined experimental and theoretical protocol for the determination of protonation states, we have systematically investigated a series of Mn model complexes by Mn K pre-edge X-ray absorption spectroscopy. An ideal test case for selective bis-μ-oxo-bridge protonation in a Mn dimer is represented by the system [Mn(IV)2(salpn)2(μ-OHn)2](n+). Although the three species [Mn(IV)2(salpn)2(μ-O)2], [Mn(IV)2(salpn)2(μ-O)(μ-OH)](+) and [Mn(IV)2(salpn)2(μ-OH)2](2+) differ only in the protonation of the oxo bridges, they exhibit distinct differences in the pre-edge region while maintaining the same edge energy. The experimental spectra are correlated in detail to theoretically calculated spectra. A time-dependent density functional theory approach for calculating the pre-edge spectra of molecules with multiple metal centers is presented, using both high spin (HS) and broken symmetry (BS) electronic structure solutions. The most intense pre-edge transitions correspond to an excitation of the Mn 1s core electrons into the unoccupied orbitals of local e(g) character (d(z)(2) and d(xy) based in the chosen coordinate system). The lowest energy experimental feature is dominated by excitations of 1s-α electrons, and the second observed feature is primarily attributed to 1s-β electron excitations. The observed energetic separation is due to spin polarization effects in spin-unrestricted density functional theory and models final state multiplet effects. The effects of spin polarization on the calculated Mn K pre-edge spectra, in

Ge K-Edge Extended X-Ray Absorption Fine Structure Study of the Local Structure of Amorphous GeTe and the Crystallization

NASA Astrophysics Data System (ADS)

Maeda, Yoshihito; Wakagi, Masatoshi

1991-01-01

The local structure and crystallization of amorphous GeTe (a-GeTe) were examined by means of Ge K-edge EXAFS. In a-GeTe, both Ge-Ge and Ge-Te bonds were observed to exist in nearest neighbors of Ge. The average coordination number around Ge is 3.7, which is close to the tetrahedral structure. A random covalent network (RCN) model seems to be suitable for the local Structure. After a-GeTe crystallizes at 129°C, the Ge-Ge bond disappears and the Ge-Te bond length increases considerably. As temperature rises, in a-GeTe the Debye-Waller factor of the Ge-Te bond increases greatly, while that of the Ge-Ge bond increases only slightly. At the crystallization, it is found that the fluctuation of the Ge-Te bond length plays a major role in the change of the local structure and bonding state around Ge.

Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice

PubMed Central

Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

2013-01-01

The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures. PMID:24253589

Utility of EXAFS in characterization and speciation of mercury-bearing mine wastes

USGS Publications Warehouse

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

1999-01-01

Extensive mining of large mercury deposits located in the California Coast Range has resulted in mercury contamination of both the local environment and water supplies. The solubility, dispersal, and ultimate fate of mercury are all affected by its chemical speciation, which can be most readily determined in a direct fashion using EXAFS spectroscopy. EXAFS spectra of mine wastes collected from several mercury mines in the California Coast Range with mercury concentrations ranging from 230 to 1060 mg/kg (ppm) have been analyzed using a spectral database of mercury minerals and sorbed mercury complexes. While some calcines have been found to consist almost exclusively of mercuric sulfide, HgS, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. This experimental approach can provide a quantitative measurement of the mercury compounds present and may serve as an indicator of the bioavailability and toxicity levels of mercury mine wastes.

MO-FG-CAMPUS-IeP1-01: Alternative K-Edge Filters for Low-Energy Image Acquisition in Contrast Enhanced Spectral Mammography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrestha, S; Vedantham, S; Karellas, A

Purpose: In Contrast Enhanced Spectral Mammography (CESM), Rh filter is often used during low-energy image acquisition. The potential for using Ag, In and Sn filters, which exhibit K-edge closer to, and just below that of Iodine, instead of the Rh filter, was investigated for the low-energy image acquisition. Methods: Analytical computations of the half-value thickness (HVT) and the photon fluence per mAs (photons/mm2/mAs) for 50µm Rh were compared with other potential K-edge filters (Ag, In and Sn), all with K-absorption edge below that of Iodine. Two strategies were investigated: fixed kVp and filter thickness (50µm for all filters) resulting inmore » HVT variation, and fixed kVp and HVT resulting in variation in Ag, In and Sn thickness. Monte Carlo simulations (GEANT4) were conducted to determine if the scatter-to-primary ratio (SPR) and the point spread function of scatter (scatter PSF) differed between Rh and other K-edge filters. Results: Ag, In and Sn filters (50µm thick) increased photon fluence/mAs by 1.3–1.4, 1.8–2, and 1.7–2 at 28-32 kVp compared to 50µm Rh, which could decrease exposure time. Additionally, the fraction of spectra closer to and just below Iodine’s K-edge increased with these filters, which could improve post-subtraction image contrast. For HVT matched to 50µm Rh filtered spectra, the thickness range for Ag, In, and Sn were (41,44)µm, (49,55)µm and (45,53)µm, and increased photon fluence/mAs by 1.5–1.7, 1.6–2, and 1.6–2.2, respectively. Monte Carlo simulations showed that neither the SPR nor the scatter PSF of Ag, In and Sn differed from Rh, indicating no additional detriment due to x-ray scatter. Conclusion: The use of Ag, In and Sn filters for low-energy image acquisition in CESM is potentially feasible and could decrease exposure time and may improve post-subtraction image contrast. Effect of these filters on radiation dose, contrast, noise and associated metrics are being investigated. Funding Support

Extended X-ray Absorption Fine Structure (EXAFS) Analysis of Vitreous Rare Earth Sodium Phosphates

NASA Astrophysics Data System (ADS)

Yoo, Changhyeon; Marasinghe, Kanishka; Segre, Carlo; Shibata, Tomohiro

2015-03-01

The local structure around rare-earth ions (RE3+) in rare-earth ultraphosphate (REUP) glasses has been studied using RE LIII edge (RE = Nd, Er, Dy, and Eu) and K edge (RE = Nd, Pr, Dy, and Eu) extended X-ray absorption fine structure (EXAFS) spectroscopy. (RE2O3)x (Na2O)y(P2O5) 1 - x - y glasses in the compositional range 0 <= x <= 0.14 and x + y = 0.3 and 0.4 were studied. RE-oxygen (RE-O) coordination number decreases from ~ 10 to ~ 7.5 with increasing RE-content for Nd, Pr, Eu, and Dy. For Er, RE-O coordination number increases from ~ 8.7 to ~ 10 with increasing RE-content. For the first oxygen shell, the RE-O distance ranges between 2.41-2.43 Å, 2.44-2.46 Å, 2.24-2.26 Å, 2.28-2.32 Å, and 2.32-2.36 Å for Nd, Pr, Er, Dy, and EU glasses, respectively. Second shell around RE ions consists of phosphorus atoms, with RE-P distance about 3.0-3.5 Å and coordination number ranging from 1 to 3. The third shell primarily contains oxygen and is at a distance about 4.0-4.1 Å from RE ions.

Photon counting x-ray imaging with K-edge filtered x-rays: A simulation study.

PubMed

Atak, Haluk; Shikhaliev, Polad M

2016-03-01

In photon counting (PC) x-ray imaging and computed tomography (CT), the broad x-ray spectrum can be split into two parts using an x-ray filter with appropriate K-edge energy, which can improve material decomposition. Recent experimental study has demonstrated substantial improvement in material decomposition with PC CT when K-edge filtered x-rays were used. The purpose of the current work was to conduct further investigations of the K-edge filtration method using comprehensive simulation studies. The study was performed in the following aspects: (1) optimization of the K-edge filter for a particular imaging configuration, (2) effects of the K-edge filter parameters on material decomposition, (3) trade-off between the energy bin separation, tube load, and beam quality with K-edge filter, (4) image quality of general (unsubtracted) images when a K-edge filter is used to improve dual energy (DE) subtracted images, and (5) improvements with K-edge filtered x-rays when PC detector has limited energy resolution. The PC x-ray images of soft tissue phantoms with 15 and 30 cm thicknesses including iodine, CaCO3, and soft tissue contrast materials, were simulated. The signal to noise ratio (SNR) of the contrast elements was determined in general and material-decomposed images using K-edge filters with different atomic numbers and thicknesses. The effect of the filter atomic number and filter thickness on energy separation factor and SNR was determined. The boundary conditions for the tube load and halfvalue layer were determined when the K-edge filters are used. The material-decomposed images were also simulated using PC detector with limited energy resolution, and improvements with K-edge filtered x-rays were quantified. The K-edge filters with atomic numbers from 56 to 71 and K-edge energies 37.4-63.4 keV, respectively, can be used for tube voltages from 60 to 150 kVp, respectively. For a particular tube voltage of 120 kVp, the Gd and Ho were the optimal filter materials

Fe K-edge XANES of Maya blue pigment

NASA Astrophysics Data System (ADS)

Río, M. Sánchez del; Sodo, A.; Eeckhout, S. G.; Neisius, T.; Martinetto, P.; Dooryhée, E.; Reyes-Valerio, C.

2005-08-01

The utilization of techniques used in Materials Science for the characterization of artefacts of interest for cultural heritage is getting more and more attention nowadays. One of the products of the ancient Maya chemistry is the "Maya blue" pigment, made with natural indigo and palygorskite. This pigment is different from any other pigment used in other parts of the world. It is durable and acid-resistant, and still keeps many secrets to scientists even though it has been studied for more than 50 years. Although the pigment is basically made of palygorskite Si8(Mg2Al2)O20(OH)2(OH2)4.4H2O and an organic colourant (indigo: C16H10N2O2), a number of other compounds have been found in previous studies on archaeological samples, like other clays and minerals, iron nanoparticles, iron oxides, impurities of transition metals (Cr, Mn, Ti, V), etc. We measured at the ESRF ID26 beamline the Fe K-edge XANES spectra of the blue pigment in ancient samples. They are compared to XANES spectra of Maya blue samples synthesized under controlled conditions, and iron oxides usually employed as pigments (hematite and goethite). Our results show that the iron found in ancient Maya blue pigment is related to the Fe exchanged in the palygorskite clay. We did not find iron in metallic form or goethite in archaeological Maya blue.

Magnesium K-Edge NEXAFS Spectroscopy of Chlorophyll a in Solution.

PubMed

Witte, Katharina; Streeck, Cornelia; Mantouvalou, Ioanna; Suchkova, Svetlana A; Lokstein, Heiko; Grötzsch, Daniel; Martyanov, Wjatscheslav; Weser, Jan; Kanngießer, Birgit; Beckhoff, Burkhard; Stiel, Holger

2016-11-17

The interaction of the central magnesium atom of chlorophyll a (Chl a) with the carbon and nitrogen backbone was investigated by magnesium K near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in fluorescence detection mode. A crude extract of Chl a was measured as a 1 × 10 -2 mol/L ethanol solution (which represents an upper limit of concentration without aggregation) and as dried droplets. For the first time, the investigation of Mg bound to Chl a in a liquid environment by means of X-ray absorption spectroscopy is demonstrated. A pre-edge feature in the dissolved as well as in dried Chl a NEXFAS spectra has been identified as a characteristic transition originating from Mg in the Chl a molecule. This result is confirmed by theoretical DFT calculations leading to molecular orbitals (MO) which are mainly situated on the magnesium atom and nitrogen and carbon atoms from the pyrrole rings. The description is the first referring to the MO distribution with respect to the central Mg ion of Chl a and the surrounding atoms. On this basis, new approaches for the investigations of dynamic processes of molecules in solution and structure-function relationships of photosynthetic pigments and pigment-protein complexes in their native environment can be developed.

Structure of short-range-ordered iron(III)-precipitates formed by iron(II) oxidation in water containing phosphate, silicate, and calcium

NASA Astrophysics Data System (ADS)

Voegelin, A.; Frommer, J.; Vantelon, D.; Kaegi, R.; Hug, S. J.

2009-04-01

The oxidation of Fe(II) in water leads to the formation of Fe(III)-precipitates that strongly affect the fate of nutrients and contaminants in natural and engineered systems. Examples include the cycling of As in rice fields irrigated with As-rich groundwater or the treatment of drinking water for As removal. Knowledge of the types of Fe(III)-precipitates forming in such systems is essential for the quantitative modeling of nutrient and contaminant dynamics and for the optimization of water purification techniques on the basis of a mechanistic understanding of the relevant biogeochemical processes. In this study, we investigated the local coordination of Fe, P, and Ca in Fe(III)-precipitates formed by aeration of synthetic Fe(II)-containing groundwater with variable composition (pH 7, 2-30 mg/L Fe(II), 2-20 mg/L phosphate-P, 2-20 mg/L silicate-Si, 8 mM Na-bicarbonate or 2.5 mM Ca-&1.5 mM Mg-bicarbonate). After 4 hours of oxidation, Fe(III)-precipitates were collected on 0.2 µm nylon filters and dried. The precipitates were analyzed by Fe K-edge EXAFS (XAS beamline, ANKA, Germany) and by P and Ca K-edge XANES spectroscopy (LUCIA beamline, SLS, Switzerland). The Fe K-edge EXAFS spectra indicated that local Fe coordination in the precipitates systematically shifted with water composition. As long as water contained P, mainly short-range-ordered Fe(III)-phosphate formed (with molar P/Fe ~0.5). In the absence of P, Fe(III) precipitated as hydrous ferric oxide at high Si/Fe>0.5, as ferrihydrite at intermediate Si/Fe, and mainly as lepidocrocite at Si/Fe<0.2. Analysis of the EXAFS by shell-fitting indicated that Fe(III)-phosphates mainly contained mono- or oligomeric (edge- or corner-sharing) Fe and that the linkage between neighboring Fe(III)-octahedra changed from predominantly edge-sharing in Si-rich hydrous ferric oxide to edge- and corner-sharing in ferrihydrite. Electron microscopic data showed that changes in local precipitate structure were systematically

First-Principles Predictions of Near-Edge X-ray Absorption Fine Structure Spectra of Semiconducting Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Gregory M.; Patel, Shrayesh N.; Pemmaraju, C. D.

The electronic structure and molecular orientation of semiconducting polymers in thin films determine their ability to transport charge. Methods based on near-edge X-ray absorption fine structure (NEXAFS) spectroscopy can be used to probe both the electronic structure and microstructure of semiconducting polymers in both crystalline and amorphous films. However, it can be challenging to interpret NEXAFS spectra on the basis of experimental data alone, and accurate, predictive calculations are needed to complement experiments. Here, we show that first-principles density functional theory (DFT) can be used to model NEXAFS spectra of semiconducting polymers and to identify the nature of transitions inmore » complicated NEXAFS spectra. Core-level X-ray absorption spectra of a set of semiconducting polymers were calculated using the excited electron and core-hole (XCH) approach based on constrained-occupancy DFT. A comparison of calculations on model oligomers and periodic structures with experimental data revealed the requirements for accurate prediction of NEXAFS spectra of both conjugated homopolymers and donor–acceptor polymers. The NEXAFS spectra predicted by the XCH approach were applied to study molecular orientation in donor–acceptor polymers using experimental spectra and revealed the complexity of using carbon edge spectra in systems with large monomeric units. The XCH approach has sufficient accuracy in predicting experimental NEXAFS spectra of polymers that it should be considered for design and analysis of measurements using soft X-ray techniques, such as resonant soft X-ray scattering and scanning transmission X-ray microscopy.« less

Molybdenum L-Edge XAS Spectra of MoFe Nitrogenase

PubMed Central

Bjornsson, Ragnar; Delgado-Jaime, Mario U; Lima, Frederico A; Sippel, Daniel; Schlesier, Julia; Weyhermüller, Thomas; Einsle, Oliver; Neese, Frank; DeBeer, Serena

2015-01-01

A molybdenum L-edge X-ray absorption spectroscopy (XAS) study is presented for native and oxidized MoFe protein of nitrogenase as well as Mo-Fe model compounds. Recently collected data on MoFe protein (in oxidized and reduced forms) is compared to previously published Mo XAS data on the isolated FeMo cofactor in NMF solution and put in context of the recent Mo K-edge XAS study, which showed a MoIII assignment for the molybdenum atom in FeMoco. The L3-edge data are interpreted within a simple ligand-field model, from which a time-dependent density functional theory (TDDFT) approach is proposed as a way to provide further insights into the analysis of the molybdenum L3-edges. The calculated results reproduce well the relative spectral trends that are observed experimentally. Ultimately, these results give further support for the MoIII assignment in protein-bound FeMoco, as well as isolated FeMoco. PMID:26213424

SU-C-207-06: In Vivo Quantification of Gold Nanoparticles Using K-Edge Imaging Via Spectrum Shaping by Gold Filter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, H; Cormack, R; Bhagwat, M

Purpose: Gold nanoparticles (AuNP) are multifunctional platforms ideal for drug delivery, targeted imaging and radiosensitization. We have investigated quantitative imaging of AuNPs using on board imager (OBI) cone beam computed tomography (CBCT). To this end, we also present, for the first time, a novel method for k-edge imaging of AuNP by filter-based spectral shaping. Methods: We used a digital 25 cm diameter water phantom, embedded with 3 cm spheres filled with AuNPs of different concentrations (0 mg/ml – 16 mg/ml). A poly-energetic X-ray spectrum of 140 kVp from a conventional X-ray tube is shaped by balanced K-edge filters to createmore » an excess of photons right above the K-edge of gold at 80.7 keV. The filters consist of gold, tin, copper and aluminum foils. The phantom with appropriately assigned attenuation coefficients is forward projected onto a detector for each energy bin and then integrated. FKD reconstruction is performed on the integrated projections. Scatter, detector efficiency and noise are included. Results: We found that subtracting the results of two filter sets (Filter A:127 µm gold foil with 254 µm tin, 330 µm copper and 1 mm aluminum, and Filter B: 635 µm tin with 264 µm copper and 1 mm aluminum), provides substantial image contrast. The resulting filtered spectra match well below 80.7 keV, while maintaining sufficient X-ray quanta just above that. Voxel intensities of AuNP containing spheres increase linearly with AuNP concentration. K-edge imaging provides 18% more sensitivity than the tin filter alone, and 38% more sensitivity than the gold filter alone. Conclusion: We have shown that it is feasible to quantitatively detect AuNP distributions in a patient-sized phantom using clinical CBCT and K-edge spectral shaping.« less

Local order structure and surface acidity properties of a Nb 2O 5/SiO 2 mixed oxide prepared by the sol-gel processing method

NASA Astrophysics Data System (ADS)

Francisco, Maria Suzana P.; Landers, Richard; Gushikem, Yoshitaka

2004-07-01

The sol-gel processing method was used as an alternative route to obtain Nb 2O 5 phase homogenously dispersed in the SiO 2 matrix, improving the thermal stability of the Brønsted acid sites, Nb-OH and Nb-OH-Si groups. The local niobium structure and the influence of the amount of niobia on the surface of the Nb 2O 5/SiO 2 system were studied by XAS and XPS, respectively. For the samples calcined at 423 and 873 K, the 3 d5/2 BE values are at ca. 208.2 eV, indicating an ionic character for Nb(V) species in the SiO 2 matrix, probably associated to Si-O-Nb linkages. The features of Nb K-edge XANES spectra of samples show the absence of NbO species. The Nb K-edge EXAFS oscillations exhibit a shoulder at ca. 5.6 Å -1, which probably arises from Nb-O-Si. This fact corroborates the EXAFS simulation data of the second coordination shell, whose best fitting is achieved with three distances, two Nb-Nb lengths and one Nb-Si.

Atomic and electronic structure of Pd40Ni40P20 bulk metallic glass from ab initio simulations

NASA Astrophysics Data System (ADS)

Kumar, Vijay; Fujita, T.; Konno, K.; Matsuura, M.; Chen, M. W.; Inoue, A.; Kawazoe, Y.

2011-10-01

The atomic structure of Pd40Ni40P20 bulk metallic glass has been simulated using an ab initio molecular dynamics method with projector-augmented wave pseudopotentials for electron-ion interaction and generalized gradient approximation for exchange-correlation energy. The calculated extended x-ray absorption fine structure (EXAFS) spectra of Pd-K and Ni-K edges, the mass density, and the electronic structure agree remarkably well with the available experimental data and the EXAFS spectra measured at the SPring-8 synchrotron radiation facility. Our results show that the atomic structure can be described in terms of P-centered polyhedra. There are no two P atoms that are nearest neighbors at this composition, and this could be a reason for the observed optimal P concentration of about 20 at.%. The neighboring polyhedra share metal (M) atoms and form a polar covalently bonded random network of P-M-P favoring certain angles. The remaining M atoms act as metallic glue with a tendency of nanoscale clustering of Pd-Pd and Ni-Ni atoms.

Structural evidence for the sorption of Ni(II) atoms on the edges of montmorillonite clay minerals: a polarized X-ray absorption fine structure study

NASA Astrophysics Data System (ADS)

Dähn, Rainer; Scheidegger, André M.; Manceau, Alain; Schlegel, Michel L.; Baeyens, Bart; Bradbury, Michael H.; Chateigner, Daniel

The nature of surface complexes formed on Ni uptake onto montmorillonite (a dioctahedral smectite) has been investigated over an extended time period by polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Self-supporting films of Ni-sorbed montmorillonite were prepared by contacting Ni and montmorillonite at pH 7.2, high ionic strength (0.3 M NaClO 4), and low Ni concentration ([Ni] initial = 19.9 μM) for 14- and 360-d reaction time. The resulting Ni concentration on the clay varied from 4 to 7 μmol/g. Quantitative texture analysis indicates that the montmorillonite particles were well orientated with respect to the plane of the film. The full width at half maximum of the orientation distribution of the c* axes of individual clay platelets about the normal to the film plane was 44.3° (14-d reaction time) and 47.1° (360-d reaction time). These values were used to correct the coordination numbers determined by P-EXAFS for texture effects. Ni K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 10, 35, 55, and 80°. Spectral analysis led to the identification of three nearest cationic subshells containing 2.0 ± 0.5 Al at 3.0 Å and 2.0 ± 0.5 Si at 3.12 Å and 4.0 ± 0.5 Si at 3.26 Å. These distances are characteristic of edge-sharing linkages between Al and Ni octahedra and of corner-sharing linkages between Ni octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Ni-Al and Ni-Si contributions indicates that Ni-Al pairs are oriented parallel to the film plane, whereas Ni-Si pairs are not. The study reveals the formation of Ni inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and thus that heavy metals binding to edge sites is a possible sorption mechanism for dioctahedral smectites. Data analysis further suggests that either the number of neighboring Al atoms slightly increases from 1.6 to 2 or that the structural order

Surface modification study of borate materials from B K-edge X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Kasrai, Masoud; Fleet, Michael E.; Muthupari, Swaminathan; Li, D.; Bancroft, G. M.

The B K-edge X-ray absorption near-edge structure (XANES) spectra of two borates with tetrahedrally-coordinated B [[4]B; natural danburite (CaB2Si2O8) and synthetic boron phosphate (BPO4)] have been recorded in total electron yield (TEY) and fluorescence yield (FY) modes to investigate the surface and bulk structure of these materials. The TEY XANES measurement shows that danburite is susceptible to surface damage involving conversion of [4]B sites to [3]B sites by reaction with moisture and/or mechanical abrasion (grinding, polishing, etc.). The bulk of the mineral is essentially unaffected. Commercial boron phosphate powder exhibits more extensive surface and bulk damage, which increases with air exposure but is recovered on heating at 650°C. In contrast to ELNES, the XANES technique is not affected by beam damage and when collected in the FY mode is capable of yielding meaningful information on the coordination and intermediate-range structure of B in borate and borosilicate materials.

Experimental and theoretical studies of dipole and quadrupole contributions to the vanadium K-edge XANES for VOPO4.2H2O xerogel

NASA Astrophysics Data System (ADS)

Poumellec, B.; Kraizman, V.; Aifa, Y.; Cortès, R.; Novakovich, A.; Vedrinskii, R.

1998-09-01

Angular dependence of the vanadium K-edge x-ray appearance near-edge structure (XANES) for the VOPO4.2H2O xerogel is thoroughly studied both experimentally and theoretically. The main attention is paid to the pre-edge fine structure (PEFS) of the spectra which was shown earlier to be a useful tool for the atomic short order investigations. Good quantitative agreement between theory and experiment obtained for both dipole and quadrupole contributions to the spectra proves validity of the calculation method developed and enables us to ascertain the nature of all the features in the PEFS's. The p-d mixture effect due to distortion of the central coordination octahedron and the quadrupole transitions are proved to be the only mechanisms responsible for the PEFS formation in the case considered. We show that in order to achieve quantitative agreement between experimental and theoretical spectra, it is necessary to include the effect of atomic vibrations, which makes the forbidden transitions to molecular orbitals of the central octahedron (MOCO's) dipole allowed, and to take into account deviation of the crystal layers from the substrate plane, which is not a single crystal but a texture.

Investigating the interstellar dust through the Fe K-edge

NASA Astrophysics Data System (ADS)

Rogantini, D.; Costantini, E.; Zeegers, S. T.; de Vries, C. P.; Bras, W.; de Groot, F.; Mutschke, H.; Waters, L. B. F. M.

2018-01-01

Context. The chemical and physical properties of interstellar dust in the densest regions of the Galaxy are still not well understood. X-rays provide a powerful probe since they can penetrate gas and dust over a wide range of column densities (up to 1024 cm-2). The interaction (scattering and absorption) with the medium imprints spectral signatures that reflect the individual atoms which constitute the gas, molecule, or solid. Aims: In this work we investigate the ability of high resolution X-ray spectroscopy to probe the properties of cosmic grains containing iron. Although iron is heavily depleted into interstellar dust, the nature of the Fe-bearing grains is still largely uncertain. Methods: In our analysis we use iron K-edge synchrotron data of minerals likely present in the ISM dust taken at the European Synchrotron Radiation Facility. We explore the prospects of determining the chemical composition and the size of astrophysical dust in the Galactic centre and in molecular clouds with future X-ray missions. The energy resolution and the effective area of the present X-ray telescopes are not sufficient to detect and study the Fe K-edge, even for bright X-ray sources. Results: From the analysis of the extinction cross sections of our dust models implemented in the spectral fitting program SPEX, the Fe K-edge is promising for investigating both the chemistry and the size distribution of the interstellar dust. We find that the chemical composition regulates the X-ray absorption fine structures in the post edge region, whereas the scattering feature in the pre-edge is sensitive to the mean grain size. Finally, we note that the Fe K-edge is insensitive to other dust properties, such as the porosity and the geometry of the dust. The absorption, scattering, and extinction cross sections of the compounds are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/609/A22

Image reconstruction for x-ray K-edge imaging with a photon counting detector

NASA Astrophysics Data System (ADS)

Meng, Bo; Cong, Wenxiang; Xi, Yan; Wang, Ge

2014-09-01

Contrast agents with high-Z elements have K-absorption edges which significantly change X-ray attenuation coefficients. The K-edge characteristics is different for various kinds of contrast agents, which offers opportunities for material decomposition in biomedical applications. In this paper, we propose a new K-edge imaging method, which not only quantifies a distribution of a contrast agent but also provides an optimized contrast ratio. Our numerical simulation tests demonstrate the feasibility and merits of the proposed methodology.

Tungsten anode spectral model using interpolating cubic splines: unfiltered x-ray spectra from 20 kV to 640 kV.

PubMed

Hernandez, Andrew M; Boone, John M

2014-04-01

Monte Carlo methods were used to generate lightly filtered high resolution x-ray spectra spanning from 20 kV to 640 kV. X-ray spectra were simulated for a conventional tungsten anode. The Monte Carlo N-Particle eXtended radiation transport code (MCNPX 2.6.0) was used to produce 35 spectra over the tube potential range from 20 kV to 640 kV, and cubic spline interpolation procedures were used to create piecewise polynomials characterizing the photon fluence per energy bin as a function of x-ray tube potential. Using these basis spectra and the cubic spline interpolation, 621 spectra were generated at 1 kV intervals from 20 to 640 kV. The tungsten anode spectral model using interpolating cubic splines (TASMICS) produces minimally filtered (0.8 mm Be) x-ray spectra with 1 keV energy resolution. The TASMICS spectra were compared mathematically with other, previously reported spectra. Using pairedt-test analyses, no statistically significant difference (i.e., p > 0.05) was observed between compared spectra over energy bins above 1% of peak bremsstrahlung fluence. For all energy bins, the correlation of determination (R(2)) demonstrated good correlation for all spectral comparisons. The mean overall difference (MOD) and mean absolute difference (MAD) were computed over energy bins (above 1% of peak bremsstrahlung fluence) and over all the kV permutations compared. MOD and MAD comparisons with previously reported spectra were 2.7% and 9.7%, respectively (TASMIP), 0.1% and 12.0%, respectively [R. Birch and M. Marshall, "Computation of bremsstrahlung x-ray spectra and comparison with spectra measured with a Ge(Li) detector," Phys. Med. Biol. 24, 505-517 (1979)], 0.4% and 8.1%, respectively (Poludniowski), and 0.4% and 8.1%, respectively (AAPM TG 195). The effective energy of TASMICS spectra with 2.5 mm of added Al filtration ranged from 17 keV (at 20 kV) to 138 keV (at 640 kV); with 0.2 mm of added Cu filtration the effective energy was 9 keV at 20 kV and 169 keV at 640 k

Tungsten anode spectral model using interpolating cubic splines: Unfiltered x-ray spectra from 20 kV to 640 kV

PubMed Central

Hernandez, Andrew M.; Boone, John M.

2014-01-01

Purpose: Monte Carlo methods were used to generate lightly filtered high resolution x-ray spectra spanning from 20 kV to 640 kV. Methods: X-ray spectra were simulated for a conventional tungsten anode. The Monte Carlo N-Particle eXtended radiation transport code (MCNPX 2.6.0) was used to produce 35 spectra over the tube potential range from 20 kV to 640 kV, and cubic spline interpolation procedures were used to create piecewise polynomials characterizing the photon fluence per energy bin as a function of x-ray tube potential. Using these basis spectra and the cubic spline interpolation, 621 spectra were generated at 1 kV intervals from 20 to 640 kV. The tungsten anode spectral model using interpolating cubic splines (TASMICS) produces minimally filtered (0.8 mm Be) x-ray spectra with 1 keV energy resolution. The TASMICS spectra were compared mathematically with other, previously reported spectra. Results: Using paired t-test analyses, no statistically significant difference (i.e., p > 0.05) was observed between compared spectra over energy bins above 1% of peak bremsstrahlung fluence. For all energy bins, the correlation of determination (R2) demonstrated good correlation for all spectral comparisons. The mean overall difference (MOD) and mean absolute difference (MAD) were computed over energy bins (above 1% of peak bremsstrahlung fluence) and over all the kV permutations compared. MOD and MAD comparisons with previously reported spectra were 2.7% and 9.7%, respectively (TASMIP), 0.1% and 12.0%, respectively [R. Birch and M. Marshall, “Computation of bremsstrahlung x-ray spectra and comparison with spectra measured with a Ge(Li) detector,” Phys. Med. Biol. 24, 505–517 (1979)], 0.4% and 8.1%, respectively (Poludniowski), and 0.4% and 8.1%, respectively (AAPM TG 195). The effective energy of TASMICS spectra with 2.5 mm of added Al filtration ranged from 17 keV (at 20 kV) to 138 keV (at 640 kV); with 0.2 mm of added Cu filtration the effective energy was 9 ke

Tungsten anode spectral model using interpolating cubic splines: Unfiltered x-ray spectra from 20 kV to 640 kV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hernandez, Andrew M.; Boone, John M., E-mail: john.boone@ucdmc.ucdavis.edu

Purpose: Monte Carlo methods were used to generate lightly filtered high resolution x-ray spectra spanning from 20 kV to 640 kV. Methods: X-ray spectra were simulated for a conventional tungsten anode. The Monte Carlo N-Particle eXtended radiation transport code (MCNPX 2.6.0) was used to produce 35 spectra over the tube potential range from 20 kV to 640 kV, and cubic spline interpolation procedures were used to create piecewise polynomials characterizing the photon fluence per energy bin as a function of x-ray tube potential. Using these basis spectra and the cubic spline interpolation, 621 spectra were generated at 1 kV intervalsmore » from 20 to 640 kV. The tungsten anode spectral model using interpolating cubic splines (TASMICS) produces minimally filtered (0.8 mm Be) x-ray spectra with 1 keV energy resolution. The TASMICS spectra were compared mathematically with other, previously reported spectra. Results: Using pairedt-test analyses, no statistically significant difference (i.e., p > 0.05) was observed between compared spectra over energy bins above 1% of peak bremsstrahlung fluence. For all energy bins, the correlation of determination (R{sup 2}) demonstrated good correlation for all spectral comparisons. The mean overall difference (MOD) and mean absolute difference (MAD) were computed over energy bins (above 1% of peak bremsstrahlung fluence) and over all the kV permutations compared. MOD and MAD comparisons with previously reported spectra were 2.7% and 9.7%, respectively (TASMIP), 0.1% and 12.0%, respectively [R. Birch and M. Marshall, “Computation of bremsstrahlung x-ray spectra and comparison with spectra measured with a Ge(Li) detector,” Phys. Med. Biol. 24, 505–517 (1979)], 0.4% and 8.1%, respectively (Poludniowski), and 0.4% and 8.1%, respectively (AAPM TG 195). The effective energy of TASMICS spectra with 2.5 mm of added Al filtration ranged from 17 keV (at 20 kV) to 138 keV (at 640 kV); with 0.2 mm of added Cu filtration the effective

SR high-speed K-edge subtraction angiography in the small animal (abstract)

NASA Astrophysics Data System (ADS)

Takeda, T.; Akisada, M.; Nakajima, T.; Anno, I.; Ueda, K.; Umetani, K.; Yamaguchi, C.

1989-07-01

To assess the ability of the high-speed K-edge energy subtraction system which was made at beamline 8C of Photon Factory, Tsukuba, we performed an animal experiment. Rabbits were used for the intravenous K-edge subtraction angiography. In this paper, the actual images of the artery obtained by this system, are demonstrated. The high-speed K-edge subtraction system consisted of movable silicon (111) monocrystals, II-ITV, and digital memory system. Image processing was performed by 68000-IP computer. The monochromatic x-ray beam size was 50×60 mm. Photon energy above and below iodine K edge was changed within 16 ms and 32 frames of images were obtained sequentially. The rabbits were anaesthetized by phenobarbital and a 5F catheter was inserted into inferior vena cava via the femoral vein. 1.5 ml/kg of contrast material (Conlaxin H) was injected at the rate of 0.5 ml/kg/s. TV images were obtained 3 s after the starting point of injection. By using this system, the clear K-edge subtracted images were obtained sequentially as a conventional DSA system. The quality of the images were better than that obtained by DSA. The dynamical blood flow was analyzed, and the best arterial image could be selected from the sequential images. The structures of aortic arch, common carotid arteries, right subclavian artery, and internal thoracic artery were obtained at the chest. Both common carotid arteries and vertebral arteries were recorded at the neck. The diameter of about 0.3-0.4 mm artery could be clearly revealed. The high-speed K-edge subtraction system demonstrates the very sharp arterial images clearly and dynamically.

Investigation of gamma radiation induced changes in local structure of borosilicate glass by TDPAC and EXAFS

NASA Astrophysics Data System (ADS)

Kumar, Ashwani; Nayak, C.; Rajput, P.; Mishra, R. K.; Bhattacharyya, D.; Kaushik, C. P.; Tomar, B. S.

2016-12-01

Gamma radiation induced changes in local structure around the probe atom (Hafnium) were investigated in sodium barium borosilicate (NBS) glass, used for immobilization of high level liquid waste generated from the reprocessing plant at Trombay, Mumbai. The (NBS) glass was doped with 181Hf as a probe for time differential perturbed angular correlation (TDPAC) spectroscopy studies, while for studies using extended X-ray absorption fine structure (EXAFS) spectroscopy, the same was doped with 0.5 and 2 % (mole %) hafnium oxide. The irradiated as well as un-irradiated glass samples were studied by TDPAC and EXAFS techniques to obtain information about the changes (if any) around the probe atom due to gamma irradiation. TDPAC spectra of unirradiated and irradiated glasses were similar and reminescent of amorphous materials, indicating negligible effect of gamma radiation on the microstructure around Hafnium probe atom, though the quaqdrupole interaction frequency ( ω Q) and asymmetry parameter ( η) did show a marginal decrease in the irradiated glass compared to that in the unirradiated glass. EXAFS measurements showed a slight decrease in the Hf-O bond distance upon gamma irradiation of Hf doped NBS glass indicating densification of the glass matrix, while the cordination number around hafnium remains unchanged.

Resonant inelastic x-ray scattering on iso-C{sub 2}H{sub 2}Cl{sub 2} around the chlorine K-edge: Structural and dynamical aspects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kawerk, Elie, E-mail: eliekawerk@hotmail.com, E-mail: ekawerk@units.it; Sorbonne Universités, UPMC Université Paris 06, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, F-75005 Paris; Laboratoire de Physique Appliquée, Faculté des Sciences II, Université Libanaise, 90656 Jdeidet el Metn, Liban

2014-10-14

We report a theoretical and experimental study of the high resolution resonant K{sub α} X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K{sub α} emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

K-shell photoabsorption edge of strongly coupled aluminum driven by laser-converted radiation

NASA Astrophysics Data System (ADS)

Zhao, Yang; Zhang, Zhiyu; Qing, Bo; Yang, Jiamin; Zhang, Jiyan; Wei, Minxi; Yang, Guohong; Song, Tianming; Xiong, Gang; Lv, Min; Hu, Zhimin; Deng, Bo; Hu, Xin; Zhang, Wenhai; Shang, Wanli; Hou, Lifei; Du, Huabing; Zhan, Xiayu; Yu, Ruizhen

2017-03-01

The first observation of the K-shell photoabsorption edge of strongly coupled aluminum generated by intense x-ray radiation-driven shocks is reported. By using a “dog bone” gold hohlraum as an x-ray converter, colliding shocks compression and preheating shielding are achieved to generate an unexplored state with a density of 5.5 g/cm3 and temperature of 0.43 eV (the ion-ion coupling parameter Γii is around 240). The time-resolved K-shell photoabsorption edges are measured with a crystal spectrometer using a short x-ray backlighter. The broadenings and redshifts of the edges are studied by using the slope fitting of the edge and quantum molecular dynamics calculations. This work shows that the K-edge of aluminum driven by laser-converted radiation provides a novel capability to probe WDM at extended conditions.

X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andrews, J.C.

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 IImore » 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.« less

Study of distorted octahedral structure in 3d transition metal complexes using XAFS

NASA Astrophysics Data System (ADS)

Gaur, A.; Nitin Nair, N.; Shrivastava, B. D.; Das, B. K.; Chakrabortty, Monideepa; Jha, S. N.; Bhattacharyya, D.

2018-01-01

Distortion in octahedral structure of 3d transition metal complexes (Mn, Fe, Co, Ni, Cu, Zn) has been studied using XAFS showing divergent nature of Cu complex. EXAFS analysis showed elongated metal-oxygen bonds for Cu complex leading to more distorted structure. Derivative XANES spectrum at Cu K-edge exhibits splitting of main edge which is correlated to elongated Cu-O bond length. Using these coordination geometry around metal centers, theoretical XANES spectra have been generated and features observed have been correlated to the corresponding metals p-DOS. It has been shown that distorted octahedral field in Cu complex is responsible for splitting of p-DOS.

Resonant inelastic x-ray scattering on iso-C2H2Cl2 around the chlorine K-edge: Structural and dynamical aspects

NASA Astrophysics Data System (ADS)

Kawerk, Elie; Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Piancastelli, Maria Novella; Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok; Kavčič, Matjaž; Céolin, Denis; Khoury, Antonio; Simon, Marc

2014-10-01

We report a theoretical and experimental study of the high resolution resonant Kα X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the Kα emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

Hydrogen bonding interaction of small acetaldehyde clusters studied with core-electron excitation spectroscopy in the oxygen K-edge region

NASA Astrophysics Data System (ADS)

Tabayashi, K.; Chohda, M.; Yamanaka, T.; Tsutsumi, Y.; Takahashi, O.; Yoshida, H.; Taniguchi, M.

2010-06-01

In order to examine inner-shell electron excitation spectra of molecular clusters with strong multipole interactions, excitation spectra and time-of-flight (TOF) fragment-mass spectra of small acetaldehyde (AA) clusters have been studied under the beam conditions. The TOF spectra at the oxygen K-edge region showed an intense growth of the protonated clusters, MnH+ (M=CH3CHO) in the cluster beams. "cluster-specific" excitation spectra could be generated by monitoring partial-ion-yields of the protonated clusters. The most intense band of O1s→π*CO was found to shift to a higher energy by 0.15 eV relative to the monomer band upon clusterization. X-ray absorption spectra (XAS) were also calculated for the representative dimer configurations using a computer modelling program based on the density functional theory. The XAS prediction for the most stable (non-planar) configuration was found to give a close comparison with the cluster-band shift observed. The band shift was interpreted as being due to the HOMO-LUMO interaction within the complex where a contribution of vibrationally blue-shifting hydrogen bonding could be identified.

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides: I. Effects of pH

USGS Publications Warehouse

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

2004-01-01

The study of mercury sorption products in model systems using appropriate in situ molecular-scale probes can provide detailed information on the modes of sorption at mineral/water interfaces. Such studies are essential for assessing the influence of sorption processes on the transport of Hg in contaminated natural systems. Macroscopic uptake of Hg(II) on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) as a function of pH has been combined with Hg L III-edge EXAFS spectroscopy, FTIR spectroscopy, and bond valence analysis of possible sorption products to provide this type of information. Macroscopic uptake measurements show that Hg(II) sorbs strongly to fine-grained powders of synthetic goethite (Hg sorption density ??=0.39-0.42 ??mol/m2) and bayerite (??=0.39-0.44 ??mol/m2), while sorbing more weakly to ??-alumina (??=0.04-0.13 ??mol/m 2). EXAFS spectroscopy on the sorption samples shows that the dominant mode of Hg sorption on these phases is as monodentate and bidentate inner-sphere complexes. The mode of Hg(II) sorption to goethite was similar over the pH range 4.3-7.4, as were those of Hg(II) sorption to bayerite over the pH range 5.1-7.9. Conversion of the ??-Al2O3 sorbent to a bayerite-like phase in addition to the apparent reduction of Hg(II) to Hg(I), possibly by photoreduction during EXAFS data collection, resulted in enhanced Hg uptake from pH 5.2-7.8 and changes in the modes of sorption that correlate with the formation of the bayerite-like phase. Bond valence calculations are consistent with the sorption modes proposed from EXAFS analysis. EXAFS analysis of Hg(II) sorption products on a natural Fe oxyhydroxide precipitate and Al/Si-bearing flocculent material showed sorption products and modes of surface attachment similar to those for the model substrates, indicating that the model substrates are useful surrogates for the natural sediments. ?? 2003 Elsevier Inc. All rights reserved.

Effect of humic acid on nickel(II) sorption to Ca-montmorillonite by batch and EXAFS techniques study.

PubMed

Hu, Jun; Tan, Xiaoli; Ren, Xuemei; Wang, Xiangke

2012-09-21

The influence of humic acid (HA) on Ni(II) sorption to Ca-montmorillonite was examined by using a combination of batch sorption experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy technique. The sorption of Ni(II) on HA-montmorillonite hybrids is strongly dependent on pH and temperature. At low pH, the sorption of Ni(II) is mainly dominated by Ni-HA-montmorillonite and outer-sphere surface complexation. The EXAFS results indicate that the first coordination shell of Ni(II) consists of ∼6 O atoms at the interatomic distances of ∼2.04 Å in an octahedral structure. At high pH, binary Ni-montmorillonite surface complexation is the dominant sorption mechanism. EXAFS analysis indicates the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5, while a Ni-Al layered double hydroxide (LDH) phase at the Ca-montmorillonite surface formed with pH 8.5. At pH 10.0, the dissolved HA-Ni(II) complexation inhibits the precipitation of Ni hydroxide, and Ni-Al LDH phase forms. The rise of temperature increases the sorption capacity of Ni(II), and promotes Ni-Al LDH phase formation and the growth of crystallites. The results are important to evaluate the physicochemical behavior of Ni(II) in the natural environment.

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

NASA Astrophysics Data System (ADS)

Ching, Wai-Yim; Rulis, Paul

2009-03-01

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

Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alperovich, Igor; Smolentsev, Grigory; Moonshiram, Dooshaye

2015-09-17

L{sub 2,3}-edge X-ray absorption spectroscopy (XAS) has demonstrated unique capabilities for the analysis of the electronic structure of di-Ru complexes such as the blue dimer cis,cis-[Ru{sub 2}{sup III}O(H{sub 2}O){sub 2}(bpy){sub 4}]{sup 4+} water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex show considerably different splitting of the Ru L{sub 2,3} absorption edge, which reflects changes in the relative energies of the Ru 4d orbitals caused by hybridization with a bridging ligand and spin-orbit coupling effects. To aid the interpretation of spectroscopic data, we developed a new approach, which computes L{sub 2,3}-edges XASmore » spectra as dipole transitions between molecular spinors of 4d transition metal complexes. This allows for careful inclusion of the spin-orbit coupling effects and the hybridization of the Ru 4d and ligand orbitals. The obtained theoretical Ru L{sub 2,3}-edge spectra are in close agreement with experiment. Critically, existing single-electron methods (FEFF, FDMNES) broadly used to simulate XAS could not reproduce the experimental Ru L-edge spectra for the [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex nor for the blue dimer, while charge transfer multiplet (CTM) calculations were not applicable due to the complexity and low symmetry of the blue dimer water oxidation catalyst. We demonstrated that L-edge spectroscopy is informative for analysis of bridging metal complexes. The developed computational approach enhances L-edge spectroscopy as a tool for analysis of the electronic structures of complexes, materials, catalysts, and reactive intermediates with 4d transition metals.« less

A quantum perturbative pair distribution for determining interatomic potentials from extended x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Piazza, F.

2002-11-01

In this paper we develop a technique for determining interatomic potentials in materials in the quantum regime from single-shell extended x-ray absorption spectroscopy (EXAFS) spectra. We introduce a pair distribution function, based on ordinary quantum time-independent perturbation theory. In the proposed scheme, the model potential parameters enter the distribution through a fourth-order Taylor expansion of the potential, and are directly refined in the fit of the model signal to the experimental spectrum. We discuss in general the validity of our theoretical framework, namely the quantum regime and perturbative treatment, and work out a simple tool for monitoring the sensitivity of our theory in determining lattice anharmonicities based on the statistical F-test. As an example, we apply our formalism to an EXAFS spectrum at the Ag K edge of AgI at T = 77 K. We determine the Ag-I potential parameters and find good agreement with previous studies.

K-edge subtraction synchrotron X-ray imaging in bio-medical research.

PubMed

Thomlinson, W; Elleaume, H; Porra, L; Suortti, P

2018-05-01

High contrast in X-ray medical imaging, while maintaining acceptable radiation dose levels to the patient, has long been a goal. One of the most promising methods is that of K-edge subtraction imaging. This technique, first advanced as long ago as 1953 by B. Jacobson, uses the large difference in the absorption coefficient of elements at energies above and below the K-edge. Two images, one taken above the edge and one below the edge, are subtracted leaving, ideally, only the image of the distribution of the target element. This paper reviews the development of the KES techniques and technology as applied to bio-medical imaging from the early low-power tube sources of X-rays to the latest high-power synchrotron sources. Applications to coronary angiography, functional lung imaging and bone growth are highlighted. A vision of possible imaging with new compact sources is presented. Copyright © 2018 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

Measurement of K Shell Photoelectric Cross Sections at a K Edge--A Laboratory Experiment

ERIC Educational Resources Information Center

Nayak, S. V.; Badiger, N. M.

2007-01-01

We describe in this paper a new method for measuring the K shell photoelectric cross sections of high-Z elemental targets at a K absorption edge. In this method the external bremsstrahlung (EB) photons produced in the Ni target foil by beta particles from a weak[superscript 90]Sr-[superscript 90]Y beta source are passed through an elemental target…

Asymptotically-Equal-To 10 eV ionization shift in Ir K{alpha}{sub 2} from a near-coincident Lu K-edge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pereira, N. R.; Weber, B. V.; Phipps, D.

Close to an x-ray filter's K-edge the transmission depends strongly on the photon energy. For a few atom pairs, the K-edge of one is only a few tens of eV higher than a K-line energy of another, so that a small change in the line's energy becomes a measurable change in intensity behind such a matching filter. Lutetium's K-edge is Asymptotically-Equal-To 27 eV above iridium's K{alpha}{sub 2} line, Asymptotically-Equal-To 63.287 keV for cold Ir. A Lu filter reduces this line's intensity by Asymptotically-Equal-To 10 % when it is emitted by a plasma, indicating an ionization shift {Delta}E Asymptotically-Equal-To 10{+-}1 eV.

XANES evidence for sulphur speciation in Mn-, Ni- and W-bearing silicate melts

NASA Astrophysics Data System (ADS)

Evans, K. A.; O'Neill, H. St. C.; Mavrogenes, J. A.; Keller, N. S.; Jang, L.-Y.; Lee, J.-F.

2009-11-01

S K-edge XANES and Mn-, W- and Ni-XANES and EXAFS spectra of silicate glasses synthesised at 1400 °C and 1 bar with compositions in the CaO-MgO-Al 2O 3-SiO 2-S plus MnO, NiO, or WO 3 systems were used to investigate sulphur speciation in silicate glasses. S K-edge spectra comprised a composite peak with an edge between 2470 and 2471.4 eV, which was attributed to S 2-, and a peak of variable height with an edge at 2480.2-2480.8 eV, which is consistent with the presence of S 6+. The latter peak was attributed to sample oxidation during sample storage. W-rich samples produced an additional lower energy peak at 2469.8 eV that is tentatively attributed to the existence of S 3p orbitals hybridised with the W 5d states. Deconvolution of the composite peak reveals that the composite peak for Mn-bearing samples fits well to a model that combines three Lorentzians at 2473.1, 2474.9 and 2476.2 eV with an arctan edge step. The composite peak for W-bearing samples fits well to the same combination plus an additional Lorentzian at 2469.8 eV. The ratio of the proportions of the signal accounted for by peaks at 2473.1 and 2476.2 eV correlates with Mn:Ca molar ratios, but not with W:Ca ratios. Spectra from Ni-bearing samples were qualitatively similar but S levels were too low to allow robust quantification of peak components. Some part of the signal accounted for by the 2473.1 eV peak was therefore taken to record the formation of Mn-S melt species, while the 2469.8 peak is interpreted to record the formation of W-S melt species. The 2474.9 and 2476.2 eV peaks were taken to be dominated by Ca-S and Mg-S interactions. However, a 1:1 relationship between peak components and specific energy transitions is not proposed. This interpretation is consistent with known features of the lower parts of the conduction band in monosulphide minerals and indicates a similarity between sulphur species in the melts and the monosulphides. S-XANES spectra cannot be reproduced by a combination of the

Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

DOE PAGES

Getsoian, Andrew "Bean"; Das, Ujjal; Camacho-Bunquin, Jeffrey; ...

2016-06-13

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order tomore » better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

Thermally activated decomposition of (Ga,Mn)As thin layer at medium temperature post growth annealing

NASA Astrophysics Data System (ADS)

Melikhov, Y.; Konstantynov, P.; Domagala, J.; Sadowski, J.; Chernyshova, M.; Wojciechowski, T.; Syryanyy, Y.; Demchenko, I. N.

2016-05-01

The redistribution of Mn atoms in Ga1-xMnxAs layer during medium-temperature annealing, 250-450 oC, by Mn K-edge X-ray absorption fine structure (XAFS) recorded at ALBA facility, was studied. For this purpose Ga1-xMnxAs thin layer with x=0.01 was grown on AlAs buffer layer deposited on GaAs(100) substrate by molecular beam epitaxy (MBE) followed by annealing. The examined layer was detached from the substrate using a “lift-off” procedure in order to eliminate elastic scattering in XAFS spectra. Fourier transform analysis of experimentally obtained EXAFS spectra allowed to propose a model which describes a redistribution/diffusion of Mn atoms in the host matrix. Theoretical XANES spectra, simulated using multiple scattering formalism (FEFF code) with the support of density functional theory (WIEN2k code), qualitatively describe the features observed in the experimental fine structure.

Investigation of Prussian Blue Analogs by XMCD at the K-edge of transition metals

NASA Astrophysics Data System (ADS)

Bordage, A.; Nataf, L.; Baudelet, F.; Bleuzen, A.

2016-05-01

Despite transition metal (TM) K-edge x-ray magnetic circular dichroism (XMCD) seems an interesting tool to get magnetic and structural information at the atomic scale, the effects originating this signal are still poorly understood. We thus initiated a deep investigation of the TM K-edge XMCD using Prussian Blue analogs (PBA) as model-compounds. In a recent study of the NiFe PBA family, we demonstrated that the XMCD signals at the TM K-edges strongly vary with external (mechanical) or internal (chemical) pressure and so that they are highly sensitive to small structural distortions. Following these first results, we extended this approach to the MnFe and CoFe families to evaluate the effect of electronic parameters (number of unpaired electrons of the M II TM) on the XMCD signal. All the results set milestones in the disentanglement of the components originating the XMCD signals at the K-edge of TM and will eventually help in a better understanding of the photomagnetic properties of PBAs.

Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

PubMed

Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

2016-05-04

The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

NO binding kinetics in myoglobin investigated by picosecond Fe K-edge absorption spectroscopy

PubMed Central

Silatani, Mahsa; Lima, Frederico A.; Penfold, Thomas J.; Rittmann, Jochen; Reinhard, Marco E.; Rittmann-Frank, Hannelore M.; Borca, Camelia; Grolimund, Daniel; Milne, Christopher J.; Chergui, Majed

2015-01-01

Diatomic ligands in hemoproteins and the way they bind to the active center are central to the protein’s function. Using picosecond Fe K-edge X-ray absorption spectroscopy, we probe the NO-heme recombination kinetics with direct sensitivity to the Fe-NO binding after 532-nm photoexcitation of nitrosylmyoglobin (MbNO) in physiological solutions. The transients at 70 and 300 ps are identical, but they deviate from the difference between the static spectra of deoxymyoglobin and MbNO, showing the formation of an intermediate species. We propose the latter to be a six-coordinated domed species that is populated on a timescale of ∼200 ps by recombination with NO ligands. This work shows the feasibility of ultrafast pump–probe X-ray spectroscopic studies of proteins in physiological media, delivering insight into the electronic and geometric structure of the active center. PMID:26438842

Automated generation and ensemble-learned matching of X-ray absorption spectra

NASA Astrophysics Data System (ADS)

Zheng, Chen; Mathew, Kiran; Chen, Chi; Chen, Yiming; Tang, Hanmei; Dozier, Alan; Kas, Joshua J.; Vila, Fernando D.; Rehr, John J.; Piper, Louis F. J.; Persson, Kristin A.; Ong, Shyue Ping

2018-12-01

X-ray absorption spectroscopy (XAS) is a widely used materials characterization technique to determine oxidation states, coordination environment, and other local atomic structure information. Analysis of XAS relies on comparison of measured spectra to reliable reference spectra. However, existing databases of XAS spectra are highly limited both in terms of the number of reference spectra available as well as the breadth of chemistry coverage. In this work, we report the development of XASdb, a large database of computed reference XAS, and an Ensemble-Learned Spectra IdEntification (ELSIE) algorithm for the matching of spectra. XASdb currently hosts more than 800,000 K-edge X-ray absorption near-edge spectra (XANES) for over 40,000 materials from the open-science Materials Project database. We discuss a high-throughput automation framework for FEFF calculations, built on robust, rigorously benchmarked parameters. FEFF is a computer program uses a real-space Green's function approach to calculate X-ray absorption spectra. We will demonstrate that the ELSIE algorithm, which combines 33 weak "learners" comprising a set of preprocessing steps and a similarity metric, can achieve up to 84.2% accuracy in identifying the correct oxidation state and coordination environment of a test set of 19 K-edge XANES spectra encompassing a diverse range of chemistries and crystal structures. The XASdb with the ELSIE algorithm has been integrated into a web application in the Materials Project, providing an important new public resource for the analysis of XAS to all materials researchers. Finally, the ELSIE algorithm itself has been made available as part of veidt, an open source machine-learning library for materials science.

Si K EDGE STRUCTURE AND VARIABILITY IN GALACTIC X-RAY BINARIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schulz, Norbert S.; Corrales, Lia; Canizares, Claude R.

2016-08-10

We survey the Si K edge structure in various absorbed Galactic low-mass X-ray binaries (LMXBs) to study states of silicon in the inter- and circum-stellar medium. The bulk of these LMXBs lie toward the Galactic bulge region and all have column densities above 10{sup 22} cm{sup −2}. The observations were performed using the Chandra High Energy Transmission Grating Spectrometer. The Si K edge in all sources appears at an energy value of 1844 ± 0.001 eV. The edge exhibits significant substructure that can be described by a near edge absorption feature at 1849 ± 0.002 eV and a far edgemore » absorption feature at 1865 ± 0.002 eV. Both of these absorption features appear variable with equivalent widths up to several mÅ. We can describe the edge structure using several components: multiple edge functions, near edge absorption excesses from silicates in dust form, signatures from X-ray scattering optical depths, and a variable warm absorber from ionized atomic silicon. The measured optical depths of the edges indicate much higher values than expected from atomic silicon cross sections and interstellar medium abundances, and they appear consistent with predictions from silicate X-ray absorption and scattering. A comparison with models also indicates a preference for larger dust grain sizes. In many cases, we identify Si xiii resonance absorption and determine ionization parameters between log ξ = 1.8 and 2.8 and turbulent velocities between 300 and 1000 km s{sup −1}. This places the warm absorber in close vicinity of the X-ray binaries. In some data, we observe a weak edge at 1.840 keV, potentially from a lesser contribution of neutral atomic silicon.« less

Hydrogen-induced structural changes at the nickel site of the regulatory [NiFe] hydrogenase from Ralstonia eutropha detected by X-ray absorption spectroscopy.

PubMed

Haumann, Michael; Porthun, Antje; Buhrke, Thorsten; Liebisch, Peter; Meyer-Klaucke, Wolfram; Friedrich, Bärbel; Dau, Holger

2003-09-23

For the first time, the nickel site of the hydrogen sensor of Ralstonia eutropha, the regulatory [NiFe] hydrogenase (RH), was investigated by X-ray absorption spectroscopy (XAS) at the nickel K-edge. The oxidation state and the atomic structure of the Ni site were investigated in the RH in the absence (air-oxidized, RH(ox)) and presence of hydrogen (RH(+H2)). Incubation with hydrogen is found to cause remarkable changes in the spectroscopic properties. The Ni-C EPR signal, indicative of Ni(III), is detectable only in the RH(+H2) state. XANES and EXAFS spectra indicate a coordination of the Ni in the RH(ox) and RH(+H2) that pronouncedly differs from the one in standard [NiFe] hydrogenases. Also, the changes induced by exposure to H(2) are unique. A drastic modification in the XANES spectra and an upshift of the K-edge energy from 8339.8 (RH(ox)) to 8341.1 eV (RH(+H2)) is observed. The EXAFS spectra indicate a change in the Ni coordination in the RH upon exposure to H(2). One likely interpretation of the data is the detachment of one sulfur ligand in RH(+H2) and the binding of additional (O,N) or H ligands. The following Ni oxidation states and coordinations are proposed: five-coordinated Ni(II)(O,N)(2)S(3) for RH(ox) and six-coordinated Ni((III))(O,N)(3)X(1)S(2) [X being either an (O,N) or H ligand] for RH(+H2). Implications of the structural features of the Ni site of the RH in relation to its function, hydrogen sensing, are discussed.

EXAFS, ab Initio Molecular Dynamics, and NICIS Spectroscopy Studies on an Organic Dye Model at the Dye-Sensitized Solar Cell Photoelectrode Interface.

PubMed

Liu, Peng; Johansson, Viktor; Trilaksana, Herri; Rosdahl, Jan; Andersson, Gunther G; Kloo, Lars

2017-06-14

The organization of dye molecules in the dye layer adsorbed on the semiconductor substrate in dye-sensitized solar cells has been studied using a combination of theoretical methods and experimental techniques. The model system is based on the simple D-π-A dye L0, which has been chemically modified by substituting the acceptor group CN with Br (L0Br) to offer better X-ray contrast. Experimental EXAFS data based on the Br K-edge backscattering show no obvious difference between dye-sensitized titania powder and titania film samples, thus allowing model systems to be based on powder slurries. Ab initio molecular dynamic (aiMD) calculations have been performed to extract less biased information from the experimental EXASF data. Using the aiMD calculation as input, the EXAFS structural models can be generated a priori that match the experimental data. Our study shows that the L0Br dye adsorbs in the trans-L0Br configuration and that adsorption involves both a proximity to other L0Br dye molecules and the titanium atoms in the TiO 2 substrate. These results indicate direct coordination of the dye molecules to the TiO 2 surface in contrast to previous results on metal-organic dyes. The molecular coverage of L0Br on mesoporous TiO 2 was also estimated using NICIS spectroscopy. The NICISS results emphasized that the L0Br dye on nanoporous titania mainly forms monolayers with a small contribution of multilayer coverage.

X-ray absorption studies of chlorine valence and local environments in borosilicate waste glasses

NASA Astrophysics Data System (ADS)

McKeown, David A.; Gan, Hao; Pegg, Ian L.; Stolte, W. C.; Demchenko, I. N.

2011-01-01

Chlorine (Cl) is a constituent of certain types of nuclear wastes and its presence can affect the physical and chemical properties of silicate melts and glasses developed for the immobilization of such wastes. Cl K-edge X-ray absorption spectra (XAS) were collected and analyzed to characterize the unknown Cl environments in borosilicate waste glass formulations, ranging in Cl-content from 0.23 to 0.94 wt.%. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data for the glasses show trends dependent on calcium (Ca) content. Near-edge data for the Ca-rich glasses are most similar to the Cl XANES of CaCl 2, where Cl - is coordinated to three Ca atoms, while the XANES for the Ca-poor glasses are more similar to the mineral davyne, where Cl is most commonly coordinated to two Ca in one site, as well as Cl and oxygen nearest-neighbors in other sites. With increasing Ca content in the glass, Cl XANES for the glasses approach that for CaCl 2, indicating more Ca nearest-neighbors around Cl. Reliable structural information obtained from the EXAFS data for the glasses is limited, however, to Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na distances; Cl sbnd Ca contributions could not be fit to the glass data, due to the narrow k-space range available for analysis. Structural models that best fit the glass EXAFS data include Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na correlations, where Cl sbnd O and Cl sbnd Na distances decrease by approximately 0.16 Å as glass Ca content increases. XAS for the glasses indicates Cl - is found in multiple sites where most Cl-sites have Ca neighbors, with oxygen, and possibly, Na second-nearest neighbors. EXAFS analyses suggest that Cl sbnd Cl environments may also exist in the glasses in minor amounts. These results are generally consistent with earlier findings for silicate glasses, where Cl - was associated with Ca 2+ and Na + in network modifier sites.

X-ray K-edge analysis of drain lines in Wilhelm Hall, Ames Laboratory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jensen, T.; Whitmore, C.

1999-01-05

From August 12--27, 1998 X-ray K-edge measurements were made on drain lines in seven rooms in Wilhelm Hall, Ames Laboratory. The purpose of these measurements was to determine the extent of thorium (and other heavy metal) contamination inside these pipes. The K-edge method is a noninvasive inspection technique that can provide accurate quantification of heavy metal contamination interior to an object. Of the seven drain lines inspected, one was found to have no significant contamination, three showed significant thorium deposits, two showed mercury contamination, and one line was found to contain mercury, thorium and uranium. The K-edge measurements were foundmore » to be consistent with readings from hand-held survey meters, and provided much greater detail on the location and amount of heavy metal contamination.« less

Lithium K(1s) synchrotron NEXAFS spectra of lithium-ion battery cathode, anode and electrolyte materials

NASA Astrophysics Data System (ADS)

Braun, Artur; Wang, Hongxin; Shim, Joongpyo; Lee, Steven S.; Cairns, Elton J.

The lithium(1s) K-edge X-ray absorption spectra of lithium-ion battery relevant materials (Li metal, Li 3N, LiPF 6, LiC 6, and LiMn 1.90Ni 0.10O 4) are presented. The Li and LiC 6 spectra are discussed and compared with literature data. The Li in lithium-intercalated carbon LiC 6, typically used as anode battery electrode material, could be clearly identified in the spectrum, and a presumed purely metallic character of the Li can be ruled out based on the chemical shift observed. The Li in corresponding cathode electrode materials, LiMn 1.90Ni 0.10O 4, could be detected with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, but the strong (self-) absorption of the spinel lattice provides an obstacle for quantitative analysis. Owing to its ionic bonding, the spectrum of the electrolyte salt LiPF 6 contains a sharp π-resonance at 61.8 eV, suggesting a distinct charge transfer between Li and the hexafluorophosphate anion. In addition, LiPF 6 resembles many spectral features of LiF, making it difficult to discriminate both from each other. Residual electrolyte on anodes or cathodes poses a problem for the spectroscopic analysis of the electrodes, because its Li spectrum overshadows the spectral features of the Li in the anode or cathode. The electrolyte must be removed from electrodes prior to spectroscopic analysis.

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

NASA Technical Reports Server (NTRS)

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

1987-01-01

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

Alternative difference analysis scheme combining R-space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy.

PubMed

Zhan, Fei; Tao, Ye; Zhao, Haifeng

2017-07-01

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions. R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3 spin crossover complex and yielded reliable distance change and excitation population.

K-edge ratio method for identification of multiple nanoparticulate contrast agents by spectral CT imaging

PubMed Central

Ghadiri, H; Ay, M R; Shiran, M B; Soltanian-Zadeh, H

2013-01-01

Objective: Recently introduced energy-sensitive X-ray CT makes it feasible to discriminate different nanoparticulate contrast materials. The purpose of this work is to present a K-edge ratio method for differentiating multiple simultaneous contrast agents using spectral CT. Methods: The ratio of two images relevant to energy bins straddling the K-edge of the materials is calculated using an analytic CT simulator. In the resulting parametric map, the selected contrast agent regions can be identified using a thresholding algorithm. The K-edge ratio algorithm is applied to spectral images of simulated phantoms to identify and differentiate up to four simultaneous and targeted CT contrast agents. Results: We show that different combinations of simultaneous CT contrast agents can be identified by the proposed K-edge ratio method when energy-sensitive CT is used. In the K-edge parametric maps, the pixel values for biological tissues and contrast agents reach a maximum of 0.95, whereas for the selected contrast agents, the pixel values are larger than 1.10. The number of contrast agents that can be discriminated is limited owing to photon starvation. For reliable material discrimination, minimum photon counts corresponding to 140 kVp, 100 mAs and 5-mm slice thickness must be used. Conclusion: The proposed K-edge ratio method is a straightforward and fast method for identification and discrimination of multiple simultaneous CT contrast agents. Advances in knowledge: A new spectral CT-based algorithm is proposed which provides a new concept of molecular CT imaging by non-iteratively identifying multiple contrast agents when they are simultaneously targeting different organs. PMID:23934964

X-ray Absorption Spectroscopy Systematics at the Tungsten L-Edge

PubMed Central

2015-01-01

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W0(PMe3)6], [WIICl2(PMePh2)4], [WIIICl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [WIVCl4(PMePh2)2], [WV(NPh)Cl3(PMe3)2], and [WVICl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [WIV(mdt)2(CO)2] and [WIV(mdt)2(CN)2]2– (mdt2– = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively WIV species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal–ligand distances, exaggerate the difference

Structure of shock compressed model basaltic glass: Insights from O K-edge X-ray Raman scattering and high-resolution 27Al NMR spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Sung Keun; Park, Sun Young; Kim, Hyo-Im; Tschauner, Oliver; Asimow, Paul; Bai, Ligang; Xiao, Yuming; Chow, Paul

2012-03-01

The detailed atomic structures of shock compressed basaltic glasses are not well understood. Here, we explore the structures of shock compressed silicate glass with a diopside-anorthite eutectic composition (Di64An36), a common Fe-free model basaltic composition, using oxygen K-edge X-ray Raman scattering and high- resolution 27Al solid-state NMR spectroscopy and report previously unknown details of shock-induced changes in the atomic configurations. A topologically driven densification of the Di64An36 glass is indicated by the increase in oxygen K-edge energy for the glass upon shock compression. The first experimental evidence of the increase in the fraction of highly coordinated Al in shock compressed glass is found in the 27Al NMR spectra. This unambiguous evidence of shock-induced changes in Al coordination environments provides atomistic insights into shock compression in basaltic glasses and allows us to microscopically constrain the magnitude of impact events or relevant processes involving natural basalts on Earth and planetary surfaces.

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

PubMed

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

2016-01-01

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

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Non-destructive chemical analyses of these compounds is important for process and environmental monitoring and X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride,more » and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. These compounds have unique spectral signatures that can be used to identify unknown samples.« less

K- and L-edge X-ray absorption spectrum calculations of closed-shell carbon, silicon, germanium, and sulfur compounds using damped four-component density functional response theory.

PubMed

Fransson, Thomas; Burdakova, Daria; Norman, Patrick

2016-05-21

X-ray absorption spectra of carbon, silicon, germanium, and sulfur compounds have been investigated by means of damped four-component density functional response theory. It is demonstrated that a reliable description of relativistic effects is obtained at both K- and L-edges. Notably, an excellent agreement with experimental results is obtained for L2,3-spectra-with spin-orbit effects well accounted for-also in cases when the experimental intensity ratio deviates from the statistical one of 2 : 1. The theoretical results are consistent with calculations using standard response theory as well as recently reported real-time propagation methods in time-dependent density functional theory, and the virtues of different approaches are discussed. As compared to silane and silicon tetrachloride, an anomalous error in the absolute energy is reported for the L2,3-spectrum of silicon tetrafluoride, amounting to an additional spectral shift of ∼1 eV. This anomaly is also observed for other exchange-correlation functionals, but it is seen neither at other silicon edges nor at the carbon K-edge of fluorine derivatives of ethene. Considering the series of molecules SiH4-XFX with X = 1, 2, 3, 4, a gradual divergence from interpolated experimental ionization potentials is observed at the level of Kohn-Sham density functional theory (DFT), and to a smaller extent with the use of Hartree-Fock. This anomalous error is thus attributed partly to difficulties in correctly emulating the electronic structure effects imposed by the very electronegative fluorines, and partly due to inconsistencies in the spurious electron self-repulsion in DFT. Substitution with one, or possibly two, fluorine atoms is estimated to yield small enough errors to allow for reliable interpretations and predictions of L2,3-spectra of more complex and extended silicon-based systems.

BRIEF COMMUNICATION: Calculation of a magnetic field effect on emission spectra of light diatomic molecules for diagnostic application to fusion edge plasmas

NASA Astrophysics Data System (ADS)

Shikama, T.; Fujii, K.; Mizushiri, K.; Hasuo, M.; Kado, S.; Zushi, H.

2009-12-01

A scheme for computation of emission spectra of light diatomic molecules under external magnetic and electric fields is presented. As model species in fusion edge plasmas, the scheme is applied to polarization-resolved emission spectra of H2, CH, C2, BH and BeH molecules. The possibility of performing spatially resolved measurements of these spectra is examined.

K β X-Ray Emission Spectra of Phosphorus Oxo Acids and Anions

NASA Astrophysics Data System (ADS)

Sugiura, Chikara

1995-03-01

With a high-resolution two-crystal vacuum spectrometer, the phosphorus Kβ emission spectra in fluorescence are measured for H3PO3 (= H2PHO3), H3PO4, Li3PO4, Na3PO4·12H2O, Na2HPO4, NaH2PO4, K3PO4·nH2O, K2HPO4, KH2PO4, Ca3(PO4)2, CaHPO4·2H2O, Ca(H2PO4)2·H2O, CaHPO3·H2O, Ca(H2PO2)2 and NH4H2PO4. In the phosphate compounds, a weak peak is observed on the high-energy side of the main peak Kβ1 and related to a molecular orbital of t2 symmetry in the PO43- ion. It is shown that the phosphorus Kβ emission spectra are influenced by ligand substitution and cations. The measured Kβ emission spectra of Li3PO4, Na3PO4·12H2O, K3PO4·nH2O and Ca3(PO4)2 are presented along with the previously reported P-K absorption spectra of these phosphate compounds. The emission and absorption spectra are interpreted in terms of available molecular orbitals of the PO43- ion.

Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements

USGS Publications Warehouse

Bargar, John R.; Reitmeyer, Rebecca; Lenhart, John J.; Davis, James A.

2000-01-01

We have measured U(VI) adsorption on hematite using EXAFS spectroscopy and electrophoresis under conditions relevant to surface waters and aquifers (0.01 to 10 μM dissolved uranium concentrations, in equilibrium with air, pH 4.5 to 8.5). Both techniques suggest the existence of anionic U(VI)-carbonato ternary complexes. Fits to EXAFS spectra indicate that U(VI) is simultaneously coordinated to surface FeO6 octahedra and carbonate (or bicarbonate) ligands in bidentate fashions, leading to the conclusion that the ternary complexes have an inner-sphere metal bridging (hematite-U(VI)-carbonato) structure. Greater than or equal to 50% of adsorbed U(VI) was comprised of monomeric hematite-U(VI)-carbonato ternary complexes, even at pH 4.5. Multimeric U(VI) species were observed at pH ≥ 6.5 and aqueous U(VI) concentrations approximately an order of magnitude more dilute than the solubility of crystalline β-UO2(OH)2. Based on structural constraints, these complexes were interpreted as dimeric hematite-U(VI)-carbonato ternary complexes. These results suggest that Fe-oxide-U(VI)-carbonato complexes are likely to be important transport-limiting species in oxic aquifers throughout a wide range of pH values.

Surface complexation model for multisite adsorption of copper(II) onto kaolinite

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2005-08-01

We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 inner-sphere complexes on variable-charge ≡AlOH sites and as Cu 2+ on ion exchangeable ≡X-H + sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH) 6 polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH) 2Cu(OH) 20, tridentate (≡Al 3O(OH) 2)Cu 2(OH) 30 and ≡X-Cu 2+ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions

Phonon stiffen and soften at zigzag- and armchair-dominated edges of exfoliated bilayer graphene ribbon presented by Raman spectra

NASA Astrophysics Data System (ADS)

Xia, Minggang; Zhou, Xiaohua; Xin, Duqiang; Xu, Qiang

2018-01-01

The Raman spectra at the edge of the exfoliated bilayer graphene ribbon (GR) were investigated in detail. Results show that both G and 2D phonons stiffen (wave number increases) at zigzag-dominated edge, while they soften at armchair-dominated edge compared with those at the middle position in the GR. Furthermore, the full widths at half maximum intensity of both G and 2D Raman peaks narrow at the zigzag-dominated edge, while they broaden at the armchair-dominated edge. The stiffness and softness are attributed to the C-C bonds at the edge. For zigzag-dominated edge, the stiffness may originate in the increase of the force constant induced by the shrinking of C-C bond. For armchair-dominated edge, the softness may be due to the decrease of the force constant induced by the unsaturated hanging bonds at edge, which is different from Kohn anomaly and charge doping. The analysis is in agreement well with others calculation results about C-C bonds and the edge energy. These results may be useful to understand physical properties at the bilayer graphene edge and for applications in the device by taking advantage of the edge states in bilayer graphene.

Planar Lattice Instability in LA2CUO4.1 across the Superconducting Transition

NASA Astrophysics Data System (ADS)

Acosta-Alejandro, Manuel; Mustre-de Leon, Jose; Conradson, Steven

2001-03-01

The local atomic structure of La2CuO4.1 around Cu K-edge is analyzed for 10K, using polarized extended x-ray absorption fine structure. We have fitted Cu-O(planar) EXAFS contribution using a Gaussian radial distribution function (RDF) and a double peeked RDF, derived from model double-well potentials. Away from the superconducting transition, we find that the spectra is consistent with a double-peeked RDF, in agreement with other studies. However, in th neighborhood of the superconducting transition the RDF becomes single peaked. This work was partially supported by Consejo Nacional de Ciencia y Tecnología (CONACYT, México) under Grant. No. 31274-U.

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

PubMed Central

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

2016-01-01

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

Efficient simultaneous reverse Monte Carlo modeling of pair-distribution functions and extended x-ray-absorption fine structure spectra of crystalline disordered materials.

PubMed

Németh, Károly; Chapman, Karena W; Balasubramanian, Mahalingam; Shyam, Badri; Chupas, Peter J; Heald, Steve M; Newville, Matt; Klingler, Robert J; Winans, Randall E; Almer, Jonathan D; Sandi, Giselle; Srajer, George

2012-02-21

An efficient implementation of simultaneous reverse Monte Carlo (RMC) modeling of pair distribution function (PDF) and EXAFS spectra is reported. This implementation is an extension of the technique established by Krayzman et al. [J. Appl. Cryst. 42, 867 (2009)] in the sense that it enables simultaneous real-space fitting of x-ray PDF with accurate treatment of Q-dependence of the scattering cross-sections and EXAFS with multiple photoelectron scattering included. The extension also allows for atom swaps during EXAFS fits thereby enabling modeling the effects of chemical disorder, such as migrating atoms and vacancies. Significant acceleration of EXAFS computation is achieved via discretization of effective path lengths and subsequent reduction of operation counts. The validity and accuracy of the approach is illustrated on small atomic clusters and on 5500-9000 atom models of bcc-Fe and α-Fe(2)O(3). The accuracy gains of combined simultaneous EXAFS and PDF fits are pointed out against PDF-only and EXAFS-only RMC fits. Our modeling approach may be widely used in PDF and EXAFS based investigations of disordered materials. © 2012 American Institute of Physics

Electronic structure and fundamental absorption edges of KPb2Br5, K0.5Rb0.5Pb2Br5, and RbPb2Br5 single crystals

NASA Astrophysics Data System (ADS)

Tarasova, A. Yu.; Isaenko, L. I.; Kesler, V. G.; Pashkov, V. M.; Yelisseyev, A. P.; Denysyuk, N. M.; Khyzhun, O. Yu.

2012-05-01

X-ray photoelectron core-level and valence-band spectra for pristine and Ar+-ion irradiated (001) surfaces of KPb2Br5, K0.5Rb0.5Pb2Br5, and RbPb2Br5 single crystals grown by the Bridgman method have been measured and fundamental absorption edges of the ternary bromides have been recorded in the polarized light at 300 K and 80 K. The present X-ray photoelectron spectroscopy (XPS) results reveal high chemical stability of (001) surfaces of KxRb1-xPb2Br5 (x=0, 0.5, and 1.0) single crystals. Substitution of potassium for rubidium in KxRb1-xPb2Br5 does not cause any changes of binding energy values and shapes of the XPS constituent element core-level spectra. Measurements of the fundamental absorption edges indicate that band gap energy, Eg, increases by about 0.14 and 0.19 eV when temperature decreases from 300 K to 80 K in KPb2Br5 and RbPb2Br5, respectively. Furthermore, there is no dependence of the Eg value for KPb2Br5 upon the light polarization, whilst the band gap energy value for RbPb2Br5 is bigger by 0.03-0.05 eV in the case of E‖c compared to those in the cases of E‖a and E‖b.

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

NASA Astrophysics Data System (ADS)

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

2014-04-01

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

Reducing radiation dose by application of optimized low-energy x-ray filters to K-edge imaging with a photon counting detector.

PubMed

Choi, Yu-Na; Lee, Seungwan; Kim, Hee-Joung

2016-01-21

K-edge imaging with photon counting x-ray detectors (PCXDs) can improve image quality compared with conventional energy integrating detectors. However, low-energy x-ray photons below the K-edge absorption energy of a target material do not contribute to image formation in the K-edge imaging and are likely to be completely absorbed by an object. In this study, we applied x-ray filters to the K-edge imaging with a PCXD based on cadmium zinc telluride for reducing radiation dose induced by low-energy x-ray photons. We used aluminum (Al) filters with different thicknesses as the low-energy x-ray filters and implemented the iodine K-edge imaging with an energy bin of 34-48 keV at the tube voltages of 50, 70 and 90 kVp. The effects of the low-energy x-ray filters on the K-edge imaging were investigated with respect to signal-difference-to-noise ratio (SDNR), entrance surface air kerma (ESAK) and figure of merit (FOM). The highest value of SDNR was observed in the K-edge imaging with a 2 mm Al filter, and the SDNR decreased as a function of the filter thicknesses. Compared to the K-edge imaging with a 2 mm Al filter, the ESAK was reduced by 66%, 48% and 39% in the K-edge imaging with a 12 mm Al filter for 50 kVp, 70 kVp and 90 kVp, respectively. The FOM values, which took into account the ESAK and SDNR, were maximized for 8, 6 to 8 and 4 mm Al filters at 50 kVp, 70 kVp and 90 kVp, respectively. We concluded that the use of an optimal low-energy filter thickness, which was determined by maximizing the FOM, could significantly reduce radiation dose while maintaining image quality in the K-edge imaging with the PCXD.

Full-Field Calcium K-Edge X-ray Absorption Near-Edge Structure Spectroscopy on Cortical Bone at the Micron-Scale: Polarization Effects Reveal Mineral Orientation.

PubMed

Hesse, Bernhard; Salome, Murielle; Castillo-Michel, Hiram; Cotte, Marine; Fayard, Barbara; Sahle, Christoph J; De Nolf, Wout; Hradilova, Jana; Masic, Admir; Kanngießer, Birgit; Bohner, Marc; Varga, Peter; Raum, Kay; Schrof, Susanne

2016-04-05

Here, we show results on X-ray absorption near edge structure spectroscopy in both transmission and X-ray fluorescence full-field mode (FF-XANES) at the calcium K-edge on human bone tissue in healthy and diseased conditions and for different tissue maturation stages. We observe that the dominating spectral differences originating from different tissue regions, which are well pronounced in the white line and postedge structures are associated with polarization effects. These polarization effects dominate the spectral variance and must be well understood and modeled before analyzing the very subtle spectral variations related to the bone tissue variations itself. However, these modulations in the fine structure of the spectra can potentially be of high interest to quantify orientations of the apatite crystals in highly structured tissue matrices such as bone. Due to the extremely short wavelengths of X-rays, FF-XANES overcomes the limited spatial resolution of other optical and spectroscopic techniques exploiting visible light. Since the field of view in FF-XANES is rather large the acquisition times for analyzing the same region are short compared to, for example, X-ray diffraction techniques. Our results on the angular absorption dependence were verified by both site-matched polarized Raman spectroscopy, which has been shown to be sensitive to the orientation of bone building blocks and by mathematical simulations of the angular absorbance dependence. As an outlook we further demonstrate the polarization based assessment of calcium-containing crystal orientation and specification of calcium in a beta-tricalcium phosphate (β-Ca3(PO4)2 scaffold implanted into ovine bone. Regarding the use of XANES to assess chemical properties of Ca in human bone tissue our data suggest that neither the anatomical site (tibia vs jaw) nor pathology (healthy vs necrotic jaw bone tissue) affected the averaged spectral shape of the XANES spectra.

X-ray absorption spectroscopy systematics at the tungsten L-edge.

PubMed

Jayarathne, Upul; Chandrasekaran, Perumalreddy; Greene, Angelique F; Mague, Joel T; DeBeer, Serena; Lancaster, Kyle M; Sproules, Stephen; Donahue, James P

2014-08-18

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W(0)(PMe3)6], [W(II)Cl2(PMePh2)4], [W(III)Cl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [W(IV)Cl4(PMePh2)2], [W(V)(NPh)Cl3(PMe3)2], and [W(VI)Cl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W(IV)(mdt)2(CO)2] and [W(IV)(mdt)2(CN)2](2-) (mdt(2-) = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W(IV) species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate

Fluorine Kα X-Ray Emission Spectra of MgF2, CaF2, SrF2 and BaF2

NASA Astrophysics Data System (ADS)

Sugiura, Chikara; Konishi, Wataru; Shoji, Shizuko; Kojima, Shinjiro

1990-11-01

The fluorine Kα emission spectra in fluorescence from a series of alkaline-earth fluorides MF2 (M=Mg, Ca, Sr and Ba) are measured with a high-resolution two-crystal vacuum spectrometer. An anomalously low intensity of the K1L1 satellite peak arising from 1s-1(2s2p)-1 initial states is observed for SrF2. The measured emission spectra are presented along with the UPS spectra of the F- 2p valence bands obtained by Poole et al. and the fluorine K absorption-edge spectra by Oizumi et al. By using these spectra, the first peak or shoulder in the fluorine K absorption-edge spectra is identified as being due to a core exciton which is formed below the bottom of the conduction band. The binding energy of the exciton is estimated to be 1.3(± 0.3), 1.1(± 0.2), 1.0(± 0.2) and 1.7(± 0.2) eV for MgF2, CaF2, SrF2 and BaF2, respectively.

The red edge in arid region vegetation: 340-1060 nm spectra

NASA Technical Reports Server (NTRS)

Ray, Terrill W.; Murray, Bruce C.; Chehbouni, A.; Njoku, Eni

1993-01-01

The remote sensing study of vegetated regions of the world has typically been focused on the use of broad-band vegetation indices such as NDVI. Various modifications of these indices have been developed in attempts to minimize the effect of soil background, e.g., SAVI, or to reduce the effect of the atmosphere, e.g., ARVI. Most of these indices depend on the so-called 'red edge,' the sharp transition between the strong absorption of chlorophyll pigment in visible wavelengths and the strong scattering in the near-infrared from the cellular structure of leaves. These broadband indices tend to become highly inaccurate as the green canopy cover becomes sparse. The advent of high spectral resolution remote sensing instrument such as the Airborne Visible and Infrared Imaging Spectrometer (AVIRIS) has allowed the detection of narrow spectral features in vegetation and there are reports of detection of the red edge even for pixels with very low levels of green vegetation cover by Vane et al. and Elvidge et al., and to characterize algal biomass in coastal areas. Spectral mixing approaches similar to those of Smith et al. can be extended into the high spectral resolution domain allowing for the analysis of more endmembers, and potentially, discrimination between material with narrow spectral differences. Vegetation in arid regions tends to be sparse, often with small leaves such as the creosote bush. Many types of arid region vegetation spend much of the year with their leaves in a senescent state, i.e., yellow, with lowered chlorophyll pigmentation. The sparseness of the leaves of many arid region plants has the dual effect of lowering the green leaf area which can be observed and of allowing more of the sub-shrub soil to be visible which further complicates the spectrum of a region covered with arid region vegetation. Elvidge examined the spectral characteristics of dry plant materials showing significant differences in the region of the red edge and the diagnostic ligno

Full multiple-scattering calculations on silicates and oxides at the Al K edge

NASA Astrophysics Data System (ADS)

Cabaret, Delphine; Sainctavit, Philippe; Ildefonse, Philippe; Flank, Anne-Marie

1996-05-01

We present full multiple-scattering calculations at the aluminium K edge that we compare with experiments for four crystalline silicates and oxide minerals. In the different minerals aluminium atoms are either fourfold or sixfold coordinated to oxygen atoms in Al sites that are poorly symmetric. The calculations are based on different choices of one-electron potentials according to aluminium coordinations and crystallographic structures of the compounds. Hence it is possible to determine how the near-edge spectral features are a sensitive probe of the effective potential seen by the photoelectron in the molecular environment. The purpose of this work is to determine on the one hand the relation between Al K-edge spectral features and the geometrical arrangements around the aluminium sites, and on the other hand the electronic structure of the compounds.

Alternative difference analysis scheme combining R -space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhan, Fei; Tao, Ye; Zhao, Haifeng

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions.R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure changemore » in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3spin crossover complex and yielded reliable distance change and excitation population.« less

Lanthanide complexes of macrocyclic polyoxovanadates by VO4 units: synthesis, characterization, and structure elucidation by X-ray crystallography and EXAFS spectroscopy.

PubMed

Nishio, Masaki; Inami, Shinnosuke; Katayama, Misaki; Ozutsumi, Kazuhiko; Hayashi, Yoshihito

2012-01-16

Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.

Model and reconstruction of a K-edge contrast agent distribution with an X-ray photon-counting detector

PubMed Central

Meng, Bo; Cong, Wenxiang; Xi, Yan; De Man, Bruno; Yang, Jian; Wang, Ge

2017-01-01

Contrast-enhanced computed tomography (CECT) helps enhance the visibility for tumor imaging. When a high-Z contrast agent interacts with X-rays across its K-edge, X-ray photoelectric absorption would experience a sudden increment, resulting in a significant difference of the X-ray transmission intensity between the left and right energy windows of the K-edge. Using photon-counting detectors, the X-ray intensity data in the left and right windows of the K-edge can be measured simultaneously. The differential information of the two kinds of intensity data reflects the contrast-agent concentration distribution. K-edge differences between various matters allow opportunities for the identification of contrast agents in biomedical applications. In this paper, a general radon transform is established to link the contrast-agent concentration to X-ray intensity measurement data. An iterative algorithm is proposed to reconstruct a contrast-agent distribution and tissue attenuation background simultaneously. Comprehensive numerical simulations are performed to demonstrate the merits of the proposed method over the existing K-edge imaging methods. Our results show that the proposed method accurately quantifies a distribution of a contrast agent, optimizing the contrast-to-noise ratio at a high dose efficiency. PMID:28437900

Influence of 300°C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions: Insights from EXAFS/XANES, XRD and FTIR (companion paper).

PubMed

Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan

2017-04-01

In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300°C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate, fluoride, bromide, and bromate. The presence of the carbonate-based Ce-component and surface sulfate in precursor samples creates favorable conditions for phase transformation, resulting in the formation of novel (unknown) layered compounds of Fe and Ce. These compounds are of the layered double hydroxide type, with sulfate in the interlayer space. In spite of general awareness of the importance of surface area in adsorptive removal, the increase in surface area upon thermal treatment did not increase adsorption of the studied anions. However, EXAFS simulations and the adsorption tests provided evidence of regularities between local structures of Fe in composites obtained at 80 and 300°C and adsorption performance of most studied anions. The best adsorption of tetrahedral anions was demonstrated by samples whose simulated outer Fe shells resulted from oscillations from both O and Fe atoms. In contrast, the loss of extended x-ray absorption fine structure was correlated with the decrease of adsorptive removal. Both Fe K-edge and Ce L 3 -edge EXAFS suggested the formation of solid solutions. For the first time, the utilization of extended x-ray absorption fine structure is suggested as a methodological approach (first expressed in the companion paper) to estimate the surface reactivity of inorganic materials intended for use as anion exchange adsorbents. Copyright © 2016 Elsevier Inc. All rights reserved.

Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

2001-07-01

Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

An extended X-Ray absorption fine structure (exafs) study of copper (II) sulphate pentahydrate

NASA Astrophysics Data System (ADS)

Joyner, Richard W.

1980-05-01

The EXAFS spectrum of copper (II) sulphate pentahydrate has been measured using synchrotron radiation. Comparison with the results of ab initio calculation gives a mean copper-oxygen distance of 1.95 Å, in reasonable agreement with the known value of 1.97 Å. The relation between the EXAFS Debye-Waller factor and thermal parameters measured by neutron diffraction is discussed. Absence in the EXAFS spectrum of evidence for the second-nearest neighbour oxygen atoms, at Cu-O ≈ 2.4 Å, is discussed.

High-resolution Measurement of Contact Ion-pair Structures in Aqueous RbCl Solutions from the Simultaneous Corefinement of their Rb and Cl K-edge XAFS and XRD Spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham, Van-Thai; Fulton, John L.

2016-06-21

In concentrated solutions of aqueous RbCl, all of the Rb+ and Cl- ions exist as contact ion pairs. This full structural assessment is derived from the refinement of three independent experimental measurements: the Rb and Cl K-edge x-ray absorption fine structure (XAFS) and the x-ray diffraction spectra (XRD). This simultaneous refinement of the XAFS and XRD data provides high accuracy since each method probes the structure of different local regions about the ions with high sensitivity. At high RbCl concentration (6 m (mol/kg )) the solution is dominated by Rb+ - Cl- contact ion pairs yielding an average of 1.5more » pairs at an Rb-Cl distance of 3.24 Å. Upon formation of these ion pairs, approximately 1.1 waters molecules are displaced from the Rb+ and 1.4 water molecules from Cl-. The hydration shells about both the cation and anion are also determined. These results greatly improve the understanding of monovalent ions and provide a basis for testing the Rb+-Cl- interaction potentials used in molecular dynamics (MD) simulation. This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.« less

Mapping the conduction band edge density of states of γ-In2Se3 by diffuse reflectance spectra

NASA Astrophysics Data System (ADS)

Kumar, Pradeep; Vedeshwar, Agnikumar G.

2018-03-01

It is demonstrated that the measured diffuse reflectance spectra of γ-In2Se3 can be used to map the conduction band edge density of states through Kubelka-Munk analysis. The Kubelka-Munk function derived from the measured spectra almost mimics the calculated density of states in the vicinity of conduction band edge. The calculation of density of states was carried out using first-principles approach yielding the structural, electronic, and optical properties. The calculations were carried out implementing various functionals and only modified Tran and Blaha (TB-MBJ) results tally closest with the experimental result of band gap. The electronic and optical properties were calculated using FP-LAPW + lo approach based on the Density Functional Theory formalism implementing only TB-mBJ functional. The electron and hole effective masses have been calculated as me * = 0.25 m 0 and mh * = 1.11 m 0 , respectively. The optical properties clearly indicate the anisotropic nature of γ-In2Se3.

X-ray edge spectra — a sea-boson perspective

NASA Astrophysics Data System (ADS)

Setlur, Girish S.; Meera, V.

2007-07-01

The well-studied X-ray-edge problem is revisited using the sea-boson method. This approach is contrasted with the well-known theories of Mahan, Nozières and De Dominicis (MND). The present approach does not use the sudden approximation and the holes carry a momentum label unlike in the MND theory. We focus on the case of doped semiconductors rather than metals. The problem of electrons in a partially filled conduction band and holes in the initially hole-depleted valence band is recast in the sea-boson language. The resulting hamiltonian is shown to be equivalent to the electron-phonon hamiltonian with the excitons taking on the role of electrons and intra-conduction band particle-hole excitations known as 'conductrons' taking on the role of phonons. It is shown that the excitonic pole in the computed absorption spectra is replaced by a branch cut with a simple radical leading to a broadening of the exicton line due to these many-body effects. A critical comparison is made with the MND theory as well as with relevant experiments.

Competition behaviour of metal uptake in cementitious systems: An XRD and EXAFS investigation of Nd- and Zn-loaded 11 Å tobermorite

NASA Astrophysics Data System (ADS)

Vespa, M.; Dähn, R.; Wieland, E.

Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of hazardous and radioactive wastes. Cement is used to condition and stabilize the waste materials and to construct the engineered barrier systems (container, backfill and liner materials) of repositories for radioactive waste. In this study, bulk-X-ray absorption spectroscopy (XAS) was used to investigate the uptake mechanism of Nd on the crystalline C-S-H phase 11 Å tobermorite in the presence of Zn (co-absorbing metal), and vice versa, as potential competitor under strongly alkaline conditions (pH = 12.5-13.3). The Zn and Nd concentration in all samples was 50,000 ppm, whereas the reaction times varied from 1 to 6 months. Extended X-ray absorption fine structure (EXAFS) data of the Nd LIII-edge indicate that the local structural environment of Nd consists of ∼7-8 O atoms at 2.42 Å, ∼7-8 Si at ∼3.67 Å and ∼5-6 Ca at ∼3.8 Å, and that this environment remains unchanged in the presence and absence of Zn. In contrary, Zn K-edge EXAFS data exhibit distinct differences in the presence and absence of Nd as co-absorbing element. Data analysis indicates that Zn is tetrahedrally coordinated (∼4 O at ∼1.96 Å) and the obtained structural data in the simultaneous presence of Nd and Zn are consistent with the formation of mixed Zn surface complexes and Zn bound in the interlayer remaining in these positions also with prolonged reaction times (up to 6 months). However, without the co-absorbing element Nd, strong structural changes in the uptake mechanisms of Zn are observable, e.g., after 3 month reaction time Zn-Zn backscattering pairs can be observed. These findings suggest that Nd has an influence on the incorporation of Zn in the tobermorite structure. In addition, the results of this study indicate that competitive uptake of metal cations with similar sorption behaviour by C-S-H phases can take place, deserving further attention in future

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

PubMed

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

2013-06-01

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

Direct deconvolution of two-state pump-probe X-ray absorption spectra and the structural changes in a 100 ps transient of Ni(II)-tetramesitylporphyrin.

PubMed

Della-Longa, S; Chen, L X; Frank, P; Hayakawa, K; Hatada, K; Benfatto, M

2009-05-04

Full multiple scattering (FMS) Minuit XANES (MXAN) has been combined with laser pump-probe K-edge X-ray absorption spectroscopy (XAS) to determine the structure of photoexcited Ni(II)tetramesitylporphyrin, Ni(II)TMP, in dilute toluene solution. It is shown that an excellent simulation of the XANES spectrum is obtained, excluding the lowest-energy bound-state transitions. In ground-state Ni(II)TMP, the first-shell and second-shell distances are, respectively, d(Ni-N) = (1.93 +/- 0.02) A and d(Ni-C) = (2.94 +/- 0.03) A, in agreement with a previous EXAFS result. The time-resolved XANES difference spectrum was obtained (1) from the spectra of Ni(II)TMP in its photoexcited T(1) state and its ground state, S(0). The XANES difference spectrum has been analyzed to obtain both the structure and the fraction of the T(1) state. If the T(1) fraction is kept fixed at the value (0.37 +/- 0.10) determined by optical transient spectroscopy, a 0.07 A elongation of the Ni-N and Ni-C distances [d(Ni-N) and d(Ni-C)] is found, in agreement with the EXAFS result. However, an evaluation of both the distance elongation and the T(1) fraction can also be obtained using XANES data only. According to experimental evidence, and MXAN simulations, the T(1) fraction is (0.60 +/- 0.15) with d(Ni-N) = (1.98 +/- 0.03) A (0.05 A elongation). The overall uncertainty of these results depends on the statistical correlation between the distances and T(1) fraction, and the chemical shift of the ionization energy because of subtle changes of metal charge between the T(1) and S(0) states. The T(1) excited-state structure results, independently obtained without the excited-state fraction from optical transient spectroscopy, are still in agreement with previous EXAFS investigations. Thus, full multiple scattering theory applied through the MXAN formalism can be used to provide structural information, not only on the ground-state molecules but also on very short-lived excited states through differential

A comparative theoretical study on core-hole excitation spectra of azafullerene and its derivatives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Yunfeng; Department of Physics, Guizhou University, Guiyang 550025; Gao, Bin, E-mail: bin.gao@uit.no

2014-03-28

The core-hole excitation spectra—near-edge x-ray absorption spectroscopy (NEXAFS), x-ray emission spectroscopy (XES), and x-ray photoelectron spectroscopy (XPS) shake-up satellites have been simulated at the level of density functional theory for the azafullerene C{sub 59}N and its derivatives (C{sub 59}N){sup +}, C{sub 59}HN, (C{sub 59}N){sub 2}, and C{sub 59}N–C{sub 60}, in which the XPS shake-up satellites were simulated using our developed equivalent core hole Kohn-Sham (ECH-KS) density functional theory approach [B. Gao, Z. Wu, and Y. Luo, J. Chem. Phys. 128, 234704 (2008)] which aims for the study of XPS shake-up satellites of large-scale molecules. Our calculated spectra are generally inmore » good agreement with available experimental results that validates the use of the ECH-KS method in the present work. The nitrogen K-edge NEXAFS, XES, and XPS shake-up satellites spectra in general can be used as fingerprints to distinguish the azafullerene C{sub 59}N and its different derivatives. Meanwhile, different carbon K-edge spectra could also provide detailed information of (local) electronic structures of different molecules. In particular, a peak (at around 284.5 eV) in the carbon K-edge NEXAFS spectrum of the heterodimer C{sub 59}N–C{sub 60} is confirmed to be related to the electron transfer from the C{sub 59}N part to the C{sub 60} part in this charge-transfer complex.« less

Local structure investigation of Ga and Yb dopants in Co 4 Sb 12 skutterudites

DOE PAGES

Hu, Yanyun; Chen, Ning; Clancy, J. P.; ...

2017-12-29

We report our x-ray absorption spectroscopy studies at both Ga K-edge and Yb L 2-edge to elucidate the local structure of Ga and Yb dopants in Yb xGa yCo 4Sb 12. Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24g site replacing Sb, and the other is the 2a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2a on-center site. At low concentrations of Yb,more » Ga 24g and Ga 2a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Mater. 23, 3194 (2013)]. The Ga 24g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24g site for the highest Yb concentration (x = 0.4). In addition to the local crystal structure evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K-edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga 2a to Ga 24g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co 4Sb 12 skutterudites is due to the increased Ga 24g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.« less

Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites

NASA Astrophysics Data System (ADS)

Hu, Yanyun; Chen, Ning; Clancy, J. P.; Salvador, James R.; Kim, Chang-Yong; Shi, Xiaoya; Li, Qiang; Kim, Young-June

2017-12-01

We report comprehensive x-ray absorption spectroscopy studies at both the Ga K edge and Yb L2 edge to elucidate the local structure of Ga and Yb dopants in YbxGayCo4Sb12 . Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24 g site replacing Sb, and the other is the 2 a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2 a on-center site. At low concentrations of Yb, Ga24 g and Ga2 a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Funct. Mater. 23, 3194 (2013), 10.1002/adfm.201202571]. The Ga24 g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24 g site for the highest Yb concentration studied (x =0.4 ). In addition to the local structural evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K -edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga2 a to Ga24 g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co4Sb12 skutterudites is due to the increased Ga24 g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.

Local structure investigation of Ga and Yb dopants in Co 4 Sb 12 skutterudites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Yanyun; Chen, Ning; Clancy, J. P.

We report our x-ray absorption spectroscopy studies at both Ga K-edge and Yb L 2-edge to elucidate the local structure of Ga and Yb dopants in Yb xGa yCo 4Sb 12. Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24g site replacing Sb, and the other is the 2a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2a on-center site. At low concentrations of Yb,more » Ga 24g and Ga 2a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Mater. 23, 3194 (2013)]. The Ga 24g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24g site for the highest Yb concentration (x = 0.4). In addition to the local crystal structure evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K-edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga 2a to Ga 24g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co 4Sb 12 skutterudites is due to the increased Ga 24g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.« less

Coupling XRD, EXAFS, and 13C NMR to study the effect of the carbon stoichiometry on the local structure of UC(1±x).

PubMed

Carvajal Nuñez, U; Martel, L; Prieur, D; Lopez Honorato, E; Eloirdi, R; Farnan, I; Vitova, T; Somers, J

2013-10-07

A series of uranium carbide samples, prepared by arc melting with a C/U ratio ranging from 0.96 to 1.04, has been studied by X-ray diffraction (XRD), (13)C nuclear magnetic resonance (NMR), and extended X-ray absorption fine structure (EXAFS). XRD determines phase uniqueness and the increase of the lattice parameter versus the carbon content. In contrast, (13)C NMR detects the different carbon environments in the lattice and in this study, clearly identifies the presence of discrete peaks for carbon in the octahedral lattice site in UC and an additional peak associated with excess carbon in hyperstoichiometric samples. Two peaks associated with different levels of carbon deficiency are detected for all hypostoichiometric compositions. More than one carbon environment is always detected by (13)C NMR. This exemplifies the difficulty in obtaining a perfect stoichiometric uranium monocarbide UC(1.00). The (13)C MAS spectra of uranium carbides exhibit the effects resulting from the carbon content on both the broadening of the peaks and on the Knight shift. An abrupt spectral change occurs between hypo- and hyperstoichiometric samples. The results obtained by EXAFS highlight subtle differences between the different stoichiometries, and in the hyperstoichiometric samples, the EXAFS results are consistent with the excess carbon atoms being in the tetrahedral interstitial position.

Aqueous and solid phase speciation of arsenic in a Bengali aquifer using IC-ICP-MS and EXAFS

NASA Astrophysics Data System (ADS)

Gault, A. G.; Davidson, L. E.; Lythgoe, P. R.; Charnock, J. M.; Chatterjee, D.; Abou-Shakra, F. R.; Walker, H. J.; Polya, D. A.

2003-04-01

Contamination of groundwater and drinking water supplies with arsenic has been reported in many parts of the world and constitutes a serious public health threat. Nowhere is this more apparent than in West Bengal and Bangladesh where arsenic concentrations exceed both World Health Organisation (WHO) and national limits in drinking water supplies leading to what has been described as the worst mass poisoning of a human population in history. Knowledge of both aqueous and solid phase speciation of arsenic in such hazardous arsenic-rich groundwaters is crucial to understanding the processes controlling arsenic release. We report here preliminary work involving the determination of dissolved arsenic speciation in West Bengali groundwaters and extended X-ray absorption fine structure (EXAFS) analysis of the associated sediment. Groundwater samples collected from Nadia district, West Bengal were analysed for arsenic speciation by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) within 14 days of collection. Total arsenic concentrations exceeding 850 ug/L were determined; inorganic arsenic constituted the bulk of the dissolved arsenic burden with As(III) as the dominant form. Minor amounts of methylated arsenicals were also detected, however, their concentration did not exceed 5 ug/L. The local coordination environment of arsenic in sediment associated with such groundwaters was probed using K-edge As EXAFS. This revealed that arsenic exists predominantly in its oxidised form, As(V), most likely adsorbed as bidentate arsenate tetrahedra on metal (Fe and/or Al) oxide/hydroxide surfaces, although incorporation of arsenic into a metal oxide structure cannot be unequivocally ruled out. Arsenic was found to occur in several different coordination environments and this, together with the low concentration (< 5 ug/g) of arsenic in the sediment, prevented the unambiguous assignment of the second coordination sphere. The analysis of the trends of key

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Niibe, Masahito; Miyamoto, Kazuyoshi; Mitamura, Tohru

2010-09-15

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

Iron K-edge X-ray absorption near-edge structure spectroscopy of aerodynamically levitated silicate melts and glasses

DOE PAGES

Alderman, O. L. G.; Wilding, M. C.; Tamalonis, A.; ...

2017-01-26

Here, the local structure about Fe(II) and Fe(III) in silicate melts was investigated in-situ using iron K-edge X-ray absorption near-edge structure (XANES) spectroscopy. An aerodynamic levitation and laser heating system was used to allow access to high temperatures without contamination, and was combined with a chamber and gas mixing system to allow the iron oxidation state, Fe 3+/ΣFe, to be varied by systematic control of the atmospheric oxygen fugacity. Eleven alkali-free, mostly iron-rich and depolymerized base compositions were chosen for the experiments, including pure oxide FeO, olivines (Fe,Mg) 2SiO 4, pyroxenes (Fe,Mg)SiO 3, calcic FeO-CaSiO 3, and a calcium aluminosilicatemore » composition, where total iron content is denoted by FeO for convenience. Melt temperatures varied between 1410 and 2160 K and oxygen fugacities between FMQ – 2.3(3) to FMQ + 9.1(3) log units (uncertainties in parentheses) relative to the fayalite-magnetite-β-quartz (FMQ) buffer.« less

Pressure induced coordination change of Al in silicate melts from Al K edge XANES of high pressure NaAlSi2O6-NaAlSi3O8 glasses

NASA Astrophysics Data System (ADS)

Li, Dien; Secco, R. A.; Bancroft, G. M.; Fleet, M. E.

Aluminum K-edge XANES spectra of high pressure and high temperature (4.4 GPa and 1575°C) glasses along the NaAlSi2O6 (Jd)-NaAlSi3O8 (Ab) join are reported using synchrotron radiation, and shown to provide direct experimental evidence for the pressure-induced coordination change of Al. Five- and six-fold coordinated Al (5Al and 6Al), characterized by Al K-edge positions at 1567.8 and 1568.7 eV, respectively, first appear in glass of composition Jd60Ab40 and increase in proportion progressively with increasing Jd content. The end-member jadeite glass contains about 6% of each of 5Al and 6Al. The present direct measurements confirm literature suggestions for the important role of Al in controlling viscosity and diffusion in mantle melts.

Localized Ras signaling at the leading edge regulates PI3K, cell polarity, and directional cell movement

PubMed Central

Sasaki, Atsuo T.; Chun, Cheryl; Takeda, Kosuke; Firtel, Richard A.

2004-01-01

During chemotaxis, receptors and heterotrimeric G-protein subunits are distributed and activated almost uniformly along the cell membrane, whereas PI(3,4,5)P3, the product of phosphatidylinositol 3-kinase (PI3K), accumulates locally at the leading edge. The key intermediate event that creates this strong PI(3,4,5)P3 asymmetry remains unclear. Here, we show that Ras is rapidly and transiently activated in response to chemoattractant stimulation and regulates PI3K activity. Ras activation occurs at the leading edge of chemotaxing cells, and this local activation is independent of the F-actin cytoskeleton, whereas PI3K localization is dependent on F-actin polymerization. Inhibition of Ras results in severe defects in directional movement, indicating that Ras is an upstream component of the cell's compass. These results support a mechanism by which localized Ras activation mediates leading edge formation through activation of basal PI3K present on the plasma membrane and other Ras effectors required for chemotaxis. A feedback loop, mediated through localized F-actin polymerization, recruits cytosolic PI3K to the leading edge to amplify the signal. PMID:15534002

Progress in Noise Thermometry at 505 K and 693 K Using Quantized Voltage Noise Ratio Spectra

NASA Astrophysics Data System (ADS)

Tew, W. L.; Benz, S. P.; Dresselhaus, P. D.; Coakley, K. J.; Rogalla, H.; White, D. R.; Labenski, J. R.

2010-09-01

Technical advances and new results in noise thermometry at temperatures near the tin freezing point and the zinc freezing point using a quantized voltage noise source (QVNS) are reported. The temperatures are derived by comparing the power spectral density of QVNS synthesized noise with that of Johnson noise from a known resistance at both 505 K and 693 K. Reference noise is digitally synthesized so that the average power spectra of the QVNS match those of the thermal noise, resulting in ratios of power spectra close to unity in the low-frequency limit. Three-parameter models are used to account for differences in impedance-related time constants in the spectra. Direct comparison of noise temperatures to the International Temperature Scale of 1990 (ITS-90) is achieved in a comparison furnace with standard platinum resistance thermometers. The observed noise temperatures determined by operating the noise thermometer in both absolute and relative modes, and related statistics together with estimated uncertainties are reported. The relative noise thermometry results are combined with results from other thermodynamic determinations at temperatures near the tin freezing point to calculate a value of T - T 90 = +4(18) mK for temperatures near the zinc freezing point. These latest results achieve a lower uncertainty than that of our earlier efforts. The present value of T - T 90 is compared to other published determinations from noise thermometry and other methods.

An accurate method for computer-generating tungsten anode x-ray spectra from 30 to 140 kV.

PubMed

Boone, J M; Seibert, J A

1997-11-01

A tungsten anode spectral model using interpolating polynomials (TASMIP) was used to compute x-ray spectra at 1 keV intervals over the range from 30 kV to 140 kV. The TASMIP is not semi-empirical and uses no physical assumptions regarding x-ray production, but rather interpolates measured constant potential x-ray spectra published by Fewell et al. [Handbook of Computed Tomography X-ray Spectra (U.S. Government Printing Office, Washington, D.C., 1981)]. X-ray output measurements (mR/mAs measured at 1 m) were made on a calibrated constant potential generator in our laboratory from 50 kV to 124 kV, and with 0-5 mm added aluminum filtration. The Fewell spectra were slightly modified (numerically hardened) and normalized based on the attenuation and output characteristics of a constant potential generator and metal-insert x-ray tube in our laboratory. Then, using the modified Fewell spectra of different kVs, the photon fluence phi at each 1 keV energy bin (E) over energies from 10 keV to 140 keV was characterized using polynomial functions of the form phi (E) = a0[E] + a1[E] kV + a2[E] kV2 + ... + a(n)[E] kVn. A total of 131 polynomial functions were used to calculate accurate x-ray spectra, each function requiring between two and four terms. The resulting TASMIP algorithm produced x-ray spectra that match both the quality and quantity characteristics of the x-ray system in our laboratory. For photon fluences above 10% of the peak fluence in the spectrum, the average percent difference (and standard deviation) between the modified Fewell spectra and the TASMIP photon fluence was -1.43% (3.8%) for the 50 kV spectrum, -0.89% (1.37%) for the 70 kV spectrum, and for the 80, 90, 100, 110, 120, 130 and 140 kV spectra, the mean differences between spectra were all less than 0.20% and the standard deviations were less than approximately 1.1%. The model was also extended to include the effects of generator-induced kV ripple. Finally, the x-ray photon fluence in the units of

Photoionization Modeling of Oxygen K Absorption in the Interstellar Medium: The Chandra Grating Spectra of XTE J1817-330

NASA Technical Reports Server (NTRS)

Gatuzz, E.; Garcia, J.; Menodza, C.; Kallman, T. R.; Witthoeft, M.; Lohfink, A.; Bautista, M. A.; Palmeri, P.; Quinet, P.

2013-01-01

We present detailed analyses of oxygen K absorption in the interstellar medium (ISM) using four high-resolution Chandra spectra towards the X-ray low-mass binary XTE J1817-330. The 11-25 A broadband is described with a simple absorption model that takes into account the pileup effect and results in an estimate of the hydrogen column density. The oxygen K-edge region (21-25 A) is fitted with the physical warmabs model, which is based on a photoionization model grid generated with the XSTAR code with the most up-to-date atomic database. This approach allows a benchmark of the atomic data which involves wavelength shifts of both the K lines and photoionization cross sections in order to fit the observed spectra accurately. As a result we obtain: a column density of N(sub H) = 1.38 +/- 0.01 x 10(exp 21) cm(exp -2); ionization parameter of log xi = .2.70 +/- 0.023; oxygen abundance of A(sub O) = 0.689(exp +0.015./-0.010); and ionization fractions of O I/O = 0.911, O II/O = 0.077, and O III/O = 0.012 that are in good agreement with previous studies. Since the oxygen abundance in warmabs is given relative to the solar standard of Grevesse and Sauval (1998), a rescaling with the revision by Asplund et al. (2009) yields A(sub O) = 0.952(exp +0.020/-0.013, a value close to solar that reinforces the new standard. We identify several atomic absorption lines.K-alpha , K-beta, and K-gamma in O I and O II; and K-alpha in O III, O VI, and O VII--last two probably residing in the neighborhood of the source rather than in the ISM. This is the first firm detection of oxygen K resonances with principal quantum numbers n greater than 2 associated to ISM cold absorption.

Photoionization Modeling of Oxygen K Absorption in the Interstellar Medium:. [The Chandra Grating Spectra of XTE J1817-330

NASA Technical Reports Server (NTRS)

Gatuzz, E.; Garcia, J.; Mendoza, C.; Kallman, T. R.; Witthoeft, M.; Lohfink, A.; Bautista, M. A.; Palmeri, P.; Quinet, P.

2013-01-01

We present detailed analyses of oxygen K absorption in the interstellar medium (ISM) using four high-resolution Chandra spectra toward the X-ray low-mass binary XTE J1817-330. The 11-25 Angstrom broadband is described with a simple absorption model that takes into account the pile-up effect and results in an estimate of the hydrogen column density. The oxygen K-edge region (21-25 Angstroms) is fitted with the physical warmabs model, which is based on a photoionization model grid generated with the xstar code with the most up-to-date atomic database. This approach allows a benchmark of the atomic data which involves wavelength shifts of both the K lines and photoionization cross sections in order to fit the observed spectra accurately. As a result we obtain a column density of N(sub H) = 1.38 +/- 0.01 × 10(exp 21) cm(exp -2); an ionization parameter of log xi = -2.70 +/- 0.023; an oxygen abundance of A(sub O) = 0.689 (+0.015/-0.010); and ionization fractions of O(sub I)/O = 0.911, O(sub II)/O = 0.077, and O(sub III)/O = 0.012 that are in good agreement with results from previous studies. Since the oxygen abundance in warmabs is given relative to the solar standard of Grevesse & Sauval, a rescaling with the revision by Asplund et al. yields A(sub O) = 0.952(+0.020/-0.013), a value close to solar that reinforces the new standard.We identify several atomic absorption lines-K(alpha), K(beta), and K(gamma) in O(sub I) and O(sub II) and K(alpha) in O(sub III), O(sub VI), and O(sub VII)-the last two probably residing in the neighborhood of the source rather than in the ISM. This is the first firm detection of oxygen K resonances with principal quantum numbers n greater than 2 associated with ISM cold absorption.

Studying the local structures of novel materials using the Extended X-ray Absorption Fine Structure technique

NASA Astrophysics Data System (ADS)

Jiang, Yu

2009-12-01

In this dissertation, investigations on the local lattice structures for a variety of novel materials using Extended X-ray Absorption Fine Structure (EXAFS) technique are presented. Different experiment schemes were applied to obtain EXAFS data with high quality, and some interesting results were obtained by careful analysis. The power of the EXAFS technique was once again proved. In Chapter 1, I first briefly introduce the EXAFS theory and experiments, then give readers who are not familiar with this technique a short introduction on data reduction and analysis, and finally discuss some problems that are easily ignored in the interpretation of the experiment results. In Chapter 2, a temperature-dependent EXAFS investigation of La 1-xCaxMnO 3 is presented for the concentration range that spans the ferromagnetic-insulator (FMI) to ferromagnetic-metal (FMM) transition region, x = 0.16, 0.18, 0.20, and 0.22; the titrated hole concentrations are slightly higher y = 0.2, 0.22, 0.24, and 0.25 respectively. In Chapter 3, I report EXAFS studies of n- and p-type Ba8Ga 16Ge30 samples (type I clathrate) at the Ga, Ge, and Ba K-edges, to probe the local structure, particularly around the Ba atoms located inside 20- and 24-atom cages (Ba1 and Ba2 sites respectively) formed of Ga/Ge atoms. In agreement with diffraction analysis we find Ba2 is off-center, with a component in the bc plane (0.15 A) comparable to that found in diffraction; however, under the assumption of a stiff cage we also require a significant a component. This suggests a coupling or attraction between the Ba2 atoms and the hexagonal rings at the top or bottom of the cage that encloses the Ba2 site. In Chapter 4, I report detailed degradation and rejuvenation studies for AC electro-luminescence (EL) devices made using the phosphor ZnS:Cu,CI. We find that the AC EL emission spectra vary considerably with AC driving frequency but all spectra can be fit to a sum of four Gaussians. The combined experiments place

Cd(II) Sorption on Montmorillonite-Humic acid-Bacteria Composites

PubMed Central

Du, Huihui; Chen, Wenli; Cai, Peng; Rong, Xingmin; Dai, Ke; Peacock, Caroline L.; Huang, Qiaoyun

2016-01-01

Soil components (e.g., clays, bacteria and humic substances) are known to produce mineral-organic composites in natural systems. Herein, batch sorption isotherms, isothermal titration calorimetry (ITC), and Cd K-edge EXAFS spectroscopy were applied to investigate the binding characteristics of Cd on montmorillonite(Mont)-humic acid(HA)-bacteria composites. Additive sorption and non-additive Cd(II) sorption behaviour is observed for the binary Mont-bacteria and ternary Mont-HA-bacteria composite, respectively. Specifically, in the ternary composite, the coexistence of HA and bacteria inhibits Cd adsorption, suggesting a “blocking effect” between humic acid and bacterial cells. Large positive entropies (68.1 ~ 114.4 J/mol/K), and linear combination fitting of the EXAFS spectra for Cd adsorbed onto Mont-bacteria and Mont-HA-bacteria composites, demonstrate that Cd is mostly bound to bacterial surface functional groups by forming inner-sphere complexes. All our results together support the assertion that there is a degree of site masking in the ternary clay mineral-humic acid-bacteria composite. Because of this, in the ternary composite, Cd preferentially binds to the higher affinity components-i.e., the bacteria. PMID:26792640

Bromine speciation in hydrous haplogranitic melts up to 7 GPa

NASA Astrophysics Data System (ADS)

Cochain, B.; de Grouchy, C.; Crepisson, C.; Kantor, I.; Irifune, T.; Sanloup, C.

2013-12-01

Halogens are minor volatiles in the Earth's mantle and crust, but they have significant and specific influences on magmatic and degassing processes. They also provide insights about subsurface magma movement and eruption likelihood in subduction-related volcanism. Their speciation in silicate melts affects volatile exsolution, rheology, and the thermodynamic properties of the melts but still remains relatively unknown. A few studies have explored halogen speciation at room conditions, i.e. in glasses but no firm conclusion has yet been reached. Furthermore, halogen speciation remains unexplored at high pressures and temperatures. In this work we investigate the speciation of Br in subduction-related melt (hydrous haplogranite melt) up to 1200°C and 7 GPa using X-ray absorption spectroscopy (XANES and EXAFS) at the Br K-edge. High P-T conditions were generated by the Paris-Edinburgh press. The use of nanocrystalline diamond capsules enabled us to avoid glitches in the EXAFS spectra. The results provide valuable information on Br speciation and its evolution with pressure. It gives insights into solubility mechanisms for halogens in magmas at depth and on their degassing from the melt. In addition, we were able to identify quench effects on the atomic environment of Br by comparison of high P-T in-situ spectra and ex-situ spectra recorded on quenched samples.

Zinc sorption to three gram-negative bacteria: combined titration, modeling, and EXAFS study.

PubMed

Guiné, V; Spadini, L; Sarret, G; Muris, M; Delolme, C; Gaudet, J P; Martins, J M F

2006-03-15

The acid-base and Zn sorption properties of three bacteria, Cupriavidus metallidurans CH34, Pseudomonas putida ATCC12633, and Escherichia coli K12DH5alpha, were investigated through an original combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and equilibrium titration studies. Acid-base titration curves of the three strains were fitted with a model accounting for three conceptual reactive sites: an acidic (carboxyl and/or phosphodiester), a neutral (phosphomonoester), and a basic (amine and/or hydroxyl) group. Calculated proton and Zn equilibrium constants and site densities compare with literature data. The nature of Zn binding sites was studied by EXAFS spectroscopy. Phosphoester, carboxyl, and unexpectedly sulfhydryl ligands were identified. Their proportions depended on Zn loading and bacterial strain and were consistent with the titration results. These findings were compared to the structure and site density of the major cell wall components. It appeared that the cumulated theoretical site density of these structures (<2 Zn nm(-2)) was much lower than the total site density of the investigated strains (16-56 Zn nm(-2)). These results suggest a dominant role of extracellular polymeric substances in Zn retention processes, although Zn binding to inner cell components cannot be excluded.

Using Solution- and Solid-State S K-edge X-ray Absorption Spectroscopy with Density Functional Theory to Evaluate M–S Bonding for MS42- (M = Cr, Mo, W) Dianions

PubMed Central

Olson, Angela C.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Daly, Scott R.; Kozimor, Stosh A.; MacInnes, Molly M.; Martin, Richard L.; Scott, Brian L.

2014-01-01

Herein, we have evaluated relative changes in M–S electronic structure and orbital mixing in Group 6 MS42- dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t2* electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as 1A1 → 1T2 transitions. For MoS42-, both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS42-, solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t2* orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO42- dianions, which allowed M–S and M–O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M–E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M–S bonds, but increased appreciably for M–O interactions. For the t2* orbitals (σ* + π*), mixing decreased slightly for M–S bonding and increased only slightly for the M–O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME42- (E = O, S) dianions. PMID:25311904

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arber, J.M.; de Boer, E.; Garner, C.D.

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 datamore » 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.« less

Sequestration of Tellurium From Seawater by Ferromanganese Crusts: A XANES/EXAFS Perspective

NASA Astrophysics Data System (ADS)

Hein, J. R.; Bargar, J.; Koschinsky, A.; Dunham, R.; Halliday, A. N.

2007-12-01

Marine iron-oxyhydroxide/manganese-oxide crusts (Fe-Mn crusts) provide the richest known source of tellurium (Te). Te averages about 50 ppm in Fe-Mn crusts distributed globally, with concentrations locally up to 210 ppm. The sorption of Te onto Fe-Mn crusts likely controls the dominant redox species and concentration of Te in the global ocean (Hein et al., 2003). However, little is known about the mechanisms by which Te is sequestered by Fe-Mn crusts and Fe-Mn colloids in the water column, and then stabilized in the Fe/Mn oxyhydroxide/oxide framework. Two primary hypotheses are being tested: (a) Te(IV) is initially the predominant adsorbed species, which is subsequently oxidized on the Fe-oxyhydroxide and/or Mn oxide phases in natural systems and in sorption experiments. (b) Once oxidized, Te(VI) remains tightly bound to the Fe phase in Fe-Mn crusts as adsorbed surface complexes. These hypotheses are being examined by using the Stanford Synchrotron Radiation Laboratory's (SSRL) synchrotron-based XANES (x-ray absorption near-edge structure) spectroscopy to assess Te oxidation state in natural samples and samples in which Te(IV) and Te(VI) were sorbed onto synthetic and natural FeOOH and Mn oxides. EXAFS (extended x-ray absorption fine structure) spectroscopy is being used to resolve the local molecular-scale structure around Te in these same samples. Data have thus far been obtained for six Fe-Mn crusts from a variety of geographic locations and water depths of occurrence, with differing chemical compositions; and two model compounds, Te(IV) sorbed on FeOOH and Te(IV) sorbed on MnO2. XANES data show that for all six Fe-Mn crust samples, 85 to 100 percent of the Te occurs as Te(VI). For the model compounds, about 65 percent of the Te(IV) sorbed onto the MnO2 had oxidized to Te(VI) by the time (one week) the sample was analyzed, whereas Te sorbed onto FeOOH remained at about 100 percent Te(IV). The most striking result from the EXAFS data is that all spectra for the

Uptake of Nickel by Synthetic Mackinawite | Science Inventory ...

EPA Pesticide Factsheets

The uptake of aqueous Ni(II) by synthetic mackinawite (FeS) was examined in anaerobic batch experiments at near-neutral pH (5.2 to 8.4). Initial molar ratios of Ni(II) to FeS ranged from 0.008 to 0.83 and maximum Ni concentrations in mackinawite, expressed as the cation mol fraction, were as high as XNi = 0.56 (Fe1-xNixS; 0  x  1). Greater than 99% Ni removal from solution occurred when Ni loading remained below 0.13 ± 0.03 (1σ) mol Ni per mol FeS due to sorption of Ni at the mackinawite surface. Characterization of experimental solids using X-ray diffraction and Raman spectroscopy showed patterns characteristic of nanocrystalline mackinawite; no evidence of nickel monosulfide (α-NiS or millerite), polydymite (Ni3S4), or godlevskite [(Ni,Fe)9S8] formation was indicated regardless of the amount of Ni loading. Slight expansion of the c-axis correlated with increasing Ni content in synthetic mackinawite, from c = 5.07 ± 0.01 Å at XNi = 0.02 to c = 5.10 ± 0.01 Å at XNi = 0.38. Ni K-edge extended X-ray absorption fine structure (EXAFS) spectra of synthetic Ni-bearing mackinawite are similar in phase and amplitude to the Fe K-edge EXAFS spectrum of Ni-free mackinawite, indicating that the molecular environment of Ni2+ in Ni-bearing mackinawite is similar to that of Fe2+ in Ni-free mackinawite. EXAFS data fitting of Ni-bearing mackinawite with XNi = 0.42 indicated a coordination number of 4.04 ± 0.30 and an average Ni-S bond distance of 2.28 Å, in good a

XAS Study at Mo and Co K-Edges of the Sulfidation of a CoMo / Al2O3 Hydrotreating Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pichon, C.; Gandubert, A. D.; Legens, C.

2007-02-02

Because of its impact on environment, the removal of sulfur is an indispensable step, called hydrotreatment, in the refining of petroleum. One of the most commonly used hydrotreating catalysts is CoMo-type catalyst which is composed of molybdenum disulfide slabs promoted by cobalt atoms (CoMoS phase) and well dispersed on a high specific area alumina. As far as the highest sulfur content allowed in gasoline and diesel is continually decreasing, more and more efficient and active hydrotreating catalysts are required. In order to optimize the reactivity of the CoMo-type catalyst in hydrotreatment, a better understanding of the processes used to producemore » the active phase (CoMoS slabs) of the catalyst is necessary. The study reported here deals with the sulfiding mechanism of the slabs and the influence of temperature on the phenomenon. Ex situ X-ray absorption spectroscopy (XANES and EXAFS) was used to study the evolution of the structure of CoMo-type catalyst sulfided at various temperatures (from 293 to 873 K). XAS analysis was performed at both molybdenum and cobalt K-edges to obtain a cross-characterization of the sulfidation of the slabs. It evidenced the formation of various compounds, including two molybdenum oxides, MoS3 (or MoS3-like compound) and Co9S8, at specific steps of the sulfiding process. It showed the role of intermediate played by MoS3 (or MoS3-like compound) during the formation of the slabs and the competition between the appearance of promoted slabs (CoMoS phase) and Co9S8. At last, it leaded to the proposal of a mechanism for the sulfidation of the catalyst.« less

Simultaneous K-edge subtraction tomography for tracing strontium using parametric X-ray radiation

NASA Astrophysics Data System (ADS)

Hayakawa, Y.; Hayakawa, K.; Kaneda, T.; Nogami, K.; Sakae, T.; Sakai, T.; Sato, I.; Takahashi, Y.; Tanaka, T.

2017-07-01

The X-ray source based on parametric X-ray radiation (PXR) has been regularly providing a coherent X-ray beam for application studies at Nihon University. Recently, three dimensional (3D) computed tomography (CT) has become one of the most important applications of the PXR source. The methodology referred to as K-edge subtraction (KES) imaging is a particularly successful application utilizing the energy selectivity of PXR. In order to demonstrate the applicability of PXR-KES, a simultaneous KES experiment for a specimen containing strontium was performed using a PXR beam having an energy near the Sr K-edge of 16.1 keV. As a result, the 3D distribution of Sr was obtained by subtraction between the two simultaneously acquired tomographic images.

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

NASA Astrophysics Data System (ADS)

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

2005-05-01

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

X-ray Absorption and Emission Spectroscopy of CrIII (Hydr)Oxides: Analysis of the K-Pre-Edge Region

NASA Astrophysics Data System (ADS)

Frommer, Jakob; Nachtegaal, Maarten; Czekaj, Izabela; Weng, Tsu-Chien; Kretzschmar, Ruben

2009-10-01

Pre-edge spectral features below the main X-ray absorption K-edge of transition metals show a pronounced chemical sensitivity and are promising sources of structural information. Nevertheless, the use of pre-edge analysis in applied research is limited because of the lack of definite theoretical peak-assignments. The aim of this study was to determine the factors affecting the chromium K-pre-edge features in trivalent chromium-bearing oxides and oxyhydroxides. The selected phases varied in the degree of octahedral polymerization and the degree of iron-for-chromium substitution in the crystal structure. We investigated the pre-edge fine structure by means of high-energy-resolution fluorescence detected X-ray absorption spectroscopy and by 1s2p resonant X-ray emission spectroscopy. Multiplet theory and full multiple-scattering calculations were used to analyze the experimental data. We show that the chromium K-pre-edge contains localized and nonlocalized transitions. Contributions arising from nonlocalized metal-metal transitions are sensitive to the nearest metal type and to the linkage mode between neighboring metal octahedra. Analyzing these transitions opens up new opportunities for investigating the local coordination environment of chromium in poorly ordered solids of environmental relevance.

Application of an oscillation-type linear cadmium telluride detector to enhanced gadolinium K-edge computed tomography

NASA Astrophysics Data System (ADS)

Matsukiyo, Hiroshi; Sato, Eiichi; Hagiwara, Osahiko; Abudurexiti, Abulajiang; Osawa, Akihiro; Enomoto, Toshiyuki; Watanabe, Manabu; Nagao, Jiro; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

2011-03-01

A linear cadmium telluride (CdTe) detector is useful for carrying out energy-discrimination X-ray imaging, including computed tomography (CT). To perform enhanced gadolinium K-edge CT, we used an oscillation-type linear CdTe detector with an energy resolution of 1.2 keV. CT is performed by repeating the linear scan and the rotation of an object. Penetrating X-ray photons from the object are detected by the CdTe detector, and event signals of X-ray photons are produced using charge-sensitive and shaping amplifiers. Both the photon energy and the energy width are selected using a multichannel analyzer, and the number of photons is counted by a counter card. In energy-discrimination CT, tube voltage and current were 80 kV and 20 μA, respectively, and X-ray intensity was 1.55 μGy/s at 1.0 m from the source at a tube voltage of 80 kV. Demonstration of enhanced gadolinium K-edge X-ray CT was carried out by selecting photons with energies just beyond gadolinium K-edge energy of 50.3 keV.

Probing single magnon excitations in Sr₂IrO₄ using O K-edge resonant inelastic x-ray scattering.

PubMed

Liu, X; Dean, M P M; Liu, J; Chiuzbăian, S G; Jaouen, N; Nicolaou, A; Yin, W G; Rayan Serrao, C; Ramesh, R; Ding, H; Hill, J P

2015-05-27

Resonant inelastic x-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr2IrO4, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolution in the hard x-ray region is usually poor.

Silicon Detector System for High Rate EXAFS Applications.

PubMed

Pullia, A; Kraner, H W; Siddons, D P; Furenlid, L R; Bertuccio, G

1995-08-01

A multichannel silicon pad detector for EXAFS (Extended X-ray Absorption Fine Structure) applications has been designed and built. The X-ray spectroscopic measurements demonstrate that an adequate energy resolution of 230 eV FWHM (corresponding to 27 rms electrons in silicon) can be achieved reliably at -35 °C. A resolution of 190 eV FWHM (corresponding to 22 rms electrons) has been obtained from individual pads at -35 °C. At room temperature (25 °C) an average energy resolution of 380 eV FWHM is achieved and a resolution of 350 eV FWHM (41 rms electrons) is the best performance. A simple cooling system constituted of Peltier cells is sufficient to reduce the reverse currents of the pads and their related shot noise contribution, in order to achieve resolutions better than 300 eV FWHM which is adequate for the EXAFS applications.

Silicon Detector System for High Rate EXAFS Applications

PubMed Central

Pullia, A.; Kraner, H. W.; Siddons, D. P.; Furenlid, L. R.; Bertuccio, G.

2015-01-01

A multichannel silicon pad detector for EXAFS (Extended X-ray Absorption Fine Structure) applications has been designed and built. The X-ray spectroscopic measurements demonstrate that an adequate energy resolution of 230 eV FWHM (corresponding to 27 rms electrons in silicon) can be achieved reliably at −35 °C. A resolution of 190 eV FWHM (corresponding to 22 rms electrons) has been obtained from individual pads at −35 °C. At room temperature (25 °C) an average energy resolution of 380 eV FWHM is achieved and a resolution of 350 eV FWHM (41 rms electrons) is the best performance. A simple cooling system constituted of Peltier cells is sufficient to reduce the reverse currents of the pads and their related shot noise contribution, in order to achieve resolutions better than 300 eV FWHM which is adequate for the EXAFS applications. PMID:26538683

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mantouvalou, I., E-mail: ioanna.mantouvalou@tu-berlin.de; Witte, K.; Martyanov, W.

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.more » Hence, investigations of radiation sensitive biological specimen become possible due to the high efficiency of the optical elements enabling low dose experiments.« less

Photoinduced Effects in the ZnO Luminescence Spectra

NASA Astrophysics Data System (ADS)

Akopyan, I. Kh.; Labzovskaya, M. E.; Novikov, B. V.; Lisachenko, A. A.; Serov, A. Yu.; Filosofov, N. G.

2018-02-01

The effect of intense UV irradiation on the photoluminescence (PL) spectra of ZnO powders and nanocrystalline films obtained by atomic layer deposition (ALD) was investigated. At room temperature, the behavior of the spectra under continuous UV irradiation in multiple vacuum-atmosphere cycles was studied. The changes in the intensities of exciton radiation and radiation in the "green" band region, associated with the phenomena of oxygen photodesorption and photoadsorption, are discussed. In the temperature range of 5-300 K, the effect of strong UV irradiation on the near-edge luminescence spectrum of ZnO films was studied. The nature of a new line arising in the photoluminescence spectra of an irradiated film in the region of emission of bound excitons is discussed.

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M-S bonding for MS4(2-) (M = Cr, Mo, W) dianions.

PubMed

Olson, Angela C; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Daly, Scott R; Kozimor, Stosh A; MacInnes, Molly M; Martin, Richard L; Scott, Brian L

2014-12-14

Herein, we have evaluated relative changes in M-S electronic structure and orbital mixing in Group 6 MS4(2-) dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as (1)A1 → (1)T2 transitions. For MoS4(2-), both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS4(2-), solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO4(2-) dianions, which allowed M-S and M-O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M-E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M-S bonds, but increased appreciably for M-O interactions. For the t orbitals (σ* + π*), mixing decreased slightly for M-S bonding and increased only slightly for the M-O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME4(2-) (E = O, S) dianions.

Sorption of Metal Ions on Clay Minerals.

PubMed

Schlegel; Manceau; Chateigner; Charlet

1999-07-01

The local structural environment of Co sorbed on hectorite (a magnesian smectite) has been investigated by polarized EXAFS (P-EXAFS) spectroscopy on a self-supporting film of Co-sorbed hectorite. This sorption sample was prepared by contacting Co and hectorite at pH 6.5 and at high ionic strength (0.3 M NaNO3) to favor pH-dependent sorption reaction over cation exchange. A self-supporting film was elaborated after 120 h of reacting time, when apparent quasi-equilibrium conditions were attained. The half-width at half maximum of the orientation distribution of c* axis of individual clay platelets off the film normal was determined by quantitative texture analysis, and found to be equal to 18.9 degrees. Co K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 0 degrees, 35 degrees, 50 degrees, and 60 degrees; the 90 degrees spectrum was obtained by extrapolation. Spectral analysis led to the identification of the two nearest cationic subshells containing 1.6 +/- 0.4 Mg at 3.03 Å and 2.2 +/- 0.5 Si at 3.27 Å. These distances are respectively characteristic of edge-sharing linkages between Mg and Co octahedra and of corner-sharing linkages between Co octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Co-Mg and Co-Si contributions indicates that Co-Mg pairs are oriented parallel to the film plane, whereas Co-Si pairs are not. These results are interpreted by the formation of Co inner-sphere mononuclear surface complexes located at the edges of hectorite platelets, in the continuity of the (Mg, Li) octahedral sheet. Copyright 1999 Academic Press.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan, Grace 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,more » 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.« less

EXAFS and XANES analysis of oxides at the nanoscale.

PubMed

Kuzmin, Alexei; Chaboy, Jesús

2014-11-01

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

Zinc speciation in mining and smelter contaminated overbank sediments by EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Van Damme, An; Degryse, Fien; Smolders, Erik; Sarret, Géraldine; Dewit, Julie; Swennen, Rudy; Manceau, Alain

2010-07-01

Overbank sediments contaminated with metalliferous minerals are a source of toxic metals that pose risks to living organisms. The overbank sediments from the Geul river in Belgium contain 4000-69,000 mg/kg Zn as a result of mining and smelting activities, principally during the 19th century. Three main Zn species were identified by powder Zn K-edge EXAFS spectroscopy: smithsonite (ZnCO 3), tetrahedrally coordinated sorbed Zn (sorbed IVZn) and Zn-containing trioctahedral phyllosilicate. Smithsonite is a primary mineral, which accounts for approximately 20-60% of the Zn in sediments affected by mining and smelting of oxidized Zn ores (mostly carbonates and silicates). This species is almost absent in sediments affected by mining and smelting of both sulphidic (ZnS, PbS) and oxidized ores, presumably because of acidic dissolution associated with the oxidation of sulphides, as suggested by the lower pH of this second type of sediment (pH(CaCl 2) <7.0 vs. pH(CaCl 2) >7.0 for the first type). Thus, sulphide minerals in sediment deposits can act as a secondary source of dissolved metals by a chemical process analogous to acid mine drainage. The sorbed IVZn component ranges up to approximately 30%, with the highest proportion occurring at pH(CaCl 2) <7.0 as a result of the readsorption of dissolved Zn 2+ on sediments constituents. Kerolite-like Zn-rich phyllosilicate is the major secondary species in all samples, and in some the only detected species, thus providing the first evidence for pervasive sequestration of Zn into this newly formed precipitate at the field scale.

GPI Spectra of HR8799 C, D, and E in H-K Bands with KLIP Forward Modeling

NASA Technical Reports Server (NTRS)

Greenbaum, Alexandra Z.; Pueyo, Laurent; Ruffio, Jean-Baptiste; Wang, Jason J.; De Rosa, Robert J.; Aguilar, Jonathan; Rameau, Julien; Barman, Travis; Marois, Christian; Marley, Mark S.;

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Westre, Tami E.

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→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 appliedmore » to the study of non-heme iron enzyme active sites.« less

Determination of the ground state of an Au-supported FePc film based on the interpretation of Fe K - and L -edge x-ray magnetic circular dichroism measurements

NASA Astrophysics Data System (ADS)

Natoli, Calogero R.; Krüger, Peter; Bartolomé, Juan; Bartolomé, Fernando

2018-04-01

We determine the magnetic ground state of the FePc molecule on Au-supported thin films based on the observed values of orbital anisotropy and spectroscopic x-ray magnetic circular dichroism (XMCD) measurements at the Fe K and L edges. Starting from ab initio molecular orbital multiplet calculations for the isolated molecule, we diagonalize the spin-orbit interaction in the subspace spanned by the three lowest spin triplet states of 3A2 g and 3Eg symmetry in the presence of a saturating magnetic field at a polar angle θ with respect to the normal to the plane of the film, plus an external perturbation representing the effect of the molecules in the stack on the FePc molecule under consideration. We find that the orbital moment of the ground state strongly depends on the magnetic field direction in agreement with the sum rule analysis of the L23-edge XMCD data. We calculate integrals over the XMCD spectra at the Fe K and L23 edges as used in the sum rules and explicitly show that they agree with the expectation values of the orbital moment and effective spin moment of the ground state. On the basis of this analysis, we can rule out alternative candidates proposed in the literature.

Molybdenum X-Ray Absorption Edges from 200 – 20,000 eV, The Benefits of Soft X-Ray Spectroscopy for Chemical Speciation

PubMed Central

George, Simon J.; Drury, Owen B.; Fu, Juxia; Friedrich, Stephan; Doonan, Christian J.; George, Graham N.; White, Jonathan M.; Young, Charles G.; Cramer, Stephen P.

2009-01-01

We have surveyed the chemical utility of the near-edge structure of molybdenum x-ray absorption edges from the hard x-ray K-edge at 20,000 eV down to the soft x-ray M4,5-edges at ~230 eV. We compared, for each edge, the spectra of two tetrahedral anions, MoO4 and MoS42-. We used three criteria for assessing near-edge structure of each edge: (i) the ratio of the observed chemical shift between MoO42- and MoS42- and the linewidth, (ii) the chemical information from analysis of the near-edge structure and (iii) the ease of measurement using fluorescence detection. Not surprisingly, the K-edge was by far the easiest to measure, but it contained the least information. The L2,3-edges, although harder to measure, had benefits with regard to selection rules and chemical speciation in that they had both a greater chemical shift as well as detailed lineshapes which could be theoretically analyzed in terms of Mo ligand field, symmetry, and covalency. The soft x-ray M2,3-edges were perhaps the least useful, in that they were difficult to measure using fluorescence detection and had very similar information content to the corresponding L2,3-edges. Interestingly, the soft x-ray, low energy (~230 eV) M4,5-edges had greatest potential chemical sensitivity and using our high resolution superconducting tunnel junction (STJ) fluorescence detector they appear to be straightforward to measure. The spectra were amenable to analysis using both the TT-multiplet approach and FEFF. The results using FEFF indicate that the sharp near-edge peaks arise from 3d → 5p transitions, while the broad edge structure has predominately 3d → 4f character. A proper understanding of the dependence of these soft x-ray spectra on ligand field and site geometry is necessary before a complete assessment of the utility of the Mo M4,5-edges can be made. This work includes crystallographic characterization of sodium tetrathiomolybdate. PMID:19041140

Sensitivity of photon-counting based K-edge imaging in X-ray computed tomography.

PubMed

Roessl, Ewald; Brendel, Bernhard; Engel, Klaus-Jürgen; Schlomka, Jens-Peter; Thran, Axel; Proksa, Roland

2011-09-01

The feasibility of K-edge imaging using energy-resolved, photon-counting transmission measurements in X-ray computed tomography (CT) has been demonstrated by simulations and experiments. The method is based on probing the discontinuities of the attenuation coefficient of heavy elements above and below the K-edge energy by using energy-sensitive, photon counting X-ray detectors. In this paper, we investigate the dependence of the sensitivity of K-edge imaging on the atomic number Z of the contrast material, on the object diameter D , on the spectral response of the X-ray detector and on the X-ray tube voltage. We assume a photon-counting detector equipped with six adjustable energy thresholds. Physical effects leading to a degradation of the energy resolution of the detector are taken into account using the concept of a spectral response function R(E,U) for which we assume four different models. As a validation of our analytical considerations and in order to investigate the influence of elliptically shaped phantoms, we provide CT simulations of an anthropomorphic Forbild-Abdomen phantom containing a gold-contrast agent. The dependence on the values of the energy thresholds is taken into account by optimizing the achievable signal-to-noise ratios (SNR) with respect to the threshold values. We find that for a given X-ray spectrum and object size the SNR in the heavy element's basis material image peaks for a certain atomic number Z. The dependence of the SNR in the high- Z basis-material image on the object diameter is the natural, exponential decrease with particularly deteriorating effects in the case where the attenuation from the object itself causes a total signal loss below the K-edge. The influence of the energy-response of the detector is very important. We observed that the optimal SNR values obtained with an ideal detector and with a CdTe pixel detector whose response, showing significant tailing, has been determined at a synchrotron differ by factors of

Dynamic study of sub-micro sized LiFePO4 cathodes by in-situ tender X-ray absorption near edge structure

NASA Astrophysics Data System (ADS)

Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong

2016-01-01

Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.

Two-Photon Absorption of Soft X-Ray Free Electron Laser Radiation by Graphite Near the Carbon K-Absorption Edge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christensen, Steven T; Lam, Royce K.; Raj, Sumana L.

We have examined the transmission of soft X-ray pulses from the FERMI free electron laser through carbon films of varying thickness, quantifying nonlinear effects of pulses above and below the carbon K-edge. At typical of soft X-ray free electron laser intensities, pulses exhibit linear absorption at photon energies above and below the K-edge, ~308 and ~260 eV, respectively; whereas two-photon absorption becomes significant slightly below the K-edge, ~284.2 eV. The measured two-photon absorption cross section at 284.18 eV (~6 x 10-48 cm4 s) is 7 orders of magnitude above what is expected from a simple theory based on hydrogen-like atomsmore » - a result of resonance effects.« less

Two-photon absorption of soft X-ray free electron laser radiation by graphite near the carbon K-absorption edge

NASA Astrophysics Data System (ADS)

Lam, Royce K.; Raj, Sumana L.; Pascal, Tod A.; Pemmaraju, C. D.; Foglia, Laura; Simoncig, Alberto; Fabris, Nicola; Miotti, Paolo; Hull, Christopher J.; Rizzuto, Anthony M.; Smith, Jacob W.; Mincigrucci, Riccardo; Masciovecchio, Claudio; Gessini, Alessandro; De Ninno, Giovanni; Diviacco, Bruno; Roussel, Eleonore; Spampinati, Simone; Penco, Giuseppe; Di Mitri, Simone; Trovò, Mauro; Danailov, Miltcho B.; Christensen, Steven T.; Sokaras, Dimosthenis; Weng, Tsu-Chien; Coreno, Marcello; Poletto, Luca; Drisdell, Walter S.; Prendergast, David; Giannessi, Luca; Principi, Emiliano; Nordlund, Dennis; Saykally, Richard J.; Schwartz, Craig P.

2018-07-01

We have examined the transmission of soft X-ray pulses from the FERMI free electron laser through carbon films of varying thickness, quantifying nonlinear effects of pulses above and below the carbon K-edge. At typical of soft X-ray free electron laser intensities, pulses exhibit linear absorption at photon energies above and below the K-edge, ∼308 and ∼260 eV, respectively; whereas two-photon absorption becomes significant slightly below the K-edge, ∼284.2 eV. The measured two-photon absorption cross section at 284.18 eV (∼6 × 10-48 cm4 s) is 7 orders of magnitude above what is expected from a simple theory based on hydrogen-like atoms - a result of resonance effects.

Synchrotron-based XAS on structure investigation of La0.99-xSrx(Na, K, Ba)0.01MnO3 nanoparticles: Evidence of magnetic properties

NASA Astrophysics Data System (ADS)

Daengsakul, Sujittra; Saengplot, Saowalak; Kidkhunthod, Pinit; Pimsawat, Adulphan; Maensiri, Santi

2018-04-01

This work presents the structural study of La0.99-xSrx(Na, K, Ba)0.01MnO3 or LSAM nanoparticles synthesized using thermal-hydro decomposition method where A denotes Na, K, Sr and Ba, respectively. The effect of ionic radii size of A dopants or rA from the substitution of A for La and Sr on the MnO6 octrahedral structure, where the average size of the cations occupying in A-site or 〈rA〉 is fixed at ∼ 1.24 Å, is focused. The LSAM nanoparticles are carefully studied using X-ray diffraction (XRD) including Rietveld refinement and X-ray Absorption Spectroscopy (XAS) including X-ray Absorption Near edge Structure (XANES) and X-ray Absorption Fine Structure (EXAFS). The Rietveld refinement shows all nano-powder samples have rhombohedral structure. By XANES technique we found that the effect of A substitutions at A-site causes a slight change of mean oxidation state of Mn between 3.54 and 3.60. Furthermore, the structural distortion of MnO6 octrahedral in samples is analysed and obtained from EXAFS. The observed trend of ferromagnetism for all LSAM samples can be clearly explained by evidences of A-site doping, structural distortion around Mn atoms and mixing Mn3+/Mn4+ valence states.

Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

DOE PAGES

Van Kuiken, Benjamin E.; Ross, Matthew R.; Strader, Matthew L.; ...

2017-05-08

Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (~2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps)more » and decays within 6 ns. The second transient species forms on a timescale of ~400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowestlying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.« less

Synchrotron speciation data for zero-valent iron nanoparticles

EPA Pesticide Factsheets

This data set encompasses a complete analysis of synchrotron speciation data for 5 iron nanoparticle samples (P1, P2, P3, S1, S2, and metallic iron) to include linear combination fitting results (Table 6 and Figure 9) and ab-initio extended x-ray absorption fine structure spectroscopy fitting (Figure 10 and Table 7).Table 6: Linear combination fitting of the XAS data for the 5 commercial nZVI/ZVI products tested. Species proportions are presented as percentages. Goodness of fit is indicated by the chi^2 value.Figure 9: Normalised Fe K-edge k3-weighted EXAFS of the 5 commercial nZVI/ZVIproducts tested. Dotted lines show the best 4-component linear combination fit ofreference spectra.Figure 10: Fourier transformed radial distribution functions (RDFs) of the five samplesand an iron metal foil. The black lines in Fig. 10 represent the sample data and the reddotted curves represent the non-linear fitting results of the EXAFS data.Table 7: Coordination parameters of Fe in the samples.This dataset is associated with the following publication:Chekli, L., B. Bayatsarmadi, R. Sekine, B. Sarkar, A. Maoz Shen, K. Scheckel , W. Skinner, R. Naidu, H. Shon, E. Lombi, and E. Donner. Analytical Characterisation of Nanoscale Zero-Valent Iron: A Methodological Review. Richard P. Baldwin ANALYTICA CHIMICA ACTA. Elsevier Science Ltd, New York, NY, USA, 903: 13-35, (2016).

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

NASA Astrophysics Data System (ADS)

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

2001-09-01

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

Evidence for Al/Si tetrahedral network in aluminosilicate glasses from Al K-edge x-ray-absorption spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Ziyu; Romano, C.; Marcelli, A.; Mottana, A.; Cibin, G.; della Ventura, G.; Giuli, G.; Courtial, P.; Dingwell, D. B.

1999-10-01

The structure of aluminosilicate melts and/or glasses plays a key role in the earth sciences for the understanding of rock-forming igneous processes, as well as in the materials sciences for their technical applications. In particular, the alkaline-earth aluminosilicate glasses are an extremely important group of materials, with a wide range of commercial application, as well as serving as an analog for natural basaltic melts. However, definition of their structure and properties is still controversial, and in particular the role and effect of Al has long been a subject of debate. Here we report a series of experimental x-ray absorption near-edge structure spectra at the Al K edge on a series of synthetic glasses of peralkaline composition in the CaO-Al2O3-SiO2 system, together with a general theoretical framework for data analysis based on an ab initio full multiple-scattering theory. We propose an Al/Si tetrahedral network model for aluminosilicate glasses based on distorted polyhedra, with varying both the T-O (T=Al or Si) bond lengths and the T-O-T angles, and with different Al/Si composition. This model achieves a significant agreement between experiments and simulations. In these glasses, experimental data and theoretical results concur to support a model in which Al is network former with a comparatively well ordered local medium-range order (up to 5 Å).

Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

NASA Astrophysics Data System (ADS)

Moon, Ellen M.; Peacock, Caroline L.

2011-11-01

Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

Identification of the iron oxidation state and coordination geometry in iron oxide- and zeolite-based catalysts using pre-edge XAS analysis.

PubMed

Boubnov, Alexey; Lichtenberg, Henning; Mangold, Stefan; Grunwaldt, Jan Dierk

2015-03-01

Analysis of the oxidation state and coordination geometry using pre-edge analysis is attractive for heterogeneous catalysis and materials science, especially for in situ and time-resolved studies or highly diluted systems. In the present study, focus is laid on iron-based catalysts. First a systematic investigation of the pre-edge region of the Fe K-edge using staurolite, FePO4, FeO and α-Fe2O3 as reference compounds for tetrahedral Fe(2+), tetrahedral Fe(3+), octahedral Fe(2+) and octahedral Fe(3+), respectively, is reported. In particular, high-resolution and conventional X-ray absorption spectra are compared, considering that in heterogeneous catalysis and material science a compromise between high-quality spectroscopic data acquisition and simultaneous analysis of functional properties is required. Results, which were obtained from reference spectra acquired with different resolution and quality, demonstrate that this analysis is also applicable to conventionally recorded pre-edge data. For this purpose, subtraction of the edge onset is preferentially carried out using an arctangent and a first-degree polynomial, independent of the resolution and quality of the data. For both standard and high-resolution data, multiplet analysis of pre-edge features has limitations due to weak transitions that cannot be identified. On the other hand, an arbitrary empirical peak fitting assists the analysis in that non-local transitions can be isolated. The analysis of the oxidation state and coordination geometry of the Fe sites using a variogram-based method is shown to be effective for standard-resolution data and leads to the same results as for high-resolution spectra. This method, validated by analysing spectra of reference compounds and their well defined mixtures, is finally applied to track structural changes in a 1% Fe/Al2O3 and a 0.5% Fe/BEA zeolite catalyst during reduction in 5% H2/He. The results, hardly accessible by other techniques, show that Fe(3+) is

Alteration of sediments by hyperalkaline K-rich cement leachate: implications for strontium adsorption and incorporation.

PubMed

Wallace, Sarah H; Shaw, Samuel; Morris, Katherine; Small, Joe S; Burke, Ian T

2013-04-16

Results are presented from 1 year batch experiments where K-rich hyperalkaline pH 13.5 young cement water (YCW) was reacted with sediments to investigate the effect of high pH, mineral alteration, and secondary mineral precipitation on (90)Sr sorption. After reaction with YCW, Sr sorption was found to be greater than 75% in all samples up to 365 days and 98% in a sample reacted for 365 days at 70 °C. Scanning electron microscopy analysis of sediment samples reacted at room temperature showed surface alteration and precipitation of a secondary phase, likely a K-rich aluminosilicate gel. The presence of Sr-Si(Al) bond distances in Sr K-edge extended X-ray absorption fine structure (EXAFS) analysis suggested that the Sr was present as an inner-sphere adsorption complex. However, sequential extractions found the majority of this Sr was still exchangeable with Mg(2+) at pH 7. For the sample reacted for 1 year at 70 °C, EXAFS analysis revealed clear evidence for ∼6 Sr-Si(Al) backscatters at 3.45 Å, consistent with Sr incorporation into the neoformed K-chabazite phase that was detected by X-ray diffraction and electron microscopy. Once incorporated into chabazite, (90)Sr was not exchangeable with Mg(2+), and chemical leaching with pH 1.5 HNO3 was required to remobilize 60% of the (90)Sr. These results indicate that, in high pH cementitious leachate, there is significantly enhanced Sr retention in sediments due to changes in the adsorption mechanism and incorporation into secondary silicate minerals. This suggests that Sr retention may be enhanced in this high pH zone and that the incorporation process may lead to irreversible exchange of the contaminant over extended time periods.

Cost and sensitivity of restricted active-space calculations of metal L-edge X-ray absorption spectra.

PubMed

Pinjari, Rahul V; Delcey, Mickaël G; Guo, Meiyuan; Odelius, Michael; Lundberg, Marcus

2016-02-15

The restricted active-space (RAS) approach can accurately simulate metal L-edge X-ray absorption spectra of first-row transition metal complexes without the use of any fitting parameters. These characteristics provide a unique capability to identify unknown chemical species and to analyze their electronic structure. To find the best balance between cost and accuracy, the sensitivity of the simulated spectra with respect to the method variables has been tested for two models, [FeCl6 ](3-) and [Fe(CN)6 ](3-) . For these systems, the reference calculations give deviations, when compared with experiment, of ≤1 eV in peak positions, ≤30% for the relative intensity of major peaks, and ≤50% for minor peaks. When compared with these deviations, the simulated spectra are sensitive to the number of final states, the inclusion of dynamical correlation, and the ionization potential electron affinity shift, in addition to the selection of the active space. The spectra are less sensitive to the quality of the basis set and even a double-ζ basis gives reasonable results. The inclusion of dynamical correlation through second-order perturbation theory can be done efficiently using the state-specific formalism without correlating the core orbitals. Although these observations are not directly transferable to other systems, they can, together with a cost analysis, aid in the design of RAS models and help to extend the use of this powerful approach to a wider range of transition metal systems. © 2015 Wiley Periodicals, Inc.

Determination of interstitial oxygen atom position in U2N3+xOy by near edge structure study

NASA Astrophysics Data System (ADS)

Jiang, A. K.; Zhao, Y. W.; Long, Z.; Hu, Y.; Wang, X. F.; Yang, R. L.; Bao, H. L.; Zeng, R. G.; Liu, K. Z.

2018-06-01

The determination of interstitial oxygen atom site in U2N3+xOy film could facilitate the understanding of the oxidation mechanism of α-U2N3 and the effect of U2N3+xOy on anti-oxidation. By comparing the similarities and variances between N K edge and O K edge electron energy loss spectra (EELS) for oxidized α-U2N3 and UO2, the present work looks at the local structure of nitrogen and oxygen atoms in U2N3+xOy film, identifying the most possible position of interstitial O atom.

High resolution spectroscopy over 8500-8750 Å for GAIA <= 7500 K. II. A library of synthetic spectra for T_eff <= 7500 K

NASA Astrophysics Data System (ADS)

Munari, U.; Castelli, F.

2000-01-01

We present a library of synthetic spectra characterized by -2.5 <= [Z/Z_sun] <= +0.5, 4.5 <= log g<= 1.0, and Teff <= 7500 K computed at the same lambda /bigtriangleup lambda = 20000 resolving power of the observed spectra given in Paper I for 131 standard stars mapping the MKK spectral classification system. This range of parameters includes the majority of the galactic stars expected to dominate the GAIA target population, i.e. F-G-K-M type stars with metallicity ranging from that of the galactic globular clusters to Population I objects. Extension to Teff > 7500 K will be given later on in this series. The 254 synthetic spectra presented here are based on Kurucz's codes and line data and have been computed over a more extended wavelength interval (7650-8750 Ä) than that currently baselined for implementation on GAIA, i.e. the 8500-8750 Ä. This last range is dominated by the near-IR Ca II triplet and the head of the Paschen series. The more extended wavelength range allows us to investigate the behaviour of other strong near-IR spectral features (severely contaminated by telluric absorptions in ground-based observed spectra) as the K I doublet (7664, 7699 Ä), the Na I doublet (8183, 8194 Ä) and the lines of Fe I multiplet N.60 at 8327 and 8388 Ä. The synthetic spectra support our previous conclusions about the superior performance of the Paschen/Ca II 8500-8750 Ä region in meeting the GAIA requirements when compared to other near-IR intervals of similar bigtriangleup lambda = 250 Ä. Table 2 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/Abstract.html Figures 5-93 are only available in electronic form at the http://www.edpsciences.org The spectra are also available in electronic form at the CDS or via the personal HomePage http://ulisse.pd.astro.it/Astro/Atlases/

In situ XANES and EXAFS Analysis of Redox Active Fe Center Ionic Liquids

DOE PAGES

Apblett, Christopher A.; Stewart, David M.; Fryer, Robert T.; ...

2015-10-23

We apply in situ X-Ray Absorption Near Edge Spectroscopy (XANES) and Extended X-Ray Absorption Fine Structure (EXAFS) techniques to a metal center ionic liquid undergoing oxidation and reduction in a three electrode spectroscopic cell. Furthermore, the determination of the extent of reduction under negative bias on the working electrode and the extent of oxidation are determined after pulse voltammetry to quiescence. While the ionic liquid undergoes full oxidation, it undergoes only partial reduction, likely due to transport issues on the timescale of the experiment. Nearest neighbor Fe-O distances in the fully oxidized state match well to expected values for similarlymore » coordinated solids, but reduction does not result in an extension of the Fe-O bond length, as would be expected from comparisons to the solid phase. Instead, little change in bond length is observed. Finally, we suggest that this may be due to a more complex interaction between the monodentate ligands of the metal center anion and the surrounding charge cloud, rather than straightforward electrostatics between the metal center and the nearest neighbor grouping.« less

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

NASA Astrophysics Data System (ADS)

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

1999-11-01

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

K-edge energy-based calibration method for photon counting detectors

NASA Astrophysics Data System (ADS)

Ge, Yongshuai; Ji, Xu; Zhang, Ran; Li, Ke; Chen, Guang-Hong

2018-01-01

In recent years, potential applications of energy-resolved photon counting detectors (PCDs) in the x-ray medical imaging field have been actively investigated. Unlike conventional x-ray energy integration detectors, PCDs count the number of incident x-ray photons within certain energy windows. For PCDs, the interactions between x-ray photons and photoconductor generate electronic voltage pulse signals. The pulse height of each signal is proportional to the energy of the incident photons. By comparing the pulse height with the preset energy threshold values, x-ray photons with specific energies are recorded and sorted into different energy bins. To quantitatively understand the meaning of the energy threshold values, and thus to assign an absolute energy value to each energy bin, energy calibration is needed to establish the quantitative relationship between the threshold values and the corresponding effective photon energies. In practice, the energy calibration is not always easy, due to the lack of well-calibrated energy references for the working energy range of the PCDs. In this paper, a new method was developed to use the precise knowledge of the characteristic K-edge energy of materials to perform energy calibration. The proposed method was demonstrated using experimental data acquired from three K-edge materials (viz., iodine, gadolinium, and gold) on two different PCDs (Hydra and Flite, XCounter, Sweden). Finally, the proposed energy calibration method was further validated using a radioactive isotope (Am-241) with a known decay energy spectrum.

Soft x-ray absorption spectra of ilmenite family.

PubMed

Agui, A; Mizumaki, M; Saitoh, Y; Matsushita, T; Nakatani, T; Fukaya, A; Torikai, E

2001-03-01

We have carried out soft x-ray absorption spectroscopy to study the electronic structure of ilmenite family, such as MnTiO3, FeTiO3, and CoTiO3 at the soft x-ray beamline, BL23SU, at the SPring-8. The Ti and M L2,3 absorption spectra of MTiO3 (M=Mn, Fe, and Co) show spectra of Ti4+ and M2+ electron configurations, respectively. Except the Fe L2,3 spectrum, those spectra were understood within the O(h) symmetry around the transition metal ions. The Fe L3-edge spectrum clearly shows a doublet peak at the L3 edge, which is attributed to Fe2+ state, moreover the very high-resolution the L-edge spectra of transition metals show fine structures. The spectra of those ilmenites are compared.

Theory and X-ray Absorption Spectroscopy for Aluminum Coordination Complexes – Al K-Edge Studies of Charge and Bonding in (BDI)Al, (BDI)AlR2, and (BDI)AlX2 Complexes.

PubMed

Altman, Alison B; Pemmaraju, C D; Camp, Clément; Arnold, John; Minasian, Stefan G; Prendergast, David; Shuh, David K; Tyliszczak, Tolek

2015-08-19

Polarized aluminum K-edge X-ray absorption near edge structure (XANES) spectroscopy and first-principles calculations were used to probe electronic structure in a series of (BDI)Al, (BDI)AlX2, and (BDI)AlR2 coordination compounds (X = F, Cl, I; R = H, Me; BDI = 2,6-diisopropylphenyl-β-diketiminate). Spectral interpretations were guided by examination of the calculated transition energies and polarization-dependent oscillator strengths, which agreed well with the XANES spectroscopy measurements. Pre-edge features were assigned to transitions associated with the Al 3p orbitals involved in metal-ligand bonding. Qualitative trends in Al 1s core energy and valence orbital occupation were established through a systematic comparison of excited states derived from Al 3p orbitals with similar symmetries in a molecular orbital framework. These trends suggested that the higher transition energies observed for (BDI)AlX2 systems with more electronegative X(1-) ligands could be ascribed to a decrease in electron density around the aluminum atom, which causes an increase in the attractive potential of the Al nucleus and concomitant increase in the binding energy of the Al 1s core orbitals. For (BDI)Al and (BDI)AlH2 the experimental Al K-edge XANES spectra and spectra calculated using the eXcited electron and Core-Hole (XCH) approach had nearly identical energies for transitions to final state orbitals of similar composition and symmetry. These results implied that the charge distributions about the aluminum atoms in (BDI)Al and (BDI)AlH2 are similar relative to the (BDI)AlX2 and (BDI)AlMe2 compounds, despite having different formal oxidation states of +1 and +3, respectively. However, (BDI)Al was unique in that it exhibited a low-energy feature that was attributed to transitions into a low-lying p-orbital of b1 symmetry that is localized on Al and orthogonal to the (BDI)Al plane. The presence of this low-energy unoccupied molecular orbital on electron-rich (BDI)Al distinguishes

Animal experiments by K-edge subtraction angiography by using SR (abstract)

NASA Astrophysics Data System (ADS)

Anno, I.; Akisada, M.; Takeda, T.; Sugishita, Y.; Kakihana, M.; Ohtsuka, S.; Nishimura, K.; Hasegawa, S.; Takenaka, E.; Hyodo, K.; Ando, M.

1989-07-01

Ischemic heart disease is one of the most popular and lethal diseases for aged peoples in the world, and is usually diagnosed by transarterial selective coronary arteriography. However, it is rather invasive and somewhat dangerous, so that the selective coronary arteriography is not feasible for prospective screening of coronary occlusive heart disease. Conventional digital subtraction angiography (DSA) is widely known as a relatively noninvasive and useful technique is making a diagnosis of arterial occlusive disease, especially in making the diagnosis of ischemic heart disease. Conventional intravenous subtraction angiography by temporal subtraction, however, has several problems when applying to the moving objects. Digital subtraction method using high-speed switching above and below the K edge could be the ideal approach to this solution. We intend to make a synchrotron radiation digital K-edge subtraction angiography in the above policy, and to apply it to the human coronary ischemic disease on an outpatient basis. The principles and experimental systems have already been described in detail by our coworkers. Our prototype experimental system is situated at the AR (accumulation ring) for TRISTAN project of high energy physics. The available beam size is 70 mm by 120 mm. The electron energy of AR is 6.5 GeV and average beam current is approximately 10 mA. This paper will show the animal experiments of our K-edge subtraction system, and discuss some problems and technical difficulties. Three dogs, weighing approximately 15 kg, were examined to evaluate the ability of our prototype synchrotron radiation DSA unit, that we are now constructing. The dogs were anaesthetized with pentobarbital sodium, intravenously (30 mg/kg). Six french-sized (1.52 mm i.d.) pigtail catheter with multiple side holes were introduced via the right femoral vein into the right atrium by the cutdown technique under conventional x-ray fluoroscopic control. Respiration of the dogs was

Restricted active space calculations of L-edge X-ray absorption spectra: from molecular orbitals to multiplet states.

PubMed

Pinjari, Rahul V; Delcey, Mickaël G; Guo, Meiyuan; Odelius, Michael; Lundberg, Marcus

2014-09-28

The metal L-edge (2p → 3d) X-ray absorption spectra are affected by a number of different interactions: electron-electron repulsion, spin-orbit coupling, and charge transfer between metal and ligands, which makes the simulation of spectra challenging. The core restricted active space (RAS) method is an accurate and flexible approach that can be used to calculate X-ray spectra of a wide range of medium-sized systems without any symmetry constraints. Here, the applicability of the method is tested in detail by simulating three ferric (3d(5)) model systems with well-known electronic structure, viz., atomic Fe(3+), high-spin [FeCl6](3-) with ligand donor bonding, and low-spin [Fe(CN)6](3-) that also has metal backbonding. For these systems, the performance of the core RAS method, which does not require any system-dependent parameters, is comparable to that of the commonly used semi-empirical charge-transfer multiplet model. It handles orbitally degenerate ground states, accurately describes metal-ligand interactions, and includes both single and multiple excitations. The results are sensitive to the choice of orbitals in the active space and this sensitivity can be used to assign spectral features. A method has also been developed to analyze the calculated X-ray spectra using a chemically intuitive molecular orbital picture.

Roman coloured and opaque glass: a chemical and spectroscopic study

NASA Astrophysics Data System (ADS)

Arletti, R.; Dalconi, M. C.; Quartieri, S.; Triscari, M.; Vezzalini, G.

2006-05-01

This work reports the results of an archaeometrical investigation of opaque Roman glass and is mainly focussed on the role of configuration and oxidation state of copper on the colour and opacity of red and green opaque finds (mosaic tesserae, game counters, and glass artefacts) from Sicily and Pompeii excavations. The glass fragments were characterised by EMPA, SEM-EDS, TEM, and XRPD analyses and the copper local environment was investigated using X-ray absorption spectroscopy. The analyses of high-resolution Cu-K edge XANES and EXAFS spectra suggest that, in red samples, copper is present as monovalent cations coordinated to the oxygen atoms of the glass framework, accompanied by metallic clusters. In green samples all the copper cations are incorporated in the glass matrix.

Simulation of Near-Edge X-ray Absorption Fine Structure with Time-Dependent Equation-of-Motion Coupled-Cluster Theory.

PubMed

Nascimento, Daniel R; DePrince, A Eugene

2017-07-06

An explicitly time-dependent (TD) approach to equation-of-motion (EOM) coupled-cluster theory with single and double excitations (CCSD) is implemented for simulating near-edge X-ray absorption fine structure in molecular systems. The TD-EOM-CCSD absorption line shape function is given by the Fourier transform of the CCSD dipole autocorrelation function. We represent this transform by its Padé approximant, which provides converged spectra in much shorter simulation times than are required by the Fourier form. The result is a powerful framework for the blackbox simulation of broadband absorption spectra. K-edge X-ray absorption spectra for carbon, nitrogen, and oxygen in several small molecules are obtained from the real part of the absorption line shape function and are compared with experiment. The computed and experimentally obtained spectra are in good agreement; the mean unsigned error in the predicted peak positions is only 1.2 eV. We also explore the spectral signatures of protonation in these molecules.

PEPSI deep spectra. II. Gaia benchmark stars and other M-K standards

NASA Astrophysics Data System (ADS)

Strassmeier, K. G.; Ilyin, I.; Weber, M.

2018-04-01

Context. High-resolution échelle spectra confine many essential stellar parameters once the data reach a quality appropriate to constrain the various physical processes that form these spectra. Aim. We provide a homogeneous library of high-resolution, high-S/N spectra for 48 bright AFGKM stars, some of them approaching the quality of solar-flux spectra. Our sample includes the northern Gaia benchmark stars, some solar analogs, and some other bright Morgan-Keenan (M-K) spectral standards. Methods: Well-exposed deep spectra were created by average-combining individual exposures. The data-reduction process relies on adaptive selection of parameters by using statistical inference and robust estimators. We employed spectrum synthesis techniques and statistics tools in order to characterize the spectra and give a first quick look at some of the science cases possible. Results: With an average spectral resolution of R ≈ 220 000 (1.36 km s-1), a continuous wavelength coverage from 383 nm to 912 nm, and S/N of between 70:1 for the faintest star in the extreme blue and 6000:1 for the brightest star in the red, these spectra are now made public for further data mining and analysis. Preliminary results include new stellar parameters for 70 Vir and α Tau, the detection of the rare-earth element dysprosium and the heavy elements uranium, thorium and neodymium in several RGB stars, and the use of the 12C to 13C isotope ratio for age-related determinations. We also found Arcturus to exhibit few-percent Ca II H&K and Hα residual profile changes with respect to the KPNO atlas taken in 1999. Based on data acquired with PEPSI using the Large Binocular Telescope (LBT) and the Vatican Advanced Technology Telescope (VATT). The LBT is an international collaboration among institutions in the United States, Italy, and Germany. LBT Corporation partners are the University of Arizona on behalf of the Arizona university system; Istituto Nazionale di Astrofisica, Italy; LBT

The effect of site geometry, Ti content and Ti oxidation state on the Ti K-edge XANES spectrum of synthetic hibonite

NASA Astrophysics Data System (ADS)

Doyle, P. M.; Berry, A. J.; Schofield, P. F.; Mosselmans, J. F. W.

2016-08-01

The Al-rich oxide hibonite (CaAl12O19) is modeled to be the second mineral to condense from a gas of solar composition and is found within calcium-aluminum-rich inclusions and the matrix of chondritic meteorites. Both Ti3+ and Ti4+ are reported in meteoritic hibonite, so hibonite has been proposed as a single mineral oxybarometer that could be used to elucidate conditions within the first 0.2 Myrs of the Solar System. Synthetic hibonites with Ti3+/(Ti3+ + Ti4+) (hereafter Ti3+/ΣTi) ranging between 0 and 1 were prepared as matrix-matched standards for meteoritic hibonite. The largest yield of both Ti-free and Ti-bearing hibonite at ∼1300 and ∼1400 °C was obtained by a single sinter under reducing conditions. In situ micro-beam Ti K-edge X-ray absorption near edge structure (XANES) spectra were recorded from the synthetic hibonites, as well as from terrestrial hibonite. Spectral features in the post-crest region were shown to correlate with the Ti4+ content. Furthermore, Ti4+ on the M2 trigonal bipyramidal and the adjoining M4 octahedral sites appears to cause variability in the post-crest region as a function of orientation. For this suite of synthetic hibonites it was observed that the pre-edge peak region is not influenced by orientation, but is controlled by Ti3+/ΣTi, site geometry and/or Ti concentration. In particular, the pre-edge peak intensities reflect Ti coordination environment and distortion of the M4 octahedral site. Therefore, although pre-edge peak intensities have previously been used to determine Ti3+/ΣTi in meteoritic minerals, we excluded use of the pre-edge peak intensities for quantifying Ti valence states in hibonite. The energy of the absorption edge at a normalized intensity of 0.8 (E0.8) and the energy of the minimum between the pre-edge region and the absorption edge (Em1) were found to vary systematically with Ti3+/ΣTi. Ti3+/ΣTi in hibonite as a function of Em1 was modeled by a quadratic function that may be used to quantify Ti3

A PKC-MARCKS-PI3K regulatory module links Ca2+ and PIP3 signals at the leading edge of polarized macrophages.

PubMed

Ziemba, Brian P; Falke, Joseph J

2018-01-01

The leukocyte chemosensory pathway detects attractant gradients and directs cell migration to sites of inflammation, infection, tissue damage, and carcinogenesis. Previous studies have revealed that local Ca2+ and PIP3 signals at the leading edge of polarized leukocytes play central roles in positive feedback loop essential to cell polarization and chemotaxis. These prior studies showed that stimulation of the leading edge Ca2+ signal can strongly activate PI3K, thereby triggering a larger PIP3 signal, but did not elucidate the mechanistic link between Ca2+ and PIP3 signaling. A hypothesis explaining this link emerged, postulating that Ca2+-activated PKC displaces the MARCKS protein from plasma membrane PIP2, thereby releasing sequestered PIP2 to serve as the target and substrate lipid of PI3K in PIP3 production. In vitro single molecule studies of the reconstituted pathway on lipid bilayers demonstrated the feasibility of this PKC-MARCKS-PI3K regulatory module linking Ca2+ and PIP3 signals in the reconstituted system. The present study tests the model predictions in live macrophages by quantifying the effects of: (a) two pathway activators-PDGF and ATP that stimulate chemoreceptors and Ca2+ influx, respectively; and (b) three pathway inhibitors-wortmannin, EGTA, and Go6976 that inhibit PI3K, Ca2+ influx, and PKC, respectively; on (c) four leading edge activity sensors-AKT-PH-mRFP, CKAR, MARCKSp-mRFP, and leading edge area that report on PIP3 density, PKC activity, MARCKS membrane binding, and leading edge expansion/contraction, respectively. The results provide additional evidence that PKC and PI3K are both essential elements of the leading edge positive feedback loop, and strongly support the existence of a PKC-MARCKS-PI3K regulatory module linking the leading edge Ca2+ and PIP3 signals. As predicted, activators stimulate leading edge PKC activity, displacement of MARCKS from the leading edge membrane and increased leading edge PIP3 levels, while inhibitors

A PKC-MARCKS-PI3K regulatory module links Ca2+ and PIP3 signals at the leading edge of polarized macrophages

PubMed Central

Ziemba, Brian P.

2018-01-01

The leukocyte chemosensory pathway detects attractant gradients and directs cell migration to sites of inflammation, infection, tissue damage, and carcinogenesis. Previous studies have revealed that local Ca2+ and PIP3 signals at the leading edge of polarized leukocytes play central roles in positive feedback loop essential to cell polarization and chemotaxis. These prior studies showed that stimulation of the leading edge Ca2+ signal can strongly activate PI3K, thereby triggering a larger PIP3 signal, but did not elucidate the mechanistic link between Ca2+ and PIP3 signaling. A hypothesis explaining this link emerged, postulating that Ca2+-activated PKC displaces the MARCKS protein from plasma membrane PIP2, thereby releasing sequestered PIP2 to serve as the target and substrate lipid of PI3K in PIP3 production. In vitro single molecule studies of the reconstituted pathway on lipid bilayers demonstrated the feasibility of this PKC-MARCKS-PI3K regulatory module linking Ca2+ and PIP3 signals in the reconstituted system. The present study tests the model predictions in live macrophages by quantifying the effects of: (a) two pathway activators—PDGF and ATP that stimulate chemoreceptors and Ca2+ influx, respectively; and (b) three pathway inhibitors—wortmannin, EGTA, and Go6976 that inhibit PI3K, Ca2+ influx, and PKC, respectively; on (c) four leading edge activity sensors—AKT-PH-mRFP, CKAR, MARCKSp-mRFP, and leading edge area that report on PIP3 density, PKC activity, MARCKS membrane binding, and leading edge expansion/contraction, respectively. The results provide additional evidence that PKC and PI3K are both essential elements of the leading edge positive feedback loop, and strongly support the existence of a PKC-MARCKS-PI3K regulatory module linking the leading edge Ca2+ and PIP3 signals. As predicted, activators stimulate leading edge PKC activity, displacement of MARCKS from the leading edge membrane and increased leading edge PIP3 levels, while inhibitors

Investigation on porous MnO microsphere anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhong, Kaifu; Zhang, Bin; Luo, Shihai; Wen, Wen; Li, Hong; Huang, Xuejie; Chen, Liquan

MnO microspheres with and without carbon coating are prepared as anode materials for lithium ion batteries. The MnO microsphere material shows a reversible capacity of 800 mAh g -1 and an initial efficiency of 71%. It can deliver 600 mAh g -1 at a rate of 400 mA g -1. Results of Mn K-edge X-ray absorption near-edge structure (XANES) spectra and extended X-ray absorption fine structure (EXAFS) confirm further the conversion reaction mechanism, indicate that pristine MnO is reduced to Mn 0 after discharging to 0 V and part of reduced Mn 0 is not oxidized to Mn 2+ after charging to 3 V. This explains the origin of the initial irreversible capacity loss partially. The quasi open circuit voltage and the relationship between the current density and the overpotential are investigated. Both indicate that there is a significant voltage difference between the charging and discharging profiles even when the current density decreases to zero.

Comparison of the Manganese Cluster in Oxygen-Evolving Photosystem II with Distorted Cubane Manganese Compounds through X-ray Absorption Spectroscopy

PubMed Central

Cinco, Roehl M.; Rompel, Annette; Visser, Hendrik; Aromí, Guillem; Christou, George; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

2014-01-01

X-ray absorption spectroscopy has been employed to assess the degree of similarity between the oxygen-evolving complex (OEC) in photosystem II (PS II) and a family of synthetic manganese complexes containing the distorted cubane [Mn4O3X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride, or bromide). These [Mn4(μ3-O)3(μ3-X)] cubanes possess C3v symmetry except for the X = benzoate species, which is slightly more distorted with only Cs symmetry. In addition, Mn4O3Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The Mn K-edge X-ray absorption near edge structure (XANES) from the oxygen-ligated complexes begin to resemble general features of the PS II (S1 state) spectrum, although the second derivatives are distinct from those in PS II. The extended X-ray absorption fine structure (EXAFS) of these Mn compounds also displays superficial resemblance to that of PS II, but major differences emerge on closer examination of the phases and amplitudes. The most obvious distinction is the smaller magnitude of the Fourier transform (FT) of the PS II EXAFS compared to the FTs from the distorted cubanes. Curve fitting of the Mn EXAFS spectra verifies the known core structures of the Mn cubanes, and shows that the number of the crucial 2.7 and 3.3 Å Mn–Mn distances differs from that observed in the OEC. The EXAFS method detects small changes in the core structures as X is varied in this series, and serves to exclude the distorted cubane of C3v symmetry as a topological model for the Mn catalytic cluster of the OEC. Instead, the method shows that even more distortion of the cubane framework, altering the ratio of the Mn–Mn distances, is required to resemble the Mn cluster in PS II. PMID:11671305

Atomistic nucleation sites of Pt nanoparticles on N-doped carbon nanotubes.

PubMed

Sun, Chia-Liang; Pao, Chih-Wen; Tsai, Huang-Ming; Chiou, Jau-Wern; Ray, Sekhar C; Wang, Houng-Wei; Hayashi, Michitoshi; Chen, Li-Chyong; Lin, Hong-Ji; Lee, Jyh-Fu; Chang, Li; Tsai, Min-Hsiung; Chen, Kuei-Hsien; Pong, Way-Faung

2013-08-07

The atomistic nucleation sites of Pt nanoparticles (Pt NPs) on N-doped carbon nanotubes (N-CNTs) were investigated using C and N K-edge and Pt L3-edge X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. Transmission electron microscopy and XANES/EXAFS results revealed that the self-organized Pt NPs on N-CNTs are uniformly distributed because of the relatively high binding energies of the adsorbed Pt atoms at the imperfect sites. During the atomistic nucleation process of Pt NPs on N-CNTs, stable Pt-C and Pt-N bonds are presumably formed, and charge transfer occurs at the surface/interface of the N-CNTs. The findings in this study were consistent with density functional theory calculations performed using cluster models for the undoped, substitutional-N-doped and pyridine-like-N-doped CNTs.

Local Environment Sensitivity of the Cu K-Edge XANES Features in Cu-SSZ-13: Analysis from First-Principles.

PubMed

Zhang, Renqin; McEwen, Jean-Sabin

2018-05-22

Cu K-edge X-ray absorption near-edge spectra (XANES) have been widely used to study the properties of Cu-SSZ-13. In this Letter, the sensitivity of the XANES features to the local environment for a Cu + cation with a linear configuration and a Cu 2+ cation with a square-linear configuration in Cu-SSZ-13 is reported. When a Cu + cation is bonded to H 2 O or NH 3 in a linear configuration, the XANES has a strong peak at around 8983 eV. The intensity of this peak decreases as the linear configuration is broken. As for the Cu 2+ cations in a square-planar configuration with a coordination number of 4, two peaks at around 8986 and 8993 eV are found. An intensity decrease for both peaks at around 8986 and 8993 eV is found in an NH 3 _4_Z 2 Cu model as the N-Cu-N angle changes from 180 to 100°. We correlate these features to the variation of the 4p state by PDOS analysis. In addition, the feature peaks for both the Cu + cation and Cu 2+ cation do not show a dependence on the Cu-N bond length. We further show that the feature peaks also change when the coordination number of the Cu cation is varied, while these feature peaks are independent of the zeolite topology. These findings help elucidate the experimental XANES features at an atomic and an electronic level.

Spectral K-edge subtraction imaging of experimental non-radioactive barium uptake in bone.

PubMed

Panahifar, Arash; Samadi, Nazanin; Swanston, Treena M; Chapman, L Dean; Cooper, David M L

2016-12-01

To evaluate the feasibility of using non-radioactive barium as a bone tracer for detection with synchrotron spectral K-edge subtraction (SKES) technique. Male rats of 1-month old (i.e., developing skeleton) and 8-month old (i.e., skeletally mature) were orally dosed with low dose of barium chloride (33mg/kg/day Ba 2+ ) for 4weeks. The fore and hind limbs were dissected for imaging in projection and computed tomography modes at 100μm and 52μm pixel sizes. The SKES method utilizes a single bent Laue monochromator to prepare a 550eV energy spectrum to encompass the K-edge of barium (37.441keV), for collecting both 'above' and 'below' the K-edge data sets in a single scan. The SKES has a very good focal size, thus limits the 'crossover' and motion artifacts. In juvenile rats, barium was mostly incorporated in the areas of high bone turnover such as at the growth plate and the trabecular surfaces, but also in the cortical bone as the animals were growing at the time of tracer administration. However, the adults incorporated approximately half the concentration and mainly in the areas where bone remodeling was predominant and occasionally in the periosteal and endosteal layers of the diaphyseal cortical bone. The presented methodology is simple to implement and provides both structural and functional information, after labeling with barium, on bone micro-architecture and thus has great potential for in vivo imaging of pre-clinical animal models of musculoskeletal diseases to better understand their mechanisms and to evaluate the efficacy of pharmaceuticals. Copyright © 2016 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

Nickel L-edge and K-edge X-ray absorption spectroscopy of non-innocent Ni[S₂C₂(CF₃)₂]₂(n) series (n = -2, -1, 0): direct probe of nickel fractional oxidation state changes.

PubMed

Gu, Weiwei; Wang, Hongxin; Wang, Kun

2014-05-07

A series of nickel dithiolene complexes Ni[S2C2(CF3)2]2(n) (n = -2, -1, 0) has been investigated using Ni L- and K-edge X-ray absorption spectroscopy (XAS). The L3 centroid shifts about 0.3 eV for a change of one unit in the formal oxidation state (or 0.3 eV per oxi), corresponding to ~33% of the shift for Ni oxides or fluorides (about 0.9 eV per oxi). The K-edge XAS edge position shifts about 0.7 eV per oxi, corresponding to ~38% of that for Ni oxides (1.85 eV per oxi). In addition, Ni L sum rule analysis found the Ni(3d) ionicity in the frontier orbitals being 50.5%, 44.0% and 38.5% respectively (for n = -2, -1, 0), in comparison with their formal oxidation states (of Ni(II), Ni(III), and Ni(IV)). For the first time, direct and quantitative measurement of the Ni fractional oxidation state changes becomes possible for Ni dithiolene complexes, illustrating the power of L-edge XAS and L sum rule analysis in such a study. The Ni L-edge and K-edge XAS can be used in a complementary manner to better assess the oxidation states for Ni.

A non-LTE kinetic model for quick analysis of K-shell spectra from Z-pinch plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, J., E-mail: s.duan@163.com; Huang, X. B., E-mail: s.duan@163.com; Cai, H. C., E-mail: s.duan@163.com

Analyzing and modeling K-shell spectra emitted by low-to moderate-atomic number plasma is a useful and effective way to retrieve temperature density of z-pinch plasmas. In this paper, a non-LTE population kinetic model for quick analysis of K-shell spectra was proposed. The model contains ionization stages from bare nucleus to neutral atoms and includes all the important atomic processes. In the present form of the model, the plasma is assumed to be both optically thin and homogeneous with constant temperature and density, and only steady-state situation is considered. According to the detailed calculations for aluminum plasmas, contours of ratios of certainmore » K-shell lines in electron temperature and density plane as well as typical synthesized spectra were presented and discussed. The usefulness of the model is demonstrated by analyzing the spectrum from a neon gas-puff Z-pinch experiment performed on a 1 MA pulsed-power accelerator.« less

Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: Arsenate on hematite (0001) and (10-12)

USGS Publications Warehouse

Waychunas, G.; Trainor, T.; Eng, P.; Catalano, J.; Brown, G.; Davis, J.; Rogers, J.; Bargar, J.

2005-01-01

X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c(0001) and r(10-12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of "edge-sharing" bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods. ?? Springer-Verlag 2005.

First Infrared Predissociation Spectra of He-TAGGED Protonated Primary Alcohols at 4 K

NASA Astrophysics Data System (ADS)

Stoffels, Alexander; Redlich, Britta; Oomens, J.; Asvany, Oskar; Brünken, Sandra; Jusko, Pavol; Thorwirth, Sven; Schlemmer, Stephan

2015-06-01

Cryogenic multipole ion traps have become popular devices in the development of sensitive action-spectroscopic techniques. The low ion temperature leads to enhanced spectral resolution, and less congested spectra. In the early 2000s, a 22-pole ion trap was coupled to the Free-Electron Laser for Infrared eXperiments (FELIX), yielding infrared Laser Induced Reaction (LIR) spectra of the molecular ions C_2H_2+ and CH_5+. This pioneering work showed the great opportunities combining cold mass-selected molecular ions with widely tunable broadband IR radiation. In the past year a cryogenic (T>3.9 K) 22-pole ion trap designed and built in Cologne (FELion) has been successfully coupled to FELIX, which in its current configuration provides continuously tunable infrared radiation from 3 μm to 150 μm, hence allowing to probe characteristic vibrational spectra in the so-called "fingerprint region" with a sufficient spectral energy density also allowing for multiple photon processes (IR-MPD). Here we present the first infrared predissociation spectra of He-tagged protonated methanol and ethanol (MeOH_2+/EtOH_2+) stored at 4 K. These vibrational spectra were recorded with both a commercial OPO and FELIX, covering a total spectral range from 3700 wn to 550 wn at a spectral resolution of a few wn. The H-O-H stretching and bending modes clearly distinguish the protonated alcohols from their neutral analoga. For EtOH_2+, also IR-MPD spectra of the bare ion could be recorded. The symmetric and antisymmetric H-O-H stretching bands at around 3 μm show no significant shift within the given spectral resolution in comparison to those recorded with He predissociation, indicating a rather small perturbation caused by the attached He. The vibrational bands were assigned using quantum-chemical calculations on different levels of theory. The computed frequencies correspond favorably to the experimental spectra. Subsequent high resolution measurements could lead to a better structural

Absorption and scattering by interstellar dust in the silicon K-edge of GX 5-1

NASA Astrophysics Data System (ADS)

Zeegers, S. T.; Costantini, E.; de Vries, C. P.; Tielens, A. G. G. M.; Chihara, H.; de Groot, F.; Mutschke, H.; Waters, L. B. F. M.; Zeidler, S.

2017-03-01

Context. We study the absorption and scattering of X-ray radiation by interstellar dust particles, which allows us to access the physical and chemical properties of dust. The interstellar dust composition is not well understood, especially on the densest sight lines of the Galactic plane. X-rays provide a powerful tool in this study. Aims: We present newly acquired laboratory measurements of silicate compounds taken at the Soleil synchrotron facility in Paris using the Lucia beamline. The dust absorption profiles resulting from this campaign were used in this pilot study to model the absorption by interstellar dust along the line of sight of the low-mass X-ray binary GX 5-1. Methods: The measured laboratory cross-sections were adapted for astrophysical data analysis and the resulting extinction profiles of the Si K-edge were implemented in the SPEX spectral fitting program. We derive the properties of the interstellar dust along the line of sight by fitting the Si K-edge seen in absorption in the spectrum of GX 5-1. Results: We measured the hydrogen column density towards GX 5-1 to be 3.40 ± 0.1 × 1022 cm-2. The best fit of the silicon edge in the spectrum of GX 5-1 is obtained by a mixture of olivine and pyroxene. In this study, our modeling is limited to Si absorption by silicates with different Mg:Fe ratios. We obtained an abundance of silicon in dust of 4.0 ± 0.3 × 10-5 per H atom and a lower limit for total abundance, considering both gas and dust of >4.4 × 10-5 per H atom, which leads to a gas to dust ratio of >0.22. Furthermore, an enhanced scattering feature in the Si K-edge may suggest the presence of large particles along the line of sight.

On the location of spectral edges in \\ {Z}-periodic media

NASA Astrophysics Data System (ADS)

Exner, Pavel; Kuchment, Peter; Winn, Brian

2010-11-01

Periodic second-order ordinary differential operators on \\ {R} are known to have the edges of their spectra to occur only at the spectra of periodic and anti-periodic boundary value problems. The multi-dimensional analog of this property is false, as was shown in a 2007 paper by some of the authors of this paper. However, one sometimes encounters the claims that in the case of a single periodicity (i.e., with respect to the lattice \\ {Z}), the 1D property still holds, and spectral edges occur at the periodic and anti-periodic spectra only. In this work, we show that even in the simplest case of quantum graphs this is not true. It is shown that this is true if the graph consists of a 1D chain of finite graphs connected by single edges, while if the connections are formed by at least two edges, the spectral edges can already occur away from the periodic and anti-periodic spectra. This paper is dedicated to the memory of P Duclos.

Excitation-Power Dependence of the Near Band-Edge PL Spectra of CdMnTe with High Mn Concentrations

NASA Astrophysics Data System (ADS)

Hwang, Younghun; Um, Youngho; Park, Hyoyeol

2011-12-01

Temperature and excitation power dependences of photoluminescence (PL) measurements were studied for the CdMnTe crystal grown by the vertical Bridgman method. The near band-edge and intra-Mn2+ emissions were investigated as a function of temperature. The observed band-edge peak of the PL spectrum showed a clear blue-shift with decreasing temperature. However, the peak energy of the intra-Mn2+ transition did not decrease monotonically with changing temperature, as can be seen above 70 K. With increasing the excitation power, the intensity of the emission peak was increased.

First demonstration of 10 keV-width energy-discrimination K-edge radiography using a cadmium-telluride X-ray camera with a tungsten-target tube

NASA Astrophysics Data System (ADS)

Watanabe, Manabu; Sato, Eiichi; Abderyim, Purkhet; Abudurexiti, Abulajiang; Hagiwara, Osahiko; Matsukiyo, Hiroshi; Osawa, Akihiro; Enomoto, Toshiyuki; Nagao, Jiro; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

2011-05-01

Energy-discrimination X-ray camera is useful to perform monochromatic radiography using polychromatic X-rays. This X-ray camera was developed to carry out K-edge radiography using cerium and gadolinium-based contrast media. In this camera, objects are irradiated by a cone beam from a tungsten-target X-ray generator, and penetrating X-ray photons are detected by a cadmium-telluride detector with amplifiers. Both optimal photon-energy level and energy width are selected using a multichannel analyzer, and the photon number is counted by a counter card. Radiography was performed by the detector scanning using an x- y stage driven by a two-stage controller, and radiograms were shown on a personal computer monitor. In radiography, tube voltage and current were 90 kV and 5.8 μA, respectively, and the X-ray intensity was 0.61 μGy/s at 1.0 m from the X-ray source. The K-edge energies of cerium and gadolinium are 40.3 and 50.3 keV, respectively, and 10 keV-width enhanced K-edge radiography was performed using X-ray photons with energies just beyond K-edge energies of cerium and gadolinium. Thus, cerium K-edge radiography was carried out using X-ray photons with an energy range from 40.3 to 50. 3 keV, and gadolinium K-edge radiography was accomplished utilizing photon energies ranging from 50.3 to 60.3 keV.

Portable X-Ray, K-Edge Heavy Metal Detector

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fricke, V.

The X-Ray, K-Edge Heavy Metal Detection System was designed and built by Ames Laboratory and the Center for Nondestructive Evaluation at Iowa State University. The system uses a C-frame inspection head with an X-ray tube mounted on one side of the frame and an imaging unit and a high purity germanium detector on the other side. the inspection head is portable and can be easily positioned around ventilation ducts and pipes up to 36 inches in diameter. Wide angle and narrow beam X-ray shots are used to identify the type of holdup material and the amount of the contaminant. Precisemore » assay data can be obtained within minutes of the interrogation. A profile of the containerized holdup material and a permanent record of the measurement are immediately available.« less

The Mg II h and k lines. II - Comparison with synthesized profiles and Ca II K. [solar spectra

NASA Technical Reports Server (NTRS)

Ayres, T. R.; Linsky, J. L.

1976-01-01

Measured high-dispersion center and limb profiles of the solar Mg II h and k resonance lines are compared with synthetic spectra computed with a partial-redistribution formalism and based on several upper-photosphere and lower-chromosphere temperature distributions. Profiles of the analogously formed Ca II K resonance line are also synthesized for the same atmospheric models. The spectrum-synthesis approach is outlined, and the collisional and fixed radiative rates appropriate to the adopted model atoms and solar atmosphere are discussed. It is found that the HSRA and VAL models predict systematically lower intensities in the h, k, and K inner wings than observed and that models with a somewhat higher minimum temperature (about 4450 K) can reproduce the measured inner wings and limb darkening. A 'Ca II' solar model with a minimum temperature of 4450 K is proposed as an alternative to the class of models based on continuum observations.

SUT-NANOTEC-SLRI beamline for X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klysubun, Wantana; Kidkhunthod, Pinit; Tarawarakarn, Pongjakr

2017-04-04

The SUT-NANOTEC-SLRI beamline was constructed in 2012 as the flagship of the SUT-NANOTEC-SLRI Joint Research Facility for Synchrotron Utilization, co-established by Suranaree University of Technology (SUT), National Nanotechnology Center (NANOTEC) and Synchrotron Light Research Institute (SLRI). It is an intermediate-energy X-ray absorption spectroscopy (XAS) beamline at SLRI. The beamline delivers an unfocused monochromatic X-ray beam of tunable photon energy (1.25–10 keV). The maximum normal incident beam size is 13 mm (width) × 1 mm (height) with a photon flux of 3 × 10 8to 2 × 10 10 photons s -1(100 mA) -1varying across photon energies. Details of the beamlinemore » and XAS instrumentation are described. To demonstrate the beamline performance,K-edge XANES spectra of MgO, Al 2O 3, S 8, FeS, FeSO 4, Cu, Cu 2O and CuO, and EXAFS spectra of Cu and CuO are presented.« less

Three-dimensional labeling of newly formed bone using synchrotron radiation barium K-edge subtraction imaging

NASA Astrophysics Data System (ADS)

Panahifar, Arash; Swanston, Treena M.; Pushie, M. Jake; Belev, George; Chapman, Dean; Weber, Lynn; Cooper, David M. L.

2016-07-01

Bone is a dynamic tissue which exhibits complex patterns of growth as well as continuous internal turnover (i.e. remodeling). Tracking such changes can be challenging and thus a high resolution imaging-based tracer would provide a powerful new perspective on bone tissue dynamics. This is, particularly so if such a tracer can be detected in 3D. Previously, strontium has been demonstrated to be an effective tracer which can be detected by synchrotron-based dual energy K-edge subtraction (KES) imaging in either 2D or 3D. The use of strontium is, however, limited to very small sample thicknesses due to its low K-edge energy (16.105 keV) and thus is not suitable for in vivo application. Here we establish proof-of-principle for the use of barium as an alternative tracer with a higher K-edge energy (37.441 keV), albeit for ex vivo imaging at the moment, which enables application in larger specimens and has the potential to be developed for in vivo imaging of preclinical animal models. New bone formation within growing rats in 2D and 3D was demonstrated at the Biomedical Imaging and Therapy bending magnet (BMIT-BM) beamline of the Canadian Light Source synchrotron. Comparative x-ray fluorescence imaging confirmed those patterns of uptake detected by KES. This initial work provides a platform for the further development of this tracer and its exploration of applications for in vivo development.

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite: II. XANES analysis and simulation

USGS Publications Warehouse

Waychunas, G.A.; Fuller, C.C.; Davis, J.A.; Rehr, J.J.

2003-01-01

X-ray absorption near-edge spectroscopy (XANES) analysis of sorption complexes has the advantages of high sensitivity (10- to 20-fold greater than extended X-ray absorption fine structure [EXAFS] analysis) and relative ease and speed of data collection (because of the short k-space range). It is thus a potentially powerful tool for characterization of environmentally significant surface complexes and precipitates at very low surface coverages. However, quantitative analysis has been limited largely to "fingerprint" comparison with model spectra because of the difficulty of obtaining accurate multiple-scattering amplitudes for small clusters with high confidence. In the present work, calculations of the XANES for 50- to 200-atom clusters of structure from Zn model compounds using the full multiple-scattering code Feff 8.0 accurately replicate experimental spectra and display features characteristic of specific first-neighbor anion coordination geometry and second-neighbor cation geometry and number. Analogous calculations of the XANES for small molecular clusters indicative of precipitation and sorption geometries for aqueous Zn on ferrihydrite, and suggested by EXAFS analysis, are in good agreement with observed spectral trends with sample composition, with Zn-oxygen coordination and with changes in second-neighbor cation coordination as a function of sorption coverage. Empirical analysis of experimental XANES features further verifies the validity of the calculations. The findings agree well with a complete EXAFS analysis previously reported for the same sample set, namely, that octahedrally coordinated aqueous Zn2+ species sorb as a tetrahedral complex on ferrihydrite with varying local geometry depending on sorption density. At significantly higher densities but below those at which Zn hydroxide is expected to precipitate, a mainly octahedral coordinated Zn2+ precipitate is observed. An analysis of the multiple scattering paths contributing to the XANES

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

DOE PAGES

Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.; ...

2017-06-22

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

EX6AFS: A data acquisition system for high-speed dispersive EXAFS measurements implemented using object-oriented programming techniques

NASA Astrophysics Data System (ADS)

Jennings, Guy; Lee, Peter L.

1995-02-01

In this paper we describe the design and implementation of a computerized data-acquisition system for high-speed energy-dispersive EXAFS experiments on the X6A beamline at the National Synchrotron Light Source. The acquisition system drives the stepper motors used to move the components of the experimental setup and controls the readout of the EXAFS spectra. The system runs on a Macintosh IIfx computer and is written entirely in the object-oriented language C++. Large segments of the system are implemented by means of commercial class libraries, specifically the MacApp application framework from Apple, the Rogue Wave class library, and the Hierarchical Data Format datafile format library from the National Center for Supercomputing Applications. This reduces the amount of code that must be written and enhances reliability. The system makes use of several advanced features of C++: Multiple inheritance allows the code to be decomposed into independent software components and the use of exception handling allows the system to be much more reliable in the event of unexpected errors. Object-oriented techniques allow the program to be extended easily as new requirements develop. All sections of the program related to a particular concept are located in a small set of source files. The program will also be used as a prototype for future software development plans for the Basic Energy Science Synchrotron Radiation Center Collaborative Access Team beamlines being designed and built at the Advanced Photon Source.

Large local disorder in superconducting K(0.8)Fe(1.6)Se2 studied by extended x-ray absorption fine structure.

PubMed

Iadecola, A; Joseph, B; Simonelli, L; Puri, A; Mizuguchi, Y; Takeya, H; Takano, Y; Saini, N L

2012-03-21

We have measured the local structure of superconducting K(0.8)Fe(1.6)Se(2) chalcogenide (T(c) = 31.8 K) by temperature dependent polarized extended x-ray absorption fine structure (EXAFS) at the Fe and Se K-edges. We find that the system is characterized by a large local disorder. The Fe-Se and Fe-Fe distances are found to be shorter than the distances measured by diffraction, while the corresponding mean square relative displacements reveal large Fe-site disorder and relatively large c-axis disorder. The local force constant for the Fe-Se bondlength (k ~ 5.8 eV Å(-2)) is similar to the one found in the binary FeSe superconductor, however, the Fe-Fe bondlength appears to be flexible (k ~ 2.1 eV Å(-2)) in comparison to the binary FeSe (k ~ 3.5 eV Å(-2)), an indication of partly relaxed Fe-Fe networks in K(0.8)Fe(1.6)Se(2). The results suggest a glassy nature for the title system, with the superconductivity being similar to that in the granular materials. © 2012 IOP Publishing Ltd

Flap Edge Aeroacoustic Measurements and Predictions

NASA Technical Reports Server (NTRS)

Brooks, Thomas F.; Humphreys, William M., Jr.

2000-01-01

An aeroacoustic model test has been conducted to investigate the mechanisms of sound generation on high-lift wing configurations. This paper presents an analysis of flap side-edge noise, which is often the most dominant source. A model of a main element wing section with a half-span flap was tested at low speeds of up to a Mach number of 0.17, corresponding to a wing chord Reynolds number of approximately 1.7 million. Results are presented for flat (or blunt), flanged, and round flap-edge geometries, with and without boundary-layer tripping, deployed at both moderate and high flap angles. The acoustic database is obtained from a Small Aperture Directional Array (SADA) of microphones, which was constructed to electronically steer to different regions of the model and to obtain farfield noise spectra and directivity from these regions. The basic flap-edge aerodynamics is established by static surface pressure data, as well as by Computational Fluid Dynamics (CFD) calculations and simplified edge flow analyses. Distributions of unsteady pressure sensors over the flap allow the noise source regions to be defined and quantified via cross-spectral diagnostics using the SADA output. It is found that shear layer instability and related pressure scatter is the primary noise mechanism. For the flat edge flap, two noise prediction methods based on unsteady surface pressure measurements are evaluated and compared to measured noise. One is a new causality spectral approach developed here. The other is a new application of an edge-noise scatter prediction method. The good comparisons for both approaches suggest that much of the physics is captured by the prediction models. Areas of disagreement appear to reveal when the assumed edge noise mechanism does not fully define the noise production. For the different edge conditions, extensive spectra and directivity are presented. Significantly, for each edge configuration, the spectra for different flow speeds, flap angles, and

Flap Edge Aeroacoustic Measurements and Predictions

NASA Technical Reports Server (NTRS)

Brooks, Thomas F.; Humphreys, William M., Jr.

2000-01-01

An aeroacoustic model test has been conducted to investigate the mechanisms of sound generation on high-lift wing configurations. This paper presents an analysis of flap side-edge noise, which is often the most dominant source. A model of a main element wing section with a half-span flap was tested at low speeds of up to a Mach number of 0.17, corresponding to a wing chord Reynolds number of approximately 1.7 million. Results are presented for flat (or blunt), flanged, and round flap-edge geometries, with and without boundary-layer tripping, deployed at both moderate and high flap angles. The acoustic database is obtained from a Small Aperture Directional Array (SADA) of microphones, which was constructed to electronically steer to different regions of the model and to obtain farfield noise spectra and directivity from these regions. The basic flap-edge aerodynamics is established by static surface pressure data, as well as by Computational Fluid Dynamics (CFD) calculations and simplified edge flow analyses. Distributions of unsteady pressure sensors over the flap allow the noise source regions to be defined and quantified via cross-spectral diagnostics using the SADA output. It is found that shear layer instability and related pressure scatter is the primary noise mechanism. For the flat edge flap, two noise prediction methods based on unsteady-surface-pressure measurements are evaluated and compared to measured noise. One is a new causality spectral approach developed here. The other is a new application of an edge-noise scatter prediction method. The good comparisons for both approaches suggest that much of the physics is captured by the prediction models. Areas of disagreement appear to reveal when the assumed edge noise mechanism does not fully define, the noise production. For the different edge conditions, extensive spectra and directivity are presented. Significantly, for each edge configuration, the spectra for different flow speeds, flap angles, and

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

PubMed Central

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

1982-01-01

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

Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

USGS Publications Warehouse

Majzlan, Juraj; Alpers, Charles N.; Bender Koch, Christian; McCleskey, R. Blaine; Myneni, Satish B.C.; Neil, John M.

2011-01-01

The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and M??ssbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe2O3/FeO): szomolnokite, rozenite, siderotil, halotrichite, r??merite, voltaite, copiapite, monoclinic Fe2(SO4)3, Fe2(SO4)3??5H2O, kornelite, coquimbite, Fe(SO4)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750-4000cm-1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe3+ octahedra and sulfate tetrahedra. M??ssbauer spectra of selected samples were obtained at room temperature and 80K for ferric minerals jarosite and rhomboclase and mixed ferric-ferrous minerals r??merite, voltaite, and copiapite. Values of Fe2+/[Fe2++Fe3+] determined by M??ssbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases. ?? 2011 Elsevier B.V.

Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

USGS Publications Warehouse

Majzlan, Juraj; Alpers, Charles N.; Bender Koch, Christian; McCleskey, R. Blaine; Myneni, Satish B.C.; Neil, John M.

2014-01-01

The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and Mössbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe2O3/FeO): szomolnokite, rozenite, siderotil, halotrichite, römerite, voltaite, copiapite, monoclinic Fe2(SO4)3, Fe2(SO4)3·5H2O, kornelite, coquimbite, Fe(SO4)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750–4000 cm−1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe3+ octahedra and sulfate tetrahedra. Mössbauer spectra of selected samples were obtained at room temperature and 80 K for ferric minerals jarosite and rhomboclase and mixed ferric–ferrous minerals römerite, voltaite, and copiapite. Values of Fe2+/[Fe2+ + Fe3+] determined by Mössbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases.

AUTOMATED UNSUPERVISED CLASSIFICATION OF THE SLOAN DIGITAL SKY SURVEY STELLAR SPECTRA USING k-MEANS CLUSTERING

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanchez Almeida, J.; Allende Prieto, C., E-mail: jos@iac.es, E-mail: callende@iac.es

2013-01-20

Large spectroscopic surveys require automated methods of analysis. This paper explores the use of k-means clustering as a tool for automated unsupervised classification of massive stellar spectral catalogs. The classification criteria are defined by the data and the algorithm, with no prior physical framework. We work with a representative set of stellar spectra associated with the Sloan Digital Sky Survey (SDSS) SEGUE and SEGUE-2 programs, which consists of 173,390 spectra from 3800 to 9200 A sampled on 3849 wavelengths. We classify the original spectra as well as the spectra with the continuum removed. The second set only contains spectral lines,more » and it is less dependent on uncertainties of the flux calibration. The classification of the spectra with continuum renders 16 major classes. Roughly speaking, stars are split according to their colors, with enough finesse to distinguish dwarfs from giants of the same effective temperature, but with difficulties to separate stars with different metallicities. There are classes corresponding to particular MK types, intrinsically blue stars, dust-reddened, stellar systems, and also classes collecting faulty spectra. Overall, there is no one-to-one correspondence between the classes we derive and the MK types. The classification of spectra without continuum renders 13 classes, the color separation is not so sharp, but it distinguishes stars of the same effective temperature and different metallicities. Some classes thus obtained present a fairly small range of physical parameters (200 K in effective temperature, 0.25 dex in surface gravity, and 0.35 dex in metallicity), so that the classification can be used to estimate the main physical parameters of some stars at a minimum computational cost. We also analyze the outliers of the classification. Most of them turn out to be failures of the reduction pipeline, but there are also high redshift QSOs, multiple stellar systems, dust-reddened stars, galaxies, and, finally

Simulations of the Fe K α Energy Spectra from Gravitationally Microlensed Quasars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krawczynski, H.; Chartas, G., E-mail: krawcz@wustl.edu

The analysis of the Chandra X-ray observations of the gravitationally lensed quasar RX J1131−1231 revealed the detection of multiple and energy-variable spectral peaks. The spectral variability is thought to result from the microlensing of the Fe K α emission, selectively amplifying the emission from certain regions of the accretion disk with certain effective frequency shifts of the Fe K α line emission. In this paper, we combine detailed simulations of the emission of Fe K α photons from the accretion disk of a Kerr black hole with calculations of the effect of gravitational microlensing on the observed energy spectra. Themore » simulations show that microlensing can indeed produce multiply peaked energy spectra. We explore the dependence of the spectral characteristics on black hole spin, accretion disk inclination, corona height, and microlensing amplification factor and show that the measurements can be used to constrain these parameters. We find that the range of observed spectral peak energies of QSO RX J1131−1231 can only be reproduced for black hole inclinations exceeding 70° and for lamppost corona heights of less than 30 gravitational radii above the black hole. We conclude by emphasizing the scientific potential of studies of the microlensed Fe K α quasar emission and the need for more detailed modeling that explores how the results change for more realistic accretion disk and corona geometries and microlensing magnification patterns. A full analysis should furthermore model the signal-to-noise ratio of the observations and the resulting detection biases.« less

EXAFS Reveals the Mechanism of U Isotope Fractionation During Adsorption to Mn Oxyhydroxide

NASA Astrophysics Data System (ADS)

Wasylenki, L. E.; Brennecka, G.; Bargar, J.; Weyer, S.; Anbar, A. D.

2010-12-01

Natural variations in the ratio of 238U/235U due to “stable” isotope fractionation have now been reported for a range of geological samples [1-3]. Among the observed variations are a small difference in 238U/235U between seawater and ferromanganese sediments (seawater slightly heavier) and a larger difference, with opposite sense, between seawater and black shales (seawater lighter). These variations suggest that long-term changes in the proportions of oxic and anoxic/sulfidic sinks for U in the ocean over Earth’s history may be recorded as shifts in the isotopic compositions of marine sediments. Thus U isotopes are a potential paleoredox proxy for the oceans, as suggested by [4]. In order to investigate the mechanism behind fractionation of U isotopes in oxidizing marine environments, we previously conducted simple adsorption experiments in which an isotopically known pool of dissolved U partly adsorbed onto synthetic birnessite, a common Mn oxyhydroxide in hydrogenetic ferromanganese crusts. Our experimental result agreed very well with that observed between seawater and natural ferromanganese sediments: δ238U/235U of adsorbed U was 0.2‰ lighter than δ238U/235U of dissolved U [5]. The magnitude of fractionation is constant as a function of experimental duration and fraction of U adsorbed, suggesting an equilibrium isotope effect. Many metal isotope effects are driven by changes in oxidation state for the metal of interest. Because both dissolved and adsorbed U are hexavalent in this system, a redox reaction cannot be causing isotope fractionation. We therefore hypothesized that a difference in uranium’s coordination environment between dissolved and adsorbed U is likely responsible for the isotope effect. We analyzed a sample from our experimental study with extended X-ray absorption fine structure (EXAFS) spectroscopy. Comparison of the EXAFS spectrum of U adsorbed on birnessite with the spectra of aqueous U species (UO22+ and UO2(CO3)34-) reveals

Flap-edge aeroacoustic measurements and predictions

NASA Astrophysics Data System (ADS)

Brooks, Thomas F.; Humphreys, William M.

2003-03-01

An aeroacoustic model test has been conducted to investigate the mechanisms of sound generation on high-lift wing configurations. This paper presents an analysis of flap side-edge noise, which is often the most dominant source. A model of a main element wing section with a half-span flap was tested at low speeds of up to a Mach number of 0.17, corresponding to a wing chord Reynolds number of approximately 1.7 million. Results are presented for flat (or blunt), flanged, and round flap-edge geometries, with and without boundary-layer tripping, deployed at both moderate and high flap angles. The acoustic database is obtained from a small aperture directional array (SADA) of microphones, which was constructed to electronically steer to different regions of the model and to obtain farfield noise spectra and directivity from these regions. The basic flap-edge aerodynamics is established by static surface pressure data, as well as by computational fluid dynamics (CFD) calculations and simplified edge flow analyses. Distributions of unsteady pressure sensors over the flap allow the noise source regions to be defined and quantified via cross-spectral diagnostics using the SADA output. It is found that shear layer instability and related pressure scatter is the primary noise mechanism. For the flat edge flap, two noise prediction methods based on unsteady-surface-pressure measurements are evaluated and compared to measured noise. One is a new causality spectral approach developed here. The other is a new application of an edge-noise scatter prediction method. The good comparisons for both approaches suggest that the prediction models capture much of the physics. Areas of disagreement appear to reveal when the assumed edge noise mechanism does not fully define the noise production. For the different edge conditions, extensive spectra and directivity are presented. The complexity of the directivity results demonstrate the strong role of edge source geometry and frequency in

Na, Mg, Ni and Cs distribution and speciation after long-term alteration of a simulated nuclear waste glass: A micro-XAS/XRF/XRD and wet chemical study

NASA Astrophysics Data System (ADS)

Curti, Enzo; Dähn, Rainer; Farges, François; Vespa, Marika

2009-04-01

Microscopic distribution and speciation of Na, Mg, Ni and Cs in a simulated (inactive) nuclear waste glass were studied using micro X-ray fluorescence (μ-XRF) and micro X-ray absorption spectroscopy (μ-XAS), after aqueous leaching during 12 years at 90 °C. Na and Mg are major constituents of the glass that can be used to determine the progress of the glass corrosion process and the nature of secondary alteration phases. Ni and Cs represent dose determining long-lived radionuclides ( 59Ni, 135Cs) in vitrified nuclear waste. The Na-Mg μ-XRF maps revealed that the core regions of the glass fragments are apparently unaltered and compositionally homogeneous, whereas rims and interstitial spaces are enriched with Mg-rich smectite formed during the leaching process. The micro X-ray absorption near edge structure (μ-XANES) spectra collected at the Mg K-edge in the altered zones show three sharp resonances typical for crystalline Mg-silicates. These resonances are distinctive of Mg occupying undistorted octahedral positions. In contrast, the μ-XANES spectra collected in the core zones of the glass fragments lack this resonance pattern and are identical to the spectra measured on the pristine (unleached) MW glass. Micro extended X-ray absorption fine structure (μ-EXAFS) and μ-XANES analyses at the Ni K-edge revealed three distinct Ni(II) species: (a) Ni uniformly distributed in the glass matrix, (b) micro-inclusions with high Ni concentrations and (c) Ni associated to the Mg-clay. The comparison with reference spectra of unleached MW and other Ni-bearing silicate glasses indicated that species (a) represents the original coordinative environment of Ni in the glass. The μ-EXAFS analyses revealed that species (b) is structural Ni in trevorite (NiFe 2O 4), which probably formed through unmixing processes during the cooling of the glass melt. The μ-EXAFS of species (c) could be successfully modeled assuming specific adsorption or incorporation of Ni into the lattice of

Local structural and chemical ordering of nanosized Pt3±δCo probed by multiple-scattering x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Greco, Giorgia; Witkowska, Agnieszka; Principi, Emiliano; Minicucci, Marco; di Cicco, Andrea

2011-04-01

This work reports a detailed investigation of the local structure and chemical disorder of a Pt3±δCo thin film and Pt3±δCo nanoparticles. We have used a combination of techniques including x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and high-resolution transmission electron microscopy (TEM). High-quality XAS spectra at the Co K edge and Pt L3 edge have been analyzed using double-edge multiple-scattering data analysis. Structural extended x-ray absorption fine structure (EXAFS) refinements have been performed accounting for the reduction of the coordination numbers and degeneracy of three-atom configurations, resulting from the measured size distribution and stoichiometry. The important effect of chemical ordering on pair and three-atom configurations has been studied using computer simulations based on a simple model accounting for substitutional disorder, defined by an order parameter s. It has been found that individual EXAFS signals related to the minority species (Co) are extremely sensitive to substitutional disorder so their intensities, especially those of the collinear three-atom configurations, can be used as a measure of the ordering level. The thin film has been found to be chemically disordered (s⩽0.4), in agreement with previous estimates. The Pt3±δCo nanoalloy has been found to be partially ordered (s=0.6±0.1) while the local structure around Co atoms is characterized by a higher level of structural disorder as compared to the bulk-like thin film. The robust approach for nanomaterial characterization used in this work combining different techniques can, in principle, be applied for structural refinements of any binary nanocrystalline functional system.

Libraries of High and Mid-Resolution Spectra of F, G, K, and M Field Stars

NASA Astrophysics Data System (ADS)

Montes, D.

1998-06-01

I have compiled here the three libraries of high and mid-resolution optical spectra of late-type stars I have recently published. The libraries include F, G, K and M field stars, from dwarfs to giants. The spectral coverage is from 3800 to 1000 Å, with spectral resolution ranging from 0.09 to 3.0 Å. These spectra include many of the spectral lines most widely used as optical and near-infrared indicators of chromospheric activity. The spectra have been obtained with the aim of providing a library of high and mid-resolution spectra to be used in the study of active chromosphere stars by applying a spectral subtraction technique. However, the data set presented here can also be utilized in a wide variety of ways. A digital version of all the fully reduced spectra is available via FTP and the World Wide Web (WWW) in FITS format.

Structure of high-resolution K β1 ,3 x-ray emission spectra for the elements from Ca to Ge

NASA Astrophysics Data System (ADS)

Ito, Y.; Tochio, T.; Yamashita, M.; Fukushima, S.; Vlaicu, A. M.; Syrocki, Ł.; Słabkowska, K.; Weder, E.; Polasik, M.; Sawicka, K.; Indelicato, P.; Marques, J. P.; Sampaio, J. M.; Guerra, M.; Santos, J. P.; Parente, F.

2018-05-01

The K β x-ray spectra of the elements from Ca to Ge have been systematically investigated using a high-resolution antiparallel double-crystal x-ray spectrometer. Each K β1 ,3 natural linewidth has been corrected using the instrumental function of this type of x-ray spectrometer, and the spin doublet energies have been obtained from the peak position values in K β1 ,3 x-ray spectra. For all studied elements the corrected K β1 x-ray lines FWHM increase linearly as a function of Z . However, for K β3 x-ray lines this dependence is generally not linear in the case of 3 d elements but increases from Sc to Co elements. It has been found that the contributions of satellite lines are considered to be [K M ] shake processes. Our theoretically predicted synthetic spectra of Ca, Mn, Cu, and Zn are in very good agreement with our high-resolution measurements, except in the case of Mn, due to the open-shell valence configuration effect (more than 7000 transitions for diagram lines and more than 100 000 transitions for satellite lines) and the influence of the complicated structure of the metallic Mn.

Charge transfer transitions in the photoluminescence spectra of Zn1-xMexO (Me = Mn, Ni, Co) oxide compounds

NASA Astrophysics Data System (ADS)

Sokolov, V. I.; Gruzdev, N. B.; Pustovarov, V. A.; Churmanov, V. N.

2013-01-01

Crystals of Zn1-xCoxO and Zn1-xNixO are studied by photoluminescence at temperatures of 8 and 90 K. By resolving the spectra into sums of gaussian distributions and using the known positions of donor and acceptor levels of 3d-impurities relative to the edges of the allowed bands, the observed peaks in the photoluminescence spectra are interpreted in terms of radiative recombination through donor and acceptor levels of nickel and cobalt ions. These results are compared with previously observed features of the photoluminescence spectra of Zn1-xMnxO crystals.

Combined mineralogical and EXAFS characterization of polluted sediments for the definition of technological variables and constraints

NASA Astrophysics Data System (ADS)

Brigatti, M. F.; Elmi, C.; Laurora, A.; Malferrari, D.; Medici, L.

2009-04-01

EXAFS spectra were used to define and optimize the technological variables of the recovery process.

Structural investigations in helium charged titanium films using grazing incidence XRD and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Wan, Chubin; Zhou, Xiaosong; Wang, Yuting; Li, Shina; Ju, Xin; Peng, Shuming

2014-01-01

The crystal structure and local atomic arrangements surrounding Ti atoms were determined for He-charged hexagonal close-packed (hcp) Ti films and measured at glancing angles by synchrotron radiation X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, respectively. The charged specimens were prepared by direct current magnetron sputtering with a He/Ar mixture. He atoms with a relatively medium concentration (He/Ti atomic ratio as high as 17 at.%) were incorporated evenly in the deposited films. XRD results showed the changes in the peak intensities in Ti films with different He contents. EXAFS Fourier Transform analysis indicated that the average Ti-Ti distance decreased significantly, and proved the existence of phase transition.

Experimental results of use of triple-energy X-ray beam with K-edge filter in multi-energy imaging

NASA Astrophysics Data System (ADS)

Kim, D.; Lee, S.; Jeon, P.-H.

2016-04-01

Multi-energy imaging is useful for contrast enhancement of lesions, quantitative analysis of specific materials and material separation in the human body. Generally, dual-energy methods are applied to discriminating two materials, but this method cannot discriminate more than two materials. Photon-counting detectors provide spectral information from polyenergetic X-rays using multiple energy bins. In this work, we developed triple-energy X-ray beams using a filter with K-edge energy and applied them experimentally. The energy spectra of triple-energy X-ray beams were assessed by using a spectrometer. The designed triple-energy X-ray beams were validated by measuring quantitative evaluations with mean energy ratio (MER), contrast variation ratio (CVR) and exposure efficiency (EE). Then, triple-energy X-ray beams were used to extract density map of three materials, iodine (I), aluminum (Al) and polymethyl methacrylate (PMMA). The results of the thickness density maps obtained with the developed triple-energy X-ray beams were compared to those acquired using the photon-counting method. As a result, it was found experimentally that the proposed triple-energy X-ray beam technique can separate the three materials as well as the photon-counting method.

Origins of extreme broadening mechanisms in near-edge x-ray spectra of nitrogen compounds

NASA Astrophysics Data System (ADS)

Vinson, John; Jach, Terrence; Elam, W. T.; Denlinger, J. D.

2014-11-01

We demonstrate the observation of many-body lifetime effects in valence-band x-ray emission. A comparison of the N K α emission of crystalline ammonium nitrate to molecular-orbital calculations revealed an unexpected, extreme broadening of the NO σ recombination—so extensively as to virtually disappear. GW calculations establish that this disappearance is due to a large imaginary component of the self-energy associated with the NO σ orbitals. Building upon density-functional theory, we have calculated radiative transitions from the nitrogen 1 s level of ammonium nitrate and ammonium chloride using a Bethe-Salpeter method to include electron-hole interactions. The absorption and emission spectra of both crystals evince large, orbital-dependent sensitivity to molecular dynamics. We demonstrate that many-body effects as well as thermal and zero-point motion are vital for understanding observed spectra. A computational approach using average atomic positions and uniform broadening to account for lifetime and phonon effects is unsatisfactory.

WREP: A wavelet-based technique for extracting the red edge position from reflectance spectra for estimating leaf and canopy chlorophyll contents of cereal crops

NASA Astrophysics Data System (ADS)

Li, Dong; Cheng, Tao; Zhou, Kai; Zheng, Hengbiao; Yao, Xia; Tian, Yongchao; Zhu, Yan; Cao, Weixing

2017-07-01

Red edge position (REP), defined as the wavelength of the inflexion point in the red edge region (680-760 nm) of the reflectance spectrum, has been widely used to estimate foliar chlorophyll content from reflectance spectra. A number of techniques have been developed for REP extraction in the past three decades, but most of them require data-specific parameterization and the consistence of their performance from leaf to canopy levels remains poorly understood. In this study, we propose a new technique (WREP) to extract REPs based on the application of continuous wavelet transform to reflectance spectra. The REP is determined by the zero-crossing wavelength in the red edge region of a wavelet transformed spectrum for a number of scales of wavelet decomposition. The new technique is simple to implement and requires no parameterization from the user as long as continuous wavelet transforms are applied to reflectance spectra. Its performance was evaluated for estimating leaf chlorophyll content (LCC) and canopy chlorophyll content (CCC) of cereal crops (i.e. rice and wheat) and compared with traditional techniques including linear interpolation, linear extrapolation, polynomial fitting and inverted Gaussian. Our results demonstrated that WREP obtained the best estimation accuracy for both LCC and CCC as compared to traditional techniques. High scales of wavelet decomposition were favorable for the estimation of CCC and low scales for the estimation of LCC. The difference in optimal scale reveals the underlying mechanism of signature transfer from leaf to canopy levels. In addition, crop-specific models were required for the estimation of CCC over the full range. However, a common model could be built with the REPs extracted with Scale 5 of the WREP technique for wheat and rice crops when CCC was less than 2 g/m2 (R2 = 0.73, RMSE = 0.26 g/m2). This insensitivity of WREP to crop type indicates the potential for aerial mapping of chlorophyll content between growth seasons

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

PubMed

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

2016-01-12

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

Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce2(C8H8)3 and Ce(C8H8)2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walter, Marc D.; Booth, Corwin H.; Lukens, Wayne W.

2009-02-02

New synthetic procedures for the preparation of Ce(cot)2, cerocene, from [Li(thf)4][Ce(cot)2], and Ce2(cot)3 in high yield and purity are reported. Heating solid Ce(cot)2 yields Ce2(cot)3 and COT while heating Ce2(cot)3 with an excess of COT in C6D6 to 65oC over four months yields Ce(cot)2. The solid state magnetic susceptibility of these three organocerium compounds shows that Ce(cot)2 behaves as a TIP (temperature independent paramagnet) over the temperature range of 5-300 K, while that of Ce2(cot)3 shows that the spin carriers are antiferromagnetically coupled below 10 K; above 10 K, the individual spins are uncorrelated, and [Ce(cot)2]- behaves as an isolatedmore » f1 paramagnet. The EPR at 1.5K for Ce2(cot)3 and [Ce(cot)2]- have ground state of MJ= +- 1/2. The LIII edge XANES of Ce(cot)2 (Booth, C.H.; Walter, M.D.; Daniel, M.; Lukens, W.W., Andersen, R.A., Phys. Rev. Lett. 2005, 95, 267202) and 2Ce2(cot)3 over 30-500 K are reported; the Ce(cot)2 XANES spectra show Ce(III) and Ce(IV) signatures up to a temperature of approximately 500 K, whereupon the Ce(IV) signature disappears, consistent with the thermal behavior observed in the melting experiment. The EXAFS of Ce(cot)2 and Ce2(cot)3 are reported at 30 K; the agreement between the molecular parameters for Ce(cot)2 derived from EXAFS and single crystal X-ray diffraction data are excellent. In the case of Ce2(cot)3 no X-ray diffraction data are known to exist, but the EXAFS are consistent with a"triple-decker" sandwich structure. A molecular rationalization is presented for the electronic structure of cerocene having a multiconfiguration ground state that is an admixture of the two configurations Ce(III, 4f1)(cot1.5-)2 and Ce(IV, 4f0)(cot2-)2; the multiconfigurational ground state has profound effects on the magnetic properties and on the nature of the chemical bond in cerocene and, perhaps, other molecules.« less

The interaction of copper ions with Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli: an X-ray absorption near-edge structure (XANES) spectroscopy study.

PubMed

Zanzen, Ulrike; Bovenkamp-Langlois, Lisa; Klysubun, Wantana; Hormes, Josef; Prange, Alexander

2018-04-01

The antimicrobial properties of copper ions have been known for a long time. However, the exact mechanism of action of the transition metal on microorganisms has long been unclear. X-ray absorption near-edge structure (XANES) spectroscopy at the Cu K edge allows the determination of copper speciation in Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa that have been treated with Cu(II) and Cu(I) solutions. The death/inactivation of the bacteria was observed using plate counting and light microscopy. The Cu K-XANES spectra of the two Gram-negative bacteria are different than those of the Gram-positive strain. The results clearly show that the Cu + -S bond contributes to the antibacterial activity of copper, as in the case of silver. The detailed evaluation of the differentiated absorption spectra shows that Cu + (not Cu 2+ ) is the dominant ion that binds to the bacteria. Because Cu + is not the most common copper ion, copper is not as effective an antibacterial agent as silver, whose common valency is actually + 1. Any reaction of copper with phosphorus from the bacteria can be excluded after the evaluation of the absorption spectra.

Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.

2017-02-01

Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

Total edge irregularity strength of (n,t)-kite graph

NASA Astrophysics Data System (ADS)

Winarsih, Tri; Indriati, Diari

2018-04-01

Let G(V, E) be a simple, connected, and undirected graph with vertex set V and edge set E. A total k-labeling is a map that carries vertices and edges of a graph G into a set of positive integer labels {1, 2, …, k}. An edge irregular total k-labeling λ :V(G)\\cup E(G)\\to \\{1,2,\\ldots,k\\} of a graph G is a labeling of vertices and edges of G in such a way that for any different edges e and f, weights wt(e) and wt(f) are distinct. The weight wt(e) of an edge e = xy is the sum of the labels of vertices x and y and the label of the edge e. The total edge irregularity strength of G, tes(G), is defined as the minimum k for which a graph G has an edge irregular total k-labeling. An (n, t)-kite graph consist of a cycle of length n with a t-edge path (the tail) attached to one vertex of a cycle. In this paper, we investigate the total edge irregularity strength of the (n, t)-kite graph, with n > 3 and t > 1. We obtain the total edge irregularity strength of the (n, t)-kite graph is tes((n, t)-kite) = \\lceil \\frac{n+t+2}{3}\\rceil .

Aluminium X-ray absorption Near Edge Structure in model compounds and Earth's surface minerals

NASA Astrophysics Data System (ADS)

Ildefonse, P.; Cabaret, D.; Sainctavit, P.; Calas, G.; Flank, A.-M.; Lagarde, P.

Aluminium K-edge X-ray absorption near edge spectra (XANES) of a suite of silicate and oxides minerals consist of electronic excitations occurring in the edge region, and multiple scattering resonances at higher energies. The main XANES feature for four-fold Al is at around 2 eV lower energy than the main XANES feature for six-fold Al. This provides a useful probe for coordination numbers in clay minerals, gels, glasses or material with unknown Al-coordination number. Six-fold aluminium yields a large variety of XANES features which can be correlated with octahedral point symmetry, number of aluminium sites and distribution of Al-O distances. These three parameters may act together, and the quantitative interpretation of XANES spectra is difficult. For a low point symmetry (1), variations are mainly related to the number of Al sites and distribution of Al-O distances: pyrophyllite, one Al site, is clearly distinguished from kaolinite and gibbsite presenting two Al sites. For a given number of Al-site (1), variations are controlled by changes in point symmetry, the number of XANES features being increased as point symmetry decreases. For a given point symmetry (1) and a given number of Al site (1), variations are related to second nearest neighbours (gibbsite versus kaolinite). The amplitude of the XANES feature at about 1566 eV is a useful probe for the assessment of AlIV/Altotal ratios in 2/1 phyllosilicates. Al-K XANES has been performed on synthetic Al-bearing goethites which cannot be studied by 27Al NMR. At low Al content, Al-K XANES is very different from that of α-AlOOH but at the highest level, XANES spectrum tends to that of diaspore. Al-K XAS is thus a promising tool for the structural study of poorly ordered materials such as clay minerals and natural alumino-silicate gels together with Al-subsituted Fe-oxyhydroxides.

Modeling L2,3-Edge X-ray Absorption Spectroscopy with Real-Time Exact Two-Component Relativistic Time-Dependent Density Functional Theory.

PubMed

Kasper, Joseph M; Lestrange, Patrick J; Stetina, Torin F; Li, Xiaosong

2018-04-10

X-ray absorption spectroscopy is a powerful technique to probe local electronic and nuclear structure. There has been extensive theoretical work modeling K-edge spectra from first principles. However, modeling L-edge spectra directly with density functional theory poses a unique challenge requiring further study. Spin-orbit coupling must be included in the model, and a noncollinear density functional theory is required. Using the real-time exact two-component method, we are able to variationally include one-electron spin-orbit coupling terms when calculating the absorption spectrum. The abilities of different basis sets and density functionals to model spectra for both closed- and open-shell systems are investigated using SiCl 4 and three transition metal complexes, TiCl 4 , CrO 2 Cl 2 , and [FeCl 6 ] 3- . Although we are working in the real-time framework, individual molecular orbital transitions can still be recovered by projecting the density onto the ground state molecular orbital space and separating contributions to the time evolving dipole moment.

Arsenic Scavenging by Al-Substituted Ferrihydrites in a Circumneutral pH River Impacted by the Acid Mine Drainage of Carnoulès, Gard, France

NASA Astrophysics Data System (ADS)

ADRA, A.; Morin, G.; ona-Nguema, G.; Maillot, F.; Casiot, C.; Bruneel, O.

2013-12-01

Ferrihydrite (Fh) is a nanocrystalline ferric oxyhydroxide involved in the retention of pollutants in natural systems and in water-treatment processes. The status and properties of major chemical impurities in natural Fh is however still scarcely documented. Here we investigated the structure and reactivity of aluminum-rich Fh from river-bed sediments collected in a circumneutral river (pH 6-7) impacted by an arsenic-rich acid mine drainage (AMD). Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge shows that Fh is the predominant mineral phase forming after neutralization of the AMD, in association with minor amount of schwertmannite transported from the AMD. EXAFS analysis indicates that Al(III) substitutes for Fe(III) ions into the Fh structure in the natural sediment samples, with local aluminum concentration within the 20-37×7 mol%Al range, in agreement with bulk chemical compositions. Synthetic aluminous Fh analogues prepared in the present study are found to be less Al-substituted (14-18×4 mol%Al). Finally, EXAFS analysis at the arsenic K-edge indicates that As(V) form similar inner-sphere surface complexes on the natural and synthetic Al-substituted Fh studied. Our results provide direct evidences for the scavenging of arsenic by natural Al- Fh, with possible implications for other pollutants in natural or engineered systems.

The potential for neurovascular intravenous angiography using K-edge digital subtraction angiography

NASA Astrophysics Data System (ADS)

Schültke, E.; Fiedler, S.; Kelly, M.; Griebel, R.; Juurlink, B.; LeDuc, G.; Estève, F.; Le Bas, J.-F.; Renier, M.; Nemoz, C.; Meguro, K.

2005-08-01

Background: Catheterization of small-caliber blood vessels in the central nervous system can be extremely challenging. Alternatively, intravenous (i.v.) administration of contrast agent is minimally invasive and therefore carries a much lower risk for the patient. With conventional X-ray equipment, volumes of contrast agent that could be safely administered to the patient do not allow acquisition of high-quality images after i.v. injection, because the contrast bolus is extremely diluted by passage through the heart. However, synchrotron-based digital K-edge subtraction angiography does allow acquisition of high-quality images after i.v. administration of relatively small doses of contrast agent. Materials and methods: Eight adult male New Zealand rabbits were used for our experiments. Animals were submitted to both angiography with conventional X-ray equipment and synchrotron-based digital subtraction angiography. Results: With conventional X-ray equipment, no contrast was seen in either cerebral or spinal blood vessels after i.v. injection of iodinated contrast agent. However, using K-edge digital subtraction angiography, as little as 1 ml iodinated contrast agent, when administered as i.v. bolus, yielded images of small-caliber blood vessels in the central nervous system (both brain and spinal cord). Conclusions: If it would be possible to image blood vessels of the same diameter in the central nervous system of human patients, the synchrotron-based technique could yield high-quality images at a significantly lower risk for the patient than conventional X-ray imaging. Images could be acquired where catheterization of feeding blood vessels has proven impossible.

Helicopter rotor trailing edge noise. [noise prediction

NASA Technical Reports Server (NTRS)

Schlinker, R. H.; Amier, R. K.

1981-01-01

A two dimensional section of a helicopter main rotor blade was tested in an acoustic wind tunnel at close to full-scale Reynolds numbers to obtain boundary layer data and acoustic data for use in developing an acoustic scaling law and testing a first principles trailing edge noise theory. Results were extended to the rotating frame coordinate system to develop a helicopter rotor trailing edge noise prediction. Comparisons of the calculated noise levels with helicopter flyover spectra demonstrate that trailing edge noise contributes significantly to the total helicopter noise spectrum at high frequencies. This noise mechanism is expected to control the minimum rotor noise. In the case of noise radiation from a local blade segment, the acoustic directivity pattern is predicted by the first principles trailing edge noise theory. Acoustic spectra are predicted by a scaling law which includes Mach number, boundary layer thickness and observer position. Spectrum shape and sound pressure level are also predicted by the first principles theory but the analysis does not predict the Strouhal value identifying the spectrum peak.

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

PubMed Central

Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

2015-01-01

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

Characterization of Flap Edge Noise Radiation from a High-Fidelity Airframe Model

NASA Technical Reports Server (NTRS)

Humphreys, William M., Jr.; Khorrami, Mehdi R.; Lockard, David P.; Neuhart, Dan H.; Bahr, Christopher J.

2015-01-01

The results of an experimental study of the noise generated by a baseline high-fidelity airframe model are presented. The test campaign was conducted in the open-jet test section of the NASA Langley 14- by 22-foot Subsonic Tunnel on an 18%-scale, semi-span Gulfstream airframe model incorporating a trailing edge flap and main landing gear. Unsteady surface pressure measurements were obtained from a series of sensors positioned along the two flap edges, and far field acoustic measurements were obtained using a 97-microphone phased array that viewed the pressure side of the airframe. The DAMAS array deconvolution method was employed to determine the locations and strengths of relevant noise sources in the vicinity of the flap edges and the landing gear. A Coherent Output Power (COP) spectral method was used to couple the unsteady surface pressures measured along the flap edges with the phased array output. The results indicate that outboard flap edge noise is dominated by the flap bulb seal cavity with very strong COP coherence over an approximate model-scale frequency range of 1 to 5 kHz observed between the array output and those unsteady pressure sensors nearest the aft end of the cavity. An examination of experimental COP spectra for the inboard flap proved inconclusive, most likely due to a combination of coherence loss caused by decorrelation of acoustic waves propagating through the thick wind tunnel shear layer and contamination of the spectra by tunnel background noise at lower frequencies. Directivity measurements obtained from integration of DAMAS pressure-squared values over defined geometric zones around the model show that the baseline flap and landing gear are only moderately directional as a function of polar emission angle.

The absorption, fluorescence and phosphorescence spectra of α and β-F, Cl, Br-naphthalenes in crystalline matrixes at 77 K

NASA Astrophysics Data System (ADS)

Iliescu, T.; Milea, I.; Abdolrahman, P. M.

1984-03-01

The paper studies the absorption, fluorescence and phosphorescence spectra of α and β-F, Cl, Br-naphtalenes (α, β-F, Cl,BrN) in different matrixes at 77 K and different concentrations. From these spectra one obtaines the vibrational frequences.

Bond compressibility and bond Grüneisen parameters of CdTe

NASA Astrophysics Data System (ADS)

Fornasini, P.; Grisenti, R.; Irifune, T.; Shinmei, T.; Mathon, O.; Pascarelli, S.; Rosa, A. D.

2018-06-01

Extended x-ray absorption fine structure (EXAFS) at the Cd K edge and diffraction patterns have been measured on CdTe as a function of pressure from 100 kPa (1 bar) to 5 GPa using a cell with nano-polycrystalline diamond anvils and an x-ray focussing scanning spectrometer. Three phases—zincblende (ZB), mixed cinnabar-ZB and rocksalt (RS)—are well distinguished in different pressure intervals. The bond compressibility measured by EXAFS in the ZB phase is slightly smaller than the one measured by diffraction and decreases significantly faster when the pressure increases; the difference is attributed to the effect of relative vibrations perpendicular to the Cd–Te bond. The parallel mean square relative displacement (MSRD) decreases, the perpendicular MSRD increases when the pressure increases, leading to an increasing anisotropy of relative atomic vibrations. A constant-temperature bond Grüneisen parameter (GP) has been evaluated for the ZB phase and compared with the constant-pressure bond GP measured in a previous experiment; an attempt is made to connect the bond GPs measured by EXAFS and the more familiar thermodynamic GP and mode GPs; the comparisons suggest the inadequacy of the quasi-harmonic approximation to deal with the local vibrational properties sampled by EXAFS.

On the Total Edge Irregularity Strength of Generalized Butterfly Graph

NASA Astrophysics Data System (ADS)

Dwi Wahyuna, Hafidhyah; Indriati, Diari

2018-04-01

Let G(V, E) be a connected, simple, and undirected graph with vertex set V and edge set E. A total k-labeling is a map that carries vertices and edges of a graph G into a set of positive integer labels {1, 2, …, k}. An edge irregular total k-labeling λ: V(G) ∪ E(G) → {1, 2, …, k} of a graph G is a total k-labeling such that the weights calculated for all edges are distinct. The weight of an edge uv in G, denoted by wt(uv), is defined as the sum of the label of u, the label of v, and the label of uv. The total edge irregularity strength of G, denoted by tes(G), is the minimum value of the largest label k over all such edge irregular total k-labelings. A generalized butterfly graph, BFn , obtained by inserting vertices to every wing with assumption that sum of inserting vertices to every wing are same then it has 2n + 1 vertices and 4n ‑ 2 edges. In this paper, we investigate the total edge irregularity strength of generalized butterfly graph, BFn , for n > 2. The result is tes(B{F}n)=\\lceil \\frac{4n}{3}\\rceil .

In situ removal of carbon contamination from a chromium-coated mirror: ideal optics to suppress higher-order harmonics in the carbon K-edge region.

PubMed

Toyoshima, Akio; Kikuchi, Takashi; Tanaka, Hirokazu; Mase, Kazuhiko; Amemiya, Kenta

2015-11-01

Carbon-free chromium-coated optics are ideal in the carbon K-edge region (280-330 eV) because the reflectivity of first-order light is larger than that of gold-coated optics while the second-order harmonics (560-660 eV) are significantly suppressed by chromium L-edge and oxygen K-edge absorption. Here, chromium-, gold- and nickel-coated mirrors have been adopted in the vacuum ultraviolet and soft X-ray branch beamline BL-13B at the Photon Factory in Tsukuba, Japan. Carbon contamination on the chromium-coated mirror was almost completely removed by exposure to oxygen at a pressure of 8 × 10(-2) Pa for 1 h under irradiation of non-monochromated synchrotron radiation. The pressure in the chamber recovered to the order of 10(-7) Pa within a few hours. The reflectivity of the chromium-coated mirror of the second-order harmonics in the carbon K-edge region (560-660 eV) was found to be a factor of 0.1-0.48 smaller than that of the gold-coated mirror.

Effect of reflection and refraction on NEXAFS spectra measured in TEY mode

PubMed Central

2018-01-01

The evolution of near-edge X-ray absorption fine structure in the vicinity of the K-absorption edge of oxygen for HfO2 over a wide range of incidence angles is analyzed by simultaneous implementation of the total-electron-yield (TEY) method and X-ray reflection spectroscopy. It is established that the effect of refraction on the TEY spectrum is greater than that of reflection and extends into the angular region up to angles 2θc. Within angles that are less than the critical angle, both the reflection and refraction strongly distort the shape of the TEY spectrum. Limitations of the technique for the calculation of optical constants from the reflection spectra using the Kramers–Kronig relation in the limited energy region in the vicinity of thresholds are discussed in detail. PMID:29271772

Cell edge detection in JPEG2000 wavelet domain - analysis on sigmoid function edge model.

PubMed

Punys, Vytenis; Maknickas, Ramunas

2011-01-01

Big virtual microscopy images (80K x 60K pixels and larger) are usually stored using the JPEG2000 image compression scheme. Diagnostic quantification, based on image analysis, might be faster if performed on compressed data (approx. 20 times less the original amount), representing the coefficients of the wavelet transform. The analysis of possible edge detection without reverse wavelet transform is presented in the paper. Two edge detection methods, suitable for JPEG2000 bi-orthogonal wavelets, are proposed. The methods are adjusted according calculated parameters of sigmoid edge model. The results of model analysis indicate more suitable method for given bi-orthogonal wavelet.

Experimental observation of the shift and width of the aluminium K absorption edge in laser shock-compressed plasmas

NASA Astrophysics Data System (ADS)

Hall, T. A.; Al-Kuzee, J.; Benuzzi, A.; Koenig, M.; Krishnan, J.; Grandjouan, N.; Batani, D.; Bossi, S.; Nicolella, S.

1998-03-01

Experimental measurements of the shift and width of the aluminium K-absorption edge in laser shock-compressed plasma is presented. The spectrometer used in these experiments allows an accurate wavelength calibration and fiduciary and hence provides precise measurements of both the shift and the width of the absorption edge. Results have been obtained for compressions up to approximately ×2 and temperatures up to about 1.5 eV. The values of shift and width are compared with a new model with which there is very good agreement.

Analysis of X-ray adsorption edges: L 2,3 edge of FeCl 4 -

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S.

We describe a detailed analysis of the features of the X-ray adsorption spectra at the Fe L 2,3 edge of FeCl 4. The objective of this analysis is to explain the origin of the complex features in relation to properties of the wavefunctions, especially for the excited states. These properties include spin-orbit and ligand field splittings where a novel aspect of the dipole selection rules is applied to understand the influence of these splittings on the spectra. We also explicitly take account of the intermediate coupling of the open core and valence shell electrons. Our analysis also includes comparison ofmore » theory and experiment for the Fe L 2,3 edge and comparison of theoretical predictions for the Fe 3+ cation and FeCl 4-. The electronic structure is obtained from theoretical wavefunctions for the ground and excited states.« less

Measurement and validation of benchmark-quality thick-target tungsten X-ray spectra below 150 kVp.

PubMed

Mercier, J R; Kopp, D T; McDavid, W D; Dove, S B; Lancaster, J L; Tucker, D M

2000-11-01

Pulse-height distributions of two constant potential X-ray tubes with fixed anode tungsten targets were measured and unfolded. The measurements employed quantitative alignment of the beam, the use of two different semiconductor detectors (high-purity germanium and cadmium-zinc-telluride), two different ion chamber systems with beam-specific calibration factors, and various filter and tube potential combinations. Monte Carlo response matrices were generated for each detector for unfolding the pulse-height distributions into spectra incident on the detectors. These response matrices were validated for the low error bars assigned to the data. A significant aspect of the validation of spectra, and a detailed characterization of the X-ray tubes, involved measuring filtered and unfiltered beams at multiple tube potentials (30-150 kVp). Full corrections to ion chamber readings were employed to convert normalized fluence spectra into absolute fluence spectra. The characterization of fixed anode pitting and its dominance over exit window plating and/or detector dead layer was determined. An Appendix of tabulated benchmark spectra with assigned error ranges was developed for future reference.

The discontinuity near 1600 A in the spectra of DA white dwarfs

NASA Technical Reports Server (NTRS)

Wegner, G.

1984-01-01

Ultraviolet spectroscopic observations of two relatively cool DA white dwarfs, L481 - 60 (= WD 1544 - 37) and BPM 1266 ( = WD 2105 - 82), with the International Ultraviolet Explorer (IUE) satellite show a strong drop in their spectral energy distributions below 1600 A. Published model atmospheres and thier visual spectra suggest that these two stars have effective temperatures in the vicinity of 9,000-10,000 K, and it is proposed that the 1600 A feature could be due to the 342(1S) 3s2(1S) photoionization edge of Mg I.

EXAFS studies of prostate cancer cell lines

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Simulation design of high reverse blocking high-K/low-K compound passivation AlGaN/GaN Schottky barrier diode with gated edge termination

NASA Astrophysics Data System (ADS)

Bai, Zhiyuan; Du, Jiangfeng; Xin, Qi; Li, Ruonan; Yu, Qi

2017-11-01

In this paper, a novel high-K/low-K compound passivation AlGaN/GaN Schottky Barrier Diode (CPG-SBD) is proposed to improve the off-state characteristics of AlGaN/GaN schottky barrier diode with gated edge termination (GET-SBD) by adding low-K blocks in to the high-K passivation layer. The reverse leakage current of CPG-SBD can be reduced to 1.6 nA/mm by reducing the thickness of high-K dielectric under GET region to 5 nm, while the forward voltage and on-state resistance keep 1 V and 3.8 Ω mm, respectively. Breakdown voltage of CPG-SBDs can be improved by inducing discontinuity of the electric field at the high-K/low-K interface. The breakdown voltage of the optimized CPG-SBD with 4 blocks of low-K can reach 1084 V with anode to cathode distance of 5 μm yielding a high FOM of 5.9 GW/cm2. From the C-V simulation results, CPG-SBDs induce no parasitic capacitance by comparison of the GET-SBDs.

Near sulfur L-edge X-ray absorption spectra of methanethiol in isolation and adsorbed on a Au(111) surface: a theoretical study using the four-component static exchange approximation.

PubMed

Villaume, Sebastien; Ekström, Ulf; Ottosson, Henrik; Norman, Patrick

2010-06-07

The relativistic four-component static exchange approach for calculation of near-edge X-ray absorption spectra has been reviewed. Application of the method is made to the Au(111) interface and the adsorption of methanethiol by a study of the near sulfur L-edge spectrum. The binding energies of the sulfur 2p(1/2) and 2p(3/2) sublevels in methanethiol are determined to be split by 1.2 eV due to spin-orbit coupling, and the binding energy of the 2p(3/2) shell is lowered from 169.2 eV for the isolated system to 167.4 and 166.7-166.8 eV for methanethiol in mono- and di-coordinated adsorption sites, respectively (with reference to vacuum). In the near L-edge X-ray absorption fine structure spectrum only the sigma*(S-C) peak at 166 eV remains intact by surface adsorption, whereas transitions of predominantly Rydberg character are largely quenched in the surface spectra. The sigma*(S-H) peak of methanethiol is replaced by low-lying, isolated, sigma*(S-Au) peak(s), where the number of peaks in the latter category and their splittings are characteristic of the local bonding situation of the sulfur.

Simulation studies for operating electron beam ion trap at very low energy for disentangling edge plasma spectra

NASA Astrophysics Data System (ADS)

Jin, Xuelong; Fei, Zejie; Xiao, Jun; Lu, Di; Hutton, Roger; Zou, Yaming

2012-07-01

Electron beam ion traps (EBITs) are very useful tools for disentanglement studies of atomic processes in plasmas. In order to assist studies on edge plasma spectroscopic diagnostics, a very low energy EBIT, SH-PermEBIT, has been set up at the Shanghai EBIT lab. In this work, simulation studies for factors which hinder an EBIT to operate at very low electron energies were made based on the Tricomp (Field Precision) codes. Longitudinal, transversal, and total kinetic energy distributions were analyzed for all the electron trajectories. Influences from the electron current and electron energy on the energy depression caused by the space charge are discussed. The simulation results show that although the energy depression is most serious along the center of the electron beam, the electrons in the outer part of the beam are more likely to be lost when an EBIT is running at very low energy. Using the simulation results to guide us, we successfully managed to reach the minimum electron beam energy of 60 eV with a beam transmission above 57% for the SH-PermEBIT. Ar and W spectra were measured from the SH-PermEBIT at the apparent electron beam energies (read from the voltage difference between the electron gun cathode and the central drift tube) of 60 eV and 1200 eV, respectively. The spectra are shown in this paper.

Arsenic scavenging by aluminum-substituted ferrihydrites in a circumneutral pH river impacted by acid mine drainage.

PubMed

Adra, Areej; Morin, Guillaume; Ona-Nguema, Georges; Menguy, Nicolas; Maillot, Fabien; Casiot, Corinne; Bruneel, Odile; Lebrun, Sophie; Juillot, Farid; Brest, Jessica

2013-11-19

Ferrihydrite (Fh) is a nanocrystalline ferric oxyhydroxide involved in the retention of pollutants in natural systems and in water-treatment processes. The status and properties of major chemical impurities in natural Fh is however still scarcely documented. Here we investigated the structure of aluminum-rich Fh, and their role in arsenic scavenging in river-bed sediments from a circumneutral river (pH 6-7) impacted by an arsenic-rich acid mine drainage (AMD). Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge shows that Fh is the predominant mineral phase forming after neutralization of the AMD, in association with minor amount of schwertmannite transported from the AMD. TEM-EDXS elemental mapping and SEM-EDXS analyses combined with EXAFS analysis indicates that Al(3+) substitutes for Fe(3+) ions into the Fh structure in the natural sediment samples, with local aluminum concentration within the 25-30 ± 10 mol %Al range. Synthetic aluminous Fh prepared in the present study are found to be less Al-substituted (14-20 ± 5 mol %Al). Finally, EXAFS analysis at the arsenic K-edge indicates that As(V) form similar inner-sphere surface complexes on the natural and synthetic Al-substituted Fh studied. Our results provide direct evidence for the scavenging of arsenic by natural Al-Fh, which emphasize the possible implication of such material for scavenging pollutants in natural or engineered systems.

Turbulence Measurements on a Flap-Edge Model

NASA Technical Reports Server (NTRS)

Moriarty, Patrick; Bradshaw, Peter; Cantwell, Brian; Ross, James

1998-01-01

Turbulence measurements have been made on a flap-edge and leading-edge slat model using hot-wire anemometry, and, later, particle image velocimetry. The properties of hot-wire anemometry were studied using facilities at NASA Ames Research Center. Hot-film probes were used because of their durability, but cross-films were limited by non-linear end effects. As a warm-up exercise, hot-film probes were used to measure velocities in the farfield wake of a cylinder with an airfoil in the near-field wake. The airfoil reduced the drag coefficient of the system by 10%. A single-wire hot-film probe was used to measure velocity profiles over the top of a NACA 63(sub 2)-215 Mod. B wing with a Fowler flap and leading,-edge slat. Results showed the size of slat wake was dependent upon the slat deflection angle. Velocity increased through the slat gap with increased deflection. The acoustically modified slat decreased the chance of separation. Measurements were taken at the flap edge with a single hot-film. Trends in the data indicate velocity and turbulence levels increase at the flap edge. The acoustically modified flap modifies the mean flow near the flap edge. Correlations were made between the hot-film signal and the unsteady pressure transducers on the wing which were published in a NASA CDTM. The principles of Particle Image Velocimetry (PIV) were studied at Florida State University. Spectral PIV was used to measure the spectra of a subsonic jet. Measured frequencies were close to the predicted frequency of jet shedding. Spectral PIV will be used to measure the spectra of the slat flow in the second 7 x lO-ft. wind tunnel test. PIV has an advantage that it can measure velocity and spectra of the entire flowfield instantaneously. However, problems arise when trying, to store this massive amount of PIV data. Support for this research has continued through a NASA Graduate Student Program Fellowship which will end in June 1999. The thesis should be completed by this time.

Studies on effective atomic numbers, electron densities from mass attenuation coefficients near the K edge in some samarium compounds.

PubMed

Akman, F; Durak, R; Turhan, M F; Kaçal, M R

2015-07-01

The effective atomic numbers and electron densities of some samarium compounds were determined using the experimental total mass attenuation coefficient values near the K edge in the X-ray energy range from 36.847 up to 57.142 keV. The measurements, in the region from 36.847 to 57.142 keV, were done in a transmission geometry utilizing the Kα2, Kα1, Kβ1 and Kβ2 X-rays from different secondary source targets excited by the 59.54 keV gamma-photons from an Am-241 annular source. This paper presents the first measurement of the effective atomic numbers and electron densities for some samarium compounds near the K edge. The results of the study showed that the measured values were in good agreement with the theoretically calculated ones. Copyright © 2015 Elsevier Ltd. All rights reserved.

Theory of K-edge resonant inelastic x-ray scattering and its application for La0.5Sr1.5MnO4

NASA Astrophysics Data System (ADS)

Seman, T. F.; Liu, X.; Hill, J. P.; van Veenendaal, M.; Ahn, K. H.

2013-03-01

We present a formula based on tight-binding approach for the calculation of K-edge resonant inelastic x-ray scattering spectrum for transition metal oxides, by extending the previous result [K. H. Ahn, A. J. Fedro, and M. van Veenendaal, Phys. Rev. B 79, 045103 (2009).] to include explicit momentum dependence and a basis with multiple core hole sites. We apply this formula to layered charge, orbital, and spin ordered manganites, La0.5Sr1.5MnO4. The K-edge RIXS spectrum is found not periodic with respect to the actual reciprocal lattice, but approximately periodic with respect to the reciprocal lattice for the hypothetical unit cell with one core hole site. With experimental strcuture and reasonable tight-binding parameters, we obtain good agreement with experimental data, in particular, with regards to the large variation of the intensity with momentum. We find that the screening in La0.5Sr1.5MnO4 is highly localized around the core hole site and demonstrate the potential of K-edge RIXS as a probe for the screening dynamics in materials. Work supported by US.DOE Contr. DE-AC02-98CH10886 (X.L.,J.H.), US.DOE Award DE-FG02-03ER46097 (M.v.V.), CMCSN under Grants DE-FG02-08ER46540 & DE-SC0007091 (T.S.,K.A.,M.v.V.), Argonne XSD Visitor Prog.(K.A.), US.DOE Contr. DE-AC02-06CH11357 (X.L.,J.H).

Self-interaction-corrected time-dependent density-functional-theory calculations of x-ray-absorption spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tu, Guangde; Rinkevicius, Zilvinas; Vahtras, Olav

We outline an approach within time-dependent density functional theory that predicts x-ray spectra on an absolute scale. The approach rests on a recent formulation of the resonant-convergent first-order polarization propagator [P. Norman et al., J. Chem. Phys. 123, 194103 (2005)] and corrects for the self-interaction energy of the core orbital. This polarization propagator approach makes it possible to directly calculate the x-ray absorption cross section at a particular frequency without explicitly addressing the excited-state spectrum. The self-interaction correction for the employed density functional accounts for an energy shift of the spectrum, and fully correlated absolute-scale x-ray spectra are thereby obtainedmore » based solely on optimization of the electronic ground state. The procedure is benchmarked against experimental spectra of a set of small organic molecules at the carbon, nitrogen, and oxygen K edges.« less

‘Postage-stamp PIV’: small velocity fields at 400 kHz for turbulence spectra measurements

NASA Astrophysics Data System (ADS)

Beresh, Steven J.; Henfling, John F.; Spillers, Russell W.; Spitzer, Seth M.

2018-03-01

Time-resolved particle image velocimetry recently has been demonstrated in high-speed flows using a pulse-burst laser at repetition rates reaching 50 kHz. Turbulent behavior can be measured at still higher frequencies if the field of view is greatly reduced and lower laser pulse energy is accepted. Current technology allows image acquisition at 400 kHz for sequences exceeding 4000 frames but for an array of only 128  ×  120 pixels, giving the moniker of ‘postage-stamp PIV’. The technique has been tested far downstream of a supersonic jet exhausting into a transonic crossflow. Two-component measurements appear valid until 120 kHz, at which point a noise floor emerges whose magnitude is dependent on the reduction of peak locking. Stereoscopic measurement offers three-component data for turbulent kinetic energy spectra, but exhibits a reduced signal bandwidth and higher noise in the out-of-plane component due to the oblique camera images. The resulting spectra reveal two regions exhibiting power-law dependence describing the turbulent decay. The frequency response of the present measurement configuration exceeds nearly all previous velocimetry measurements in high speed flow.

An Aeroacoustic Study of a Leading Edge Slat Configuration

NASA Technical Reports Server (NTRS)

Mendoza, J. M.; Brooks, T. F.; Humphreys, W. M., Jr.

2002-01-01

Aeroacoustic evaluations of high-lift devices have been carried out in the Quiet Flow Facility of the NASA Langley Research Center. The present paper describes detailed flow and acoustic measurements that have been made in order to better understand the noise generated from airflow over a wing leading edge slat configuration, and to possibly predict and reduce this noise source. The acoustic database is obtained by a moveable Small Aperture Directional Array of microphones designed to electronically steer to different portions of models under study. The slat is shown to be a uniform distributed noise source. The data was processed such that spectra and directivity were determined with respect to a one-foot span of slat. The spectra are normalized in various fashions to demonstrate slat noise character. In order to equate portions of the spectra to different slat noise components, trailing edge noise predictions using measured slat boundary layer parameters as inputs are compared to the measured slat noise spectra.

Identification of jasmine flower (Jasminum sp.) based on the shape of the flower using sobel edge and k-nearest neighbour

NASA Astrophysics Data System (ADS)

Qur’ania, A.; Sarinah, I.

2018-03-01

People often wrong in knowing the type of jasmine by just looking at the white color of the jasmine, while not all white flowers including jasmine and not all jasmine flowers have white. There is a jasmine that is yellow and there is a jasmine that is white and purple.The aim of this research is to identify Jasmine flower (Jasminum sp.) based on the shape of the flower image-based using Sobel edge detection and k-Nearest Neighbor. Edge detection is used to detect the type of flower from the flower shape. Edge detection aims to improve the appearance of the border of a digital image. While k-Nearest Neighbor method is used to classify the classification of test objects into classes that have neighbouring properties closest to the object of training. The data used in this study are three types of jasmine namely jasmine white (Jasminum sambac), jasmine gambir (Jasminum pubescens), and jasmine japan (Pseuderanthemum reticulatum). Testing of jasmine flower image resized 50 × 50 pixels, 100 × 100 pixels, 150 × 150 pixels yields an accuracy of 84%. Tests on distance values of the k-NN method with spacing 5, 10 and 15 resulted in different accuracy rates for 5 and 10 closest distances yielding the same accuracy rate of 84%, for the 15 shortest distance resulted in a small accuracy of 65.2%.

Comprehensive studies of structural, electronic and magnetic properties of Zn{sub 0.95}Co{sub 0.05}O nanopowders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Radisavljević, Ivana, E-mail: iva@vin.bg.ac.rs; Novaković, Nikola; Matović, Branko

2016-02-15

Highlights: • Zn{sub 0.95}Co{sub 0.05}O nanopowders are characterized by high structural order. • Co atoms show no tendency for Co–Co clustering and Co–Ov complexes formation. • Co–O–Co clustering along the c-axis has not lead to ferromagnetic order. • XMCD provides no evidence of magnetic polarization of O 2p and Co 3d states. - Abstract: X-ray absorption (XANES, EXAFS, XMCD) and photoelectron (XPS) spectroscopic techniques were employed to study local structural, electronic and magnetic properties of Zn{sub 0.95}Co{sub 0.05}O nanopowders. The substitutional Co{sup 2+} ions are incorporated in ZnO lattice at regular Zn sites and the sample is characterized by highmore » structural order. There was no sign of ferromagnetic ordering of Co magnetic moments and the sample is in paramagnetic state at all temperatures down to 5 K. The possible connection of the structural defects with the absence of ferromagnetism is discussed on the basis of theoretical calculations of the O K-edge absorption spectra.« less

X-Ray Absorption Near-Edge Structure (XANES) Spectroscopy Study of the Interaction of Silver Ions with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli

PubMed Central

Zanzen, Ulrike; Krishna, Katla Sai; Hormes, Josef

2013-01-01

Silver ions are widely used as antibacterial agents, but the basic molecular mechanism of this effect is still poorly understood. X-ray absorption near-edge structure (XANES) spectroscopy at the Ag LIII, S K, and P K edges reveals the chemical forms of silver in Staphylococcus aureus and Escherichia coli (Ag+ treated). The Ag LIII-edge XANES spectra of the bacteria are all slightly different and very different from the spectra of silver ions (silver nitrate and silver acetate), which confirms that a reaction occurs. Death or inactivation of bacteria was observed by plate counting and light microscopy. Silver bonding to sulfhydryl groups (Ag-S) in cysteine and Ag-N or Ag-O bonding in histidine, alanine, and dl-aspartic acid was detected by using synthesized silver-amino acids. Significantly lower silver-cysteine content, coupled with higher silver-histidine content, in Gram-positive S. aureus and Listeria monocytogenes cells indicates that the peptidoglycan multilayer could be buffering the biocidal effect of silver on Gram-positive bacteria, at least in part. Bonding of silver to phosphate groups was not detected. Interaction with DNA or proteins can occur through Ag-N bonding. The formation of silver-cysteine can be confirmed for both bacterial cell types, which supports the hypothesis that enzyme-catalyzed reactions and the electron transport chain within the cell are disrupted. PMID:23934494

Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques.

PubMed

Yang, Jianjun; Liu, Jin; Dynes, James J; Peak, Derek; Regier, Tom; Wang, Jian; Zhu, Shenhai; Shi, Jiyan; Tse, John S

2014-02-01

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu2S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.

EMPCA and Cluster Analysis of Quasar Spectra: Construction and Application to Simulated Spectra

NASA Astrophysics Data System (ADS)

Marrs, Adam; Leighly, Karen; Wagner, Cassidy; Macinnis, Francis

2017-01-01

Quasars have complex spectra with emission lines influenced by many factors. Therefore, to fully describe the spectrum requires specification of a large number of parameters, such as line equivalent width, blueshift, and ratios. Principal Component Analysis (PCA) aims to construct eigenvectors-or principal components-from the data with the goal of finding a few key parameters that can be used to predict the rest of the spectrum fairly well. Analysis of simulated quasar spectra was used to verify and justify our modified application of PCA.We used a variant of PCA called Weighted Expectation Maximization PCA (EMPCA; Bailey 2012) along with k-means cluster analysis to analyze simulated quasar spectra. Our approach combines both analytical methods to address two known problems with classical PCA. EMPCA uses weights to account for uncertainty and missing points in the spectra. K-means groups similar spectra together to address the nonlinearity of quasar spectra, specifically variance in blueshifts and widths of the emission lines.In producing and analyzing simulations, we first tested the effects of varying equivalent widths and blueshifts on the derived principal components, and explored the differences between standard PCA and EMPCA. We also tested the effects of varying signal-to-noise ratio. Next we used the results of fits to composite quasar spectra (see accompanying poster by Wagner et al.) to construct a set of realistic simulated spectra, and subjected those spectra to the EMPCA /k-means analysis. We concluded that our approach was validated when we found that the mean spectra from our k-means clusters derived from PCA projection coefficients reproduced the trends observed in the composite spectra.Furthermore, our method needed only two eigenvectors to identify both sets of correlations used to construct the simulations, as well as indicating the linear and nonlinear segments. Comparing this to regular PCA, which can require a dozen or more components, or to

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robblee, John Henry

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

The binuclear nickel center in the A-cluster of acetyl-CoA synthase (ACS) and two biomimetic dinickel complexes studied by X-ray absorption and emission spectroscopy

NASA Astrophysics Data System (ADS)

Schrapers, P.; Mebs, S.; Ilina, Y.; Warner, D. S.; Wörmann, C.; Schuth, N.; Kositzki, R.; Dau, H.; Limberg, C.; Dobbek, H.; Haumann, M.

2016-05-01

Acetyl-CoA synthase (ACS) is involved in the bacterial carbon oxide conversion pathway. The binuclear nickel sites in ACS enzyme and two biomimetic synthetic compounds containing a Ni(II)Ni(II) unit (1 and 2) were compared using XAS/XES. EXAFS analysis of ACS proteins revealed similar Ni-N/O/S bond lengths and Ni-Ni/Fe distances as in the crystal structure in oxidized ACS, but elongated Ni-ligand bonds in reduced ACS, suggesting more reduced nickel species. The XANES spectra of ACS and the dinickel complexes showed overall similar shapes, but less resolved pre-edge and edge features in ACS, attributed to more distorted square-planar nickel sites in particular in reduced ACS. DFT calculation of pre-edge absorption and Kβ2,5 emission features reproduced the experimental spectra of the synthetic complexes, was sensitive even to the small geometry differences in 1 and 2, and indicated low-spin Ni(II) sites. Comparison of nickel sites in proteins and biomimetic compounds is valuable for deducing structural and electronic differences in response to ligation and redox changes.

Gaussian quadrature exponential sum modeling of near infrared methane laboratory spectra obtained at temperatures from 106 to 297 K

NASA Technical Reports Server (NTRS)

Giver, Lawrence P.; Benner, D. C.; Tomasko, M. G.; Fink, U.; Kerola, D.

1990-01-01

Transmission measurements made on near-infrared laboratory methane spectra have previously been fit using a Malkmus band model. The laboratory spectra were obtained in three groups at temperatures averaging 112, 188, and 295 K; band model fitting was done separately for each temperature group. These band model parameters cannot be used directly in scattering atmosphere model computations, so an exponential sum model is being developed which includes pressure and temperature fitting parameters. The goal is to obtain model parameters by least square fits at 10/cm intervals from 3800 to 9100/cm. These results will be useful in the interpretation of current planetary spectra and also NIMS spectra of Jupiter anticipated from the Galileo mission.

Killing of Bacillus Megaterium Spores by X-rays at the Phosphorus K-edge

NASA Technical Reports Server (NTRS)

Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

2001-01-01

This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10(exp 18) photons/sec/sq mm. The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140 eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

Killing of Bacillus Megaterium Spores by X-Rays at the Phosphorus K-Edge

NASA Technical Reports Server (NTRS)

Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

2001-01-01

This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10 photons/sec/mm . The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

Tetrahedral hydrocarbon nanoparticles in space: X-ray spectra

NASA Astrophysics Data System (ADS)

Bilalbegović, G.; Maksimović, A.; Valencic, L. A.

2018-06-01

It has been proposed, or confirmed, that diamond nanoparticles exist in various environments in space: close to active galactic nuclei, in the vicinity of supernovae and pulsars, in the interior of several planets in the Solar system, in carbon planets, and other exoplanets, carbon-rich stars, meteorites, in X-ray active Herbig Ae/Be stars, and in the interstellar medium. Using density functional theory methods, we calculate the carbon K-edge X-ray absorption spectrum of two large tetrahedral nanodiamonds: C26H32 and C51H52. We also study and test our methods on the astrophysical molecule CH4, the smallest C-H tetrahedral structure. A possible detection of nanodiamonds from X-ray spectra by future telescopes, such as the project Arcus, is proposed. Simulated spectra of the diffuse interstellar medium using Cyg X-2 as a source show that nanodiamonds studied in this work can be detected by Arcus, a high-resolution X-ray spectrometer mission selected by NASA for a Phase A concept study.

Anisotropic spectra of acoustic type turbulence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuznetsov, E.; P.N. Lebedev Physical Institute, 53 Leninsky Ave., 119991 Moscow; Krasnoselskikh, V.

2008-06-15

The problem of spectra for acoustic type of turbulence generated by shocks being randomly distributed in space is considered. It is shown that for turbulence with a weak anisotropy, such spectra have the same dependence in k-space as the Kadomtsev-Petviashvili spectrum: E(k){approx}k{sup -2}. However, the frequency spectrum has always the falling {approx}{omega}{sup -2}, independent of anisotropy. In the strong anisotropic case the energy distribution relative to wave vectors takes anisotropic dependence, forming in the large-k region spectra of the jet type.

The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

NASA Astrophysics Data System (ADS)

Majzlan, Juraj; Lalinská, Bronislava; Chovan, Martin; Jurkovič, L.'ubomír; Milovská, Stanislava; Göttlicher, Jörg

2007-09-01

The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ˜380,000 m 3 of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS 2; arsenopyrite, FeAsS; berthierite, FeSb 2S 4) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ μ-XANES experiments indicate that As in the weathering rims is fully oxidized (As 5+). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As 2O 5 and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As 5+. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 Å, that is, increasing polymerization of the iron

Pristine Basal- and Edge-Plane-Oriented Molybdenite MoS2 Exhibiting Highly Anisotropic Properties.

PubMed

Tan, Shu Min; Ambrosi, Adriano; Sofer, Zdenĕk; Huber, Štěpán; Sedmidubský, David; Pumera, Martin

2015-05-04

The layered structure of molybdenum disulfide (MoS2 ) is structurally similar to that of graphite, with individual sheets strongly covalently bonded within but held together through weak van der Waals interactions. This results in two distinct surfaces of MoS2 : basal and edge planes. The edge plane was theoretically predicted to be more electroactive than the basal plane, but evidence from direct experimental comparison is elusive. Herein, the first study comparing the two surfaces of MoS2 by using macroscopic crystals is presented. A careful investigation of the electrochemical properties of macroscopic MoS2 pristine crystals with precise control over the exposure of one plane surface, that is, basal plane or edge plane, was performed. These crystals were characterized thoroughly by AFM, Raman spectroscopy, X-ray photoelectron spectroscopy, voltammetry, digital simulation, and DFT calculations. In the Raman spectra, the basal and edge planes show anisotropy in the preferred excitation of E2g and A1g phonon modes, respectively. The edge plane exhibits a much larger heterogeneous electron transfer rate constant k(0) of 4.96×10(-5) and 1.1×10(-3)  cm s(-1) for [Fe(CN)6 ](3-/4-) and [Ru(NH3 )6 ](3+/2+) redox probes, respectively, compared to the basal plane, which yielded k(0) tending towards zero for [Fe(CN)6 ](3-/4-) and about 9.3×10(-4)  cm s(-1) for [Ru(NH3 )6 ](3+/2+) . The industrially important hydrogen evolution reaction follows the trend observed for [Fe(CN)6 ](3-/4-) in that the basal plane is basically inactive. The experimental comparison of the edge and basal planes of MoS2 crystals is supported by DFT calculations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Demonstration of iodine K-edge imaging by use of an energy-discrimination X-ray computed tomography system with a cadmium telluride detector.

PubMed

Abudurexiti, Abulajiang; Kameda, Masashi; Sato, Eiichi; Abderyim, Purkhet; Enomoto, Toshiyuki; Watanabe, Manabu; Hitomi, Keitaro; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Takahashi, Kiyomi; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

2010-07-01

An energy-discrimination K-edge X-ray computed tomography (CT) system is useful for increasing the contrast resolution of a target region by utilizing contrast media. The CT system has a cadmium telluride (CdTe) detector, and a projection curve is obtained by linear scanning with use of the CdTe detector in conjunction with an X-stage. An object is rotated by a rotation step angle with use of a turntable between the linear scans. Thus, CT is carried out by repetition of the linear scanning and the rotation of an object. Penetrating X-ray photons from the object are detected by the CdTe detector, and event signals of X-ray photons are produced with use of charge-sensitive and shaping amplifiers. Both the photon energy and the energy width are selected by use of a multi-channel analyzer, and the number of photons is counted by a counter card. For performing energy discrimination, a low-dose-rate X-ray generator for photon counting was developed; the maximum tube voltage and the minimum tube current were 110 kV and 1.0 microA, respectively. In energy-discrimination CT, the tube voltage and the current were 60 kV and 20.0 microA, respectively, and the X-ray intensity was 0.735 microGy/s at 1.0 m from the source and with a tube voltage of 60 kV. Demonstration of enhanced iodine K-edge X-ray CT was carried out by selection of photons with energies just beyond the iodine K-edge energy of 33.2 keV.

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

PubMed Central

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

2014-01-01

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

High resolution spectroscopy over 8500-8750 Å for GAIA <= 50 000 K. III. A library of synthetic spectra for 7750 <= Teff

NASA Astrophysics Data System (ADS)

Castelli, F.; Munari, U.

2001-02-01

In this paper we complete the library of synthetic spectra for the range 7650-8750 Å, which includes the 8500-8750 Å interval currently base-lined for the spectroscopic observations by GAIA, candidate ESA Cornerstone 5 mission. As for Paper II, the spectra are based on Kurucz's codes and line data. The explored metallicity, gravity and temperature ranges are -2.5<= [Z/Zsun]<= +0.5, 4.5<=log g<= 2.0 and 7750<=Teff <=50 000 K, respectively. The 698 new spectra are computed at the same lambda / bigtriangleup lambda =20 000 resolving power of the observed spectra given in Paper I (131 standard stars mapping the MKK spectral classification system) and the 254 synthetic spectra of Paper II (characterized by Teff <= 7 500 K). Tables 2-4 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/366/1003 or via the personal HomePage http://ulisse.pd.astro.it/Astro/Atlases/ The spectra are available in electronic form at the CDS. Figures 5-224 are only available in electronic form at http://www.edpsciences.org

Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1993-06-01

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

Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1993-06-01

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

Edge states in a ferromagnetic honeycomb lattice with armchair boundaries

NASA Astrophysics Data System (ADS)

Pantaleón, Pierre A.; Xian, Y.

2018-02-01

We investigate the properties of magnon edge states in a ferromagnetic honeycomb lattice with armchair boundaries. In contrast with fermionic graphene, we find novel edge states due to the missing bonds along the boundary sites. After introducing an external on-site potential at the outermost sites we find that the energy spectra of the edge states are tunable. Additionally, when a non-trivial gap is induced, we find that some of the edge states are topologically protected and also tunable. Our results may explain the origin of the novel edge states recently observed in photonic lattices. We also discuss the behavior of these edge states for further experimental confirmations.

Observation of yttrium oxide nanoparticles in cabbage (Brassica oleracea) through dual energy K-edge subtraction imaging

DOE PAGES

Chen, Yunyun; Sanchez, Carlos; Yue, Yuan; ...

2016-03-25

Background: The potential transfer of engineered nanoparticles (ENPs) from plants into the food chain has raised widespread concerns. In order to investigate the effects of ENPs on plants, young cabbage plants (Brassica oleracea) were exposed to a hydroponic system containing yttrium oxide (yttria) ENPs. The objective of this study was to reveal the impacts of NPs on plants by using K-edge subtraction imaging technique. Results: Using synchrotron dual-e nergy X-ray micro-tomography with K-edge subtraction technique, we studied the uptake, accumulation, distribution and concentration mapping of yttria ENPs in cabbage plants. It was found that yttria ENPs were uptaken by themore » cabbage roots but did not effectively transferred and mobilized through the cabbage stem and leaves. This could be due to the accumulation of yttria ENPs blocked at primary-lateral-root junction. Instead, non-yttria minerals were found in the xylem vessels of roots and stem. Conclusions: Synchrotron dual-energy X-ray micro-tomography is an effective method to observe yttria NPs inside the cabbage plants in both whole body and microscale level. Furthermore, the blockage of a plant's roots by nanoparticles is likely the first and potentially fatal environmental effect of such type of nanoparticles.« less

Arsenic speciation in biological samples using XAS and mixed oxidation state calibration standards of inorganic arsenic.

PubMed

Parsons, J G; Lopez, M L; Castillo-Michel, H; Peralta-Videa, J R; Gardea-Torresdey, J L

2009-08-01

The speciation of elements without pre-edge features preformed with X-ray absorption near edge structure (XANES) can lead to problems when the energy difference between two species is small. The speciation of arsenic (As) in plant samples was investigated using the mixtures As2S3/As2O5, As2S3/As2O3, or As2O3/As2O5. The data showed that the energy separation (eV) between As2O5 and As2S3 was 5.8, between As2O3 and As2O5 was 3.6, and between As2S3 and As2O3 was 2.1. From the intensity of the white-line feature and the concentration of As species, calibration curves showing a limit of detection of approximately 10% were generated. In addition, an error of +/-10% was determined for the linear combination-XANES (LC-XANES) fitting technique. The difference between the LC-XANES fittings and calculations from the calibration curves was <10%. The data also showed that the speciation of As in a sample can be determined using EXAFS (extended X-ray absorption fine structure). Finally, it was also shown that both EXAFS and XANES of the sample should be examined to determine the true speciation of an element. Even though there is a difference of 2 eV between As(III) bound to O and As(III) bound to S, in the EXAFS region the As(III)-S and As(III)-O ligands are clearly visible. However, distinction between the As(III)-O and As(V)-O ligands in the EXAFS spectra was not clearly visible in this study.

DAVs: Red Edge and Outbursts

NASA Astrophysics Data System (ADS)

Luan, Jing

2018-04-01

As established by ground based surveys, white dwarfs with hydrogen atmospheres pulsate as they cool across the temperature range, 12500K< Teff < 10800K . Known as DAVs or ZZ Ceti stars, their oscillations are attributed to overstable g-modes excited by convective driving. The effective temperature at the blue edge of the instability strip is slightly lower than that at which a surface convection zone appears. The temperature at the red edge is a two-decade old puzzle. Recently, Kepler discovered a number of cool DAVs exhibiting sporadic outbursts separated by days, each lasting several hours, and releasing \\sim 10^{33}-10^{34} {erg}. We provide quantitative explanations for both the red edge and the outbursts. The minimal frequency for overstable modes rises abruptly near the red edge. Although high frequency overstable modes exist below the red edge, their photometric amplitudes are generally too small to be detected by ground based observations. Nevertheless, these overstable parent modes can manifest themselves through nonlinear mode couplings to damped daughter modes which generate limit cycles giving rise to photometric outbursts.

A versatile in situ spectroscopic cell for fluorescence/transmission EXAFS and X-ray diffraction of heterogeneous catalysts in gas and liquid phase.

PubMed

Hannemann, Stefan; Casapu, Maria; Grunwaldt, Jan Dierk; Haider, Peter; Trüssel, Philippe; Baiker, Alfons; Welter, Edmund

2007-07-01

A new spectroscopic cell suitable for the analysis of heterogeneous catalysts by fluorescence EXAFS (extended X-ray absorption fine structure), transmission EXAFS and X-ray diffraction during in situ treatments and during catalysis is described. Both gas-phase and liquid-phase reactions can be investigated combined with on-line product analysis performed either by mass spectrometry or infrared spectroscopy. The set-up allows measurements from liquid-nitrogen temperature to 973 K. The catalysts are loaded preferentially as powders, but also as self-supporting wafers. The reaction cell was tested in various case studies demonstrating its flexibility and its wide applicability from model studies at liquid-nitrogen temperature to operando studies under realistic reaction conditions. Examples include structural studies during (i) the reduction of alumina-supported noble metal particles prepared by flame-spray pyrolysis and analysis of alloying in bimetallic noble metal particles (0.1%Pt-0.1%Pd/Al(2)O(3), 0.1%Pt-0.1%Ru/Al(2)O(3), 0.1%Pt-0.1%Rh/Al(2)O(3), 0.1%Au-0.1%Pd/Al(2)O(3)), (ii) reactivation of aged 0.8%Pt-16%BaO-CeO(2) NO(x) storage-reduction catalysts including the NO(x) storage/reduction cycle, and (iii) alcohol oxidation over gold catalysts (0.6%Au-20%CuO-CeO(2)).

Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

PubMed

Sheng, Guodong; Yang, Shitong; Sheng, Jiang; Hu, Jun; Tan, Xiaoli; Wang, Xiangke

2011-09-15

Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ∼6 O at R(Ni-O) ≈ 2.05 Å. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

X-ray absorption spectra: Graphene, h-BN, and their alloy

NASA Astrophysics Data System (ADS)

Bhowmick, Somnath; Rusz, Jan; Eriksson, Olle

2013-04-01

Using first-principles density functional theory calculations, in conjunction with the Mahan-Nozières-de Dominicis theory, we calculate the x-ray absorption spectra of the alloys of graphene and monolayer hexagonal boron nitride on a Ni (111) substrate. The chemical neighborhood of the constituent atoms (B, C, and N) inside the alloy differs from that of the parent phases. In a systematic way, we capture the change in the K-edge spectral shape, depending on the chemical neighborhood of B, C, and N. Our work also reiterates the importance of the dynamical core-hole screening for a proper description of the x-ray absorption process in sp2-bonded layered materials.

Magnetism of Nanographene-Based Microporous Carbon and Its Applications: Interplay of Edge Geometry and Chemistry Details in the Edge State

NASA Astrophysics Data System (ADS)

Enoki, Toshiaki; Kiguchi, Manabu

2018-03-01

This paper is a contribution to the Physical Review Applied collection in memory of Mildred S. Dresselhaus. Nanographenes have important edge geometry dependence in their electronic structures. In armchair edges, electron wave interference works to contribute to energetic stability. Meanwhile, zigzag edges possess an edge-localized and spin-polarized nonbonding edge state, which causes electronic, magnetic, and chemical activities. In addition to the geometry dependence, the electronic structures are seriously affected by edge chemistry details. The edge chemistry dependence together with edge geometries on the electronic structures are discussed with samples of randomly networked nanographenes (microporous activated carbon fibers) in pristine state and under high-temperature annealing. In the pristine sample with the edges oxidized in ambient atmospheric conditions, the edge state, which is otherwise unstable, can be stabilized because of the charge transfer from nanographene to terminating oxygen. Nanographene, whose edges consist of a combination of magnetic zigzag edges and nonmagnetic armchair edges, is found to be ferrimagnetic with a nonzero net magnetic moment created under the interplay between a strong intrazigzag-edge ferromagnetic interaction and intermediate-strength interzigzag-edge antiferromagnetic-ferromagnetic interaction. At heat-treatment temperatures just below the fusion start (approximately 1500 K), the edge-terminating structure is changed from oxygen-containing groups to hydrogen in the nanographene network. Additionally, hydrogen-terminated zigzag edges, which are present as the majority and chemically unstable, play a triggering role in fusion above 1500 K. The fusion start brings about an insulator-to-metal transition at TI -M˜1500 K . Local fusions taking place percolatively between nanographenes work to expand the π -bond network, eventually resulting in the development of antiferromagnetic short-range order toward spin glass in the

Investigation of a Spin Transition in a LaCoO3 Single Crystal by the Method of X-Ray Magnetic Circular Dichroism at the Cobalt K- and L 2,3-Edges

NASA Astrophysics Data System (ADS)

Sikolenko, V. V.; Troyanchuk, I. O.; Karpinsky, D. V.; Rogalev, A.; Wilhelm, F.; Rosenberg, R.; Prabhakaran, D.; Efimova, E. A.; Efimov, V. V.; Tiutiunnikov, S. I.; Bobrikov, I. A.

2018-02-01

Spin transitions of cobalt ions in LaCoO3 single crystals have been studied by the method of X-ray magnetic circular dichroism (XMCD) at the K- and L 2,3-edges of Co3+ ions. The orbital momentum of cobalt ions obtained for the K-edge at the 3 d level in the region of the spin transition in the temperature range from 25 to 120 K increases by a factor of approximately 1.6, whereas the slope of the magnetization curve value in the same temperature range and magnetic field increases by a factor of more than 10. XMCD experiments at the cobalt L 2,3-edges demonstrate gradual growth of the ratio of the orbital momentum to the spin one L/ S from 0.48 to 0.53 in the temperature range from 60 K to 120 K.

An EXAFS study on the so-called {open_quotes}Co-Mo-S{close_quotes} phase in Co/C and CoMo/C, compared with a Moessbauer emission spectroscopy study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Craje, M.W.J.; Kraan, A.M. van der; Louwers, S.P.A.

1992-06-25

EXAFS was used in this paper to study 4 sulfided catalysts that have the same structure as their {sup 57}Co counterparts characterized by Mossbauer emission spectroscopy. The {open_quotes}Co-Mo-S{close_quotes} phase in Co/C is similar to CoMo/C due to a very highly dispersed Co species. Without Mo, the sulfidic Co results in a Co{sub 9}S{sub 8} phase during sulfidation at 673K, Mo prevents Co sintering in CoMo/C. 37 refs., 6 figs., 2 tabs.

Cerium LIII-edge x-ray absorption study of the CexFe4-yCoySb12 skutterudites

NASA Astrophysics Data System (ADS)

Grandjean, Fernande; Long, Gary J.; Cortes, Robert; Morelli, Donald T.; Meisner, Gregory P.

2000-11-01

The cerium LIII-edge x-ray absorption near-edge spectra of the CexFe4-yCoySb12 compounds have been obtained at 295 K and unambiguously indicate that cerium is in the 4f1 electronic ground state for all values of 0.22<=x<=0.98 and 0.0<=y<=3.5. This stable trivalent state of cerium is in agreement with the proposed (CeFe4Sb12)1-α(□Co4Sb12)α, solid solution structure, in which the cerium atoms are always surrounded by twelve antimony first neighbors and six iron second neighbors, the observed magnetic properties of CeFe4Sb12 and Ce0.9Fe3CoSb12, and the electronic structure of CeFe4Sb12 obtained from band-structure calculations.

Edge states at the interface of non-Hermitian systems

NASA Astrophysics Data System (ADS)

Yuce, C.

2018-04-01

Topological edge states appear at the interface of two topologically distinct Hermitian insulators. We study the extension of this idea to non-Hermitian systems. We consider P T -symmetric and topologically distinct non-Hermitian insulators with real spectra and study topological edge states at the interface of them. We show that P T symmetry is spontaneously broken at the interface during the topological phase transition. Therefore, topological edge states with complex energy eigenvalues appear at the interface. We apply our idea to a complex extension of the Su-Schrieffer-Heeger model.

Adsorption of antimony onto iron oxyhydroxides: adsorption behavior and surface structure.

PubMed

Guo, Xuejun; Wu, Zhijun; He, Mengchang; Meng, Xiaoguang; Jin, Xin; Qiu, Nan; Zhang, Jing

2014-07-15

Antimony is detected in soil and water with elevated concentration due to a variety of industrial applications and mining activities. Though antimony is classified as a pollutant of priority interest by the United States Environmental Protection Agency (USEPA) and Europe Union (EU), very little is known about its environmental behavior and adsorption mechanism. In this study, the adsorption behaviors and surface structure of antimony (III/V) on iron oxides were investigated using batch adsorption techniques, surface complexation modeling (SCM), X-ray photon spectroscopy (XPS) and extended X-ray absorption fine structure spectroscopy (EXAFS). The adsorption isotherms and edges indicated that the affinity of Sb(V) and Sb(III) toward the iron oxides depended on the Sb species, solution pH, and the characteristics of iron oxides. Sb(V) adsorption was favored at acidic pH and decreased dramatically with increasing pH, while Sb(III) adsorption was constant over a broad pH range. When pH is higher than 7, Sb(III) adsorption by goethite and hydrous ferric oxide (HFO) was greater than Sb(V). EXAFS analysis indicated that the majority of Sb(III), either adsorbed onto HFO or co-precipitated by FeCl3, was oxidized into Sb(V) probably due to the involvement of O2 in the long duration of sample preservation. Only one Sb-Fe subshell was filtered in the EXAFS spectra of antimony adsorption onto HFO, with the coordination number of 1.0-1.9 attributed to bidentate mononuclear edge-sharing ((2)E) between Sb and HFO. Copyright © 2014 Elsevier B.V. All rights reserved.

Ultraviolet absorption spectra of shock-heated carbon dioxide and water between 900 and 3050 K

NASA Astrophysics Data System (ADS)

Schulz, C.; Koch, J. D.; Davidson, D. F.; Jeffries, J. B.; Hanson, R. K.

2002-03-01

Spectrally resolved UV absorption cross-sections between 190 and 320 nm were measured in shock-heated CO 2 between 880 and 3050 K and H 2O between 1230 and 2860 K. Absorption spectra were acquired with 10 μs time resolution using a unique kinetic spectrograph, thereby enabling comparisons with time-dependent chemical kinetic modeling of post-shock thermal decomposition and chemical reactions. Although room temperature CO 2 is transparent (σ<10 -22 cm2) at wavelengths longer than 200 nm, hot CO 2 has significant absorption (σ>10 -20 cm2) extending to wavelengths longer than 300 nm. The temperature dependence of CO 2 absorption strongly suggests sharply increased transition probabilities from excited vibrational levels.

Local structural effects in Sr 3NiRhO 6 across magnetic transitions

DOE PAGES

Singh, Navneet; Khalid, S.; Bindu, R.

2016-04-06

Here, we investigate the temperature dependence of the structural parameters of quasi-one-dimensional Sr 3NiRhO 6 across the region of magnetic phase transitions using Ni K-edge and Sr K-edge x-ray absorption spectroscopy (XAS). The features in the x-ray absorption near-edge region are identified using multiple scattering calculations. The temperature-dependent extended x-ray absorption fine structure (EXAFS) studies show that the setting of the intra-chain super exchange interaction starts at ~200 K, which is well above the first transition temperature (45 K) revealed by magnetic susceptibility studies. The onset of the inter-chain super–super exchange interaction appears to be at ~125 K. Interestingly, themore » role played by direct exchange interaction between the Ni 3d and Rh 4d states in stabilising the magnetic interaction is less significant. The present results shed light on the generic features exhibited by isostructural compounds and may help in identifying the magnetic exchange pathways useful for understanding the unusual properties exhibited by such compounds.« less

Low resistivity of graphene nanoribbons with zigzag-dominated edge fabricated by hydrogen plasma etching combined with Zn/HCl pretreatment

NASA Astrophysics Data System (ADS)

Liu, Fengkui; Li, Qi; Wang, Rubing; Xu, Jianbao; Hu, Junxiong; Li, Weiwei; Guo, Yufen; Qian, Yuting; Deng, Wei; Ullah, Zaka; Zeng, Zhongming; Sun, Mengtao; Liu, Liwei

2017-11-01

Graphene nanoribbons (GNRs) have attracted intensive research interest owing to their potential applications in high performance graphene-based electronics. However, the deterioration of electrical performance caused by edge disorder is still an important obstacle to the applications. Here, we report the fabrication of low resistivity GNRs with a zigzag-dominated edge through hydrogen plasma etching combined with the Zn/HCl pretreatment method. This method is based on the anisotropic etching properties of hydrogen plasma in the vicinity of defects created by sputtering zinc (Zn) onto planar graphene. The polarized Raman spectra measurement of GNRs exhibits highly polarization dependence, which reveals the appearance of the zigzag-dominated edge. The as-prepared GNRs exhibit high carrier mobility (˜1332.4 cm2 v-1 s-1) and low resistivity (˜0.7 kΩ) at room temperature. Particularly, the GNRs can carry large current density (5.02 × 108 A cm-2) at high voltage (20.0 V) in the air atmosphere. Our study develops a controllable method to fabricate zigzag edge dominated GNRs for promising applications in transistors, sensors, nanoelectronics, and interconnects.

Oxygen K- and Mn L-Edges of La_xMn_yO_3-d Films

NASA Astrophysics Data System (ADS)

Deleon, Michael; Tyson, Trevor; Qian, Q.; Dubourdieu, C.; Senateur, J. P.; Bosak, A.; Arena, D. A.

2003-03-01

The La_xMn_yO_3-d system holds much interest due to it's wide range of magnetic and transport properties with varying compositions. Oxygen defects and lanthanum deficiencies in the parent compound LaMnO3 induce a mixture of valences at the Mn site which enables transitions to a ferromagnetic metallic state through double exchange [1-5]. We have measured the oxygen K-edges and Mn L-edges for La_xMn_yO_3-d films of varying x deposited on (100) SrTiO3 and x=0.8 on varying thickness deposited on (001) LaAlO_3. These results are interpreted by multiplet structure computations. In addition, band structure results will be used to track changes in unoccupied levels on the Mn and O sites. This work is supported by NSF Career Grant DMR-9733862 and DMR-0209243. [1]A. Gupta, T.R. McGuire, P.R. Duncombe, M. Rupp, J. Z. Sun, W. J. Gallagher, G. Xiao. Appl. Phys. Let. 67, 3494 (1995) [2]P. S. I. P. N. de Silva, F.M. Richards, L. F. Cohen, J. A. Alonso, M. J. Martinez-Lope, M. T. Casais, K. A. Thomas, J. L. MacManus-Driscoll. J. A. Phys. 83, 3394(1998) [3] C. Chen, A. de Lozanne. A. Phys. Let. 73, 3950(1998) [4] S. J. Kim, C. S. Kim, S. Park, B. W. Lee. J. A. Phys. 89, 7416 (2001) [5] J. Topfer, J. B. Goodenough. Sol. St. Ionics 101, 1215 (1997)

AN EMPIRICAL METHOD FOR IMPROVING THE QUALITY OF RXTE HEXTE SPECTRA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garcia, Javier A.; Steiner, James F.; McClintock, Jeffrey E.

2016-03-01

We have developed a correction tool to improve the quality of Rossi X-ray Timing Explorer (RXTE) High Energy X-ray Timing Experiment (HEXTE) spectra by employing the same method we used earlier to improve the quality of RXTE Proportional Counter Array (PCA) spectra. We fit all of the hundreds of HEXTE spectra of the Crab individually to a simple power-law model, some 37 million counts in total for Cluster A and 39 million counts for Cluster B, and we create for each cluster a combined spectrum of residuals. We find that the residual spectrum of Cluster A is free of instrumental artifacts while that of Clustermore » B contains significant features with amplitudes ∼1%; the most prominent is in the energy range 30–50 keV, which coincides with the iodine K edge. Starting with the residual spectrum for Cluster B, via an iterative procedure we created the calibration tool hexBcorr for correcting any Cluster B spectrum of interest. We demonstrate the efficacy of the tool by applying it to Cluster B spectra of two bright black holes, which contain several million counts apiece. For these spectra, application of the tool significantly improves the goodness of fit, while affecting only slightly the broadband fit parameters. The tool may be important for the study of spectral features, such as cyclotron lines, a topic that is beyond the scope of this paper.« less

Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

PubMed

Chakroune, Nassira; Viau, Guillaume; Ammar, Souad; Poul, Laurence; Veautier, Delphine; Chehimi, Mohamed M; Mangeney, Claire; Villain, Françoise; Fiévet, Fernand

2005-07-19

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.

Large Charge-Transfer Energy in LiFePO4 Revealed by Full-Multiplet Calculation for the Fe L3 -edge Soft X-ray Emission Spectra.

PubMed

Asakura, Daisuke; Nanba, Yusuke; Makinose, Yuki; Matsuda, Hirofumi; Glans, Per-Anders; Guo, Jinghua; Hosono, Eiji

2018-04-17

We analyzed the Fe 3d electronic structure in LiFePO 4 /FePO 4 (LFP/FP) nanowire with a high cyclability by using soft X-ray emission spectroscopy (XES) combined with configuration-interaction full-multiplet (CIFM) calculation. The ex situ Fe L 2,3 -edge resonant XES (RXES) spectra for LFP and FP are ascribed to oxidation states of Fe 2+ and Fe 3+ , respectively. CIFM calculations for Fe 2+ and Fe 3+ states reproduced the Fe L 3 RXES spectra for LFP and FP, respectively. In the calculations for both states, the charge-transfer energy was considerably larger than those for typical iron oxides, indicating very little electron transfer from the O 2p to Fe 3d orbitals and a weak hybridization on the Fe-O bond during the charge-discharge reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silver and copper nanoclusters in the lustre decoration of Italian Renaissance pottery: an EXAFS study

NASA Astrophysics Data System (ADS)

Padovani, S.; Borgia, I.; Brunetti, B.; Sgamellotti, A.; Giulivi, A.; D'Acapito, F.; Mazzoldi, P.; Sada, C.; Battaglin, G.

Lustre is one of the most important decorative techniques of the Medieval and Renaissance pottery of the Mediterranean basin, capable of producing brilliant metallic reflections and iridescence. Following the recent finding that the colour of lustre decorations is mainly determined by copper and silver nanoclusters dispersed in the glaze layer, the local environment of copper and silver atoms has been studied by extended X-ray absorption fine structure (EXAFS) spectroscopy on original samples of gold and red lustre. It has been found that, in gold lustre, whose colour is attributed mainly to the silver nanocluster dispersion, silver is only partially present in the metallic form and copper is almost completely oxidised. In the red lustre, whose colour is attributed mainly to the copper nanocluster dispersion, only a fraction of copper is present in the metallic form. EXAFS measurements on red lustre, carried out in the total electron yield mode to probe only the first 150 nm of the glaze layer, indicated that in some cases lustre nanoclusters may be confined in a very thin layer close to the surface.

Characterization by 27Al NMR, X-ray absorption spectroscopy, and density functional theory techniques of the species responsible for benzene hydrogenation in Y zeolite-supported carburized molybdenum catalysts.

PubMed

Rocha, Angela S; da Silva, Victor Teixeira; Eon, Jean G; de Menezes, Sônia M C; Faro, Arnaldo C; Rocha, Alexandre B

2006-08-17

Carburized molybdenum catalysts supported on a dealuminated NaH-Y zeolite were prepared by carburization under a 20% methane in hydrogen flow of two precursors obtained by adsorption of molybdenum hexacarbonyl, one containing 5 wt % and the other 10 wt % Mo, and a third one was prepared by impregnation with aqueous ammonium heptamolybdate, containing 5 wt % Mo. The three catalysts displayed very distinct behaviors in the benzene hydrogenation reaction at atmospheric pressure and 363 K. By using XANES spectroscopy at the molybdenum L edge, EXAFS and XANES spectroscopy at the molybdenum K edge, and 27Al solid-state NMR spectroscopy, it was shown that different carburized molybdenum species exist in each sample. In the catalyst containing 10 wt % Mo, formation of molybdenum carbide nanoparticles was observed, with an estimated diameter of 1.8 nm. In the catalyst containing 5 wt % Mo and prepared by carburization of adsorbed molybdenum hexacarbonyl, formation of molybdenum oxycarbide dimers is proposed. In the latter case, density functional theory calculations have led to a dimer structure which is compatible with EXAFS results. In the catalyst prepared by impregnation with ammonium heptamolybdate solution followed by carburization, the molybdenum seems to interact with extraframework alumina to produce highly disordered mixed molybdenum-aluminum oxycarbides.

On Super Edge-magic Total Labeling of Modified Watermill Graph

NASA Astrophysics Data System (ADS)

Nurdin; Ungko, T. S.; Gormantara, J.; Abdullah, A.; Aulyah, S.; Nikita

2018-03-01

An edge-magic total labeling on a graph G is one-to-one map from V(G) ∪ E(G) onto the set of integers 1,2, ...,ν + e, where ν = |V(G)| and e = |E(G)|, with the property that, given any edge uv, f(u) + f(u, ν}) + f(ν) = k for every u,v ∈ V(G), and k is called magic valuation. An edge-magic total labeling f is called super edge-magic total if f(v(G)) = {1,2 ...,|V(G)|} and f(E(G)) = {|V(G)| + 1, |V(G)| + 2,... |V(G) + E(G)|}. In this paper we investigate edge-magic total labeling of a new graph called modified Watermill graph. Furthermore, the magic valuation of the modified Watermill graph WM(n) is k=\\frac{1}{2}(21n+3), for n odd, n ≥ 3.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

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

PubMed

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

2015-07-01

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

Functionalized polyethylene fibers for the selective capture of palladium ions from aqueous solution

NASA Astrophysics Data System (ADS)

Pang, Li-juan; Li, Rong; Hu, Jiang-tao; Zhang, Lin-juan; Zhang, Ming-xing; Yang, Chen-guang; Wu, Guo-zhong

2018-03-01

An innovative ultrahigh molecular weight polyethylene (UHMWPE) fibrous adsorbent was successfully synthesized via radiation grafting and applied to the selective capture of palladium ions from dilute aqueous solutions. The influence of the pH, initial Pd(II) concentration, and temperature on the adsorption performance was examined in a batch adsorption experiment. Pd K-edge extended X-ray absorption fine structure (EXAFS) spectra indicated that Pd(II) was immobilized on the adsorbent surface via a ligand exchange reaction that formed a stable UHMWPE-PMDA-Pd complex. Although the concentrations of coexisting ions (Cu(II), Zn(II), Cr(VI), Fe(III), and Ni(II)) in the solution were much higher than that of Pd(II), the adsorption capacity for Pd(II) of the as-prepared absorbent was significantly greater than that for other metal ions. Kinetic studies showed good correlation with the pseudo-second-order model. The maximum capacity for Pd(II) adsorption was approximately 221.8 mg·g-1 at 298 K. The adsorption behavior conformed to the Langmuir isotherm model. Thermodynamic studies revealed that the adsorption of Pd(II) was a feasible, spontaneous, and endothermic process.

High-performance thermoelectricity in edge-over-edge zinc-porphyrin molecular wires.

PubMed

Noori, Mohammed; Sadeghi, Hatef; Lambert, Colin J

2017-04-20

If high efficiency organic thermoelectric materials could be identified, then these would open the way to a range of energy harvesting technologies and Peltier coolers using flexible and transparent thin-film materials. We have compared the thermoelectric properties of three zinc porphyrin (ZnP) dimers and a ZnP monomer and found that the "edge-over-edge" dimer formed from stacked ZnP rings possesses a high electrical conductance, negligible phonon thermal conductance and a high Seebeck coefficient of the order of 300 μV K -1 . These combine to yield a predicted room-temperature figure of merit of ZT ≈ 4, which is the highest room-temperature ZT ever reported for a single organic molecule. This high value of ZT is a consequence of the low phonon thermal conductance arising from the stacked nature of the porphyrin rings, which hinders phonon transport through the edge-over-edge molecule and enhances the Seebeck coefficient.

Quantifying edge significance on maintaining global connectivity

PubMed Central

Qian, Yuhua; Li, Yebin; Zhang, Min; Ma, Guoshuai; Lu, Furong

2017-01-01

Global connectivity is a quite important issue for networks. The failures of some key edges may lead to breakdown of the whole system. How to find them will provide a better understanding on system robustness. Based on topological information, we propose an approach named LE (link entropy) to quantify the edge significance on maintaining global connectivity. Then we compare the LE with the other six acknowledged indices on the edge significance: the edge betweenness centrality, degree product, bridgeness, diffusion importance, topological overlap and k-path edge centrality. Experimental results show that the LE approach outperforms in quantifying edge significance on maintaining global connectivity. PMID:28349923

Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution.

PubMed

Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre

2011-07-04

The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ⇆ (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, δ = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt → Tl) and LMCT (dmso → Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

DOE PAGES

Baker, Michael L.; Mara, Michael W.; Yan, James J.; ...

2017-02-09

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, Michael L.; Mara, Michael W.; Yan, James J.

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

Studies of EXAFSSpectra using Copper (II) Schiff Base complexes and Determination of Bond lengths Using Synchrotron Radiation

NASA Astrophysics Data System (ADS)

Mishra, A.; Vibhute, V.; Ninama, S.; Parsai, N.; Jha, S. N.; Sharma, P.

2016-10-01

X-ray absorption fine structure (XAFS) at the K-edge of copper has been studied in some copper (II) complexes with substituted anilines like (2Cl, 4Br, 2NO2, 4NO2 and pure aniline) with o-PDA (orthophenylenediamine) as ligand. The X-ray absorption measurements have been performed at the recently developed BL-8 dispersive EXAFS beam line at 2.5 GeV Indus-2 Synchrotron Source at RRCAT, Indore, India. The data obtained has been processed using EXAFS data analysis program Athena.The graphical method gives the useful information about bond length and also the environment of the absorbing atom. The theoretical bond lengths of the complexes were calculated by using interactive fitting of EXAFS using fast Fourier inverse transformation (IFEFFIT) method. This method is also called as Fourier transform method. The Lytle, Sayers and Stern method and Levy's method have been used for determination of bond lengths experimentally of the studied complexes. The results of both methods have been compared with theoretical IFEFFIT method.

Towards Standardization of X-ray Beam Filters in Digital Mammography and Digital Breast Tomosynthesis: Monte Carlo simulations and analytical modelling

PubMed Central

Shrestha, Suman; Vedantham, Srinivasan; Karellas, Andrew

2017-01-01

In digital breast tomosynthesis and digital mammography, the x-ray beam filter material and thickness vary between systems. Replacing K-edge filters with Al was investigated with the intent to reduce exposure duration and to simplify system design. Tungsten target x-ray spectra were simulated with K-edge filters (50μm Rh; 50μm Ag) and Al filters of varying thickness. Monte Carlo simulations were conducted to quantify the x-ray scatter from various filters alone, scatter-to-primary ratio (SPR) with compressed breasts, and to determine the radiation dose to the breast. These data were used to analytically compute the signal-difference-to-noise ratio (SDNR) at unit (1 mGy) mean glandular dose (MGD) for W/Rh and W/Ag spectra. At SDNR matched between K-edge and Al filtered spectra, the reductions in exposure duration and MGD were quantified for three strategies: (i) fixed Al thickness and matched tube potential in kilovolts (kV); (ii) fixed Al thickness and varying the kV to match the half-value layer (HVL) between Al and K-edge filtered spectra; and, (iii) matched kV and varying the Al thickness to match the HVL between Al and K-edge filtered spectra. Monte Carlo simulations indicate that the SPR with and without the breast were not different between Al and K-edge filters. Modelling for fixed Al thickness (700μm) and kV matched to K-edge filtered spectra, identical SDNR was achieved with 37–57% reduction in exposure duration and with 2–20% reduction in MGD, depending on breast thickness. Modelling for fixed Al thickness (700μm) and HVL matched by increasing the kV over [0,4] range, identical SDNR was achieved with 62–65% decrease in exposure duration and with 2–24% reduction in MGD, depending on breast thickness. For kV and HVL matched to K-edge filtered spectra by varying Al filter thickness over [700,880]μm range, identical SDNR was achieved with 23–56% reduction in exposure duration and 2–20% reduction in MGD, depending on breast thickness. These

New frontiers in water purification: highly stable amphopolycarboxyglycinate-stabilized Ag-AgCl nanocomposite and its newly discovered potential

NASA Astrophysics Data System (ADS)

Krutyakov, Yurii A.; Zherebin, Pavel M.; Kudrinskiy, Alexey A.; Zubavichus, Yan V.; Presniakov, Mikhail Yu; Yapryntsev, Alexey D.; Karabtseva, Anastasia V.; Mikhaylov, Dmitry M.; Lisichkin, Georgii V.

2016-09-01

A simple synthetic procedure for high-stable dispersions of porous composite Ag/AgCl nanoparticles stabilized with amphoteric surfactant sodium tallow amphopolycarboxyglycinate has been proposed for the first time. The prepared samples were characterized by UV-vis spectroscopy, x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy, small area electron diffraction (SAED), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electron probe micro-analysis. In addition, measurements (carried out at the Kurchatov synchrotron radiation source stations) of the Ag K-edge extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) spectra and XRD of the prepared nanoparticles have been performed. The obtained results suggest that small-sized Ag clusters are homogeneously distributed in the mass of the AgCl nanoparticle (~80 nm) formed during the synthesis. The Ag/AgCl dispersion demonstrates photocatalytic activity (with respect to methyl orange) and high bactericidal activity against E. coli. This activity is superior to the activity of both Ag and AgCl nanoparticles stabilized by the same surfactant. Thus, porous composite Ag/AgCl nanoparticles can be used as a multifunctional agent that is able to remove both pollutants and bacterium from water.

Uranium association with iron-bearing phases in mill tailings from Gunnar, Canada.

PubMed

Othmane, Guillaume; Allard, Thierry; Morin, Guillaume; Sélo, Madeleine; Brest, Jessica; Llorens, Isabelle; Chen, Ning; Bargar, John R; Fayek, Mostafa; Calas, Georges

2013-11-19

The speciation of uranium was studied in the mill tailings of the Gunnar uranium mine (Saskatchewan, Canada), which operated in the 1950s and 1960s. The nature, quantification, and spatial distribution of uranium-bearing phases were investigated by chemical and mineralogical analyses, fission track mapping, electron microscopy, and X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies at the U LIII-edge and Fe K-edge. In addition to uranium-containing phases from the ore, uranium is mostly associated with iron-bearing minerals in all tailing sites. XANES and EXAFS data and transmission electron microscopy analyses of the samples with the highest uranium concentrations (∼400-700 mg kg(-1) of U) demonstrate that uranium primarily occurs as monomeric uranyl ions (UO2(2+)), forming inner-sphere surface complexes bound to ferrihydrite (50-70% of the total U) and to a lesser extent to chlorite (30-40% of the total U). Thus, the stability and mobility of uranium at the Gunnar site are mainly influenced by sorption/desorption processes. In this context, acidic pH or alkaline pH with the presence of UO2(2+)- and/or Fe(3+)-complexing agents (e.g., carbonate) could potentially solubilize U in the tailings pore waters.

XANES and EXAFS investigation of uranium incorporation on nZVI in the presence of phosphate.

PubMed

Qiu, Muqing; Wang, Min; Zhao, Qingzhou; Hu, Baowei; Zhu, Yuling

2018-06-01

Effect of phosphate on the reduction of U(VI) on nZVI was determined by batch, XPS, XANES and EXAFS techniques. The batch experiments showed that nZVI was quite effective for the removal of uranium under the anaerobic conditions, whereas the addition of phosphate enhanced uranium removal over wide pH range. At low pH, the reduction of U(VI) to U(IV) significantly decreased with increasing phosphate concentration by XPS and XANES analysis. According to EXAFS analysis, the occurrence of UU shell at 10 mg/L phosphate and pH 4.0 was similar to that of U (IV) O 2 (s), whereas the UP and UFe shells were observed at 50 mg/L phosphate, revealing that reductive co-precipitate (U (IV) O 2 (s)) and precipitation of uranyl-phosphate were observed at low and high phosphate, respectively. The findings are crucial for the prediction of the effect of phosphate on the speciation and binding of uranium by nZVI at low pH, which is significant in controlling the mobility of U(VI) in contaminated environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Edge-entanglement spectrum correspondence in a nonchiral topological phase and Kramers-Wannier duality

NASA Astrophysics Data System (ADS)

Ho, Wen Wei; Cincio, Lukasz; Moradi, Heidar; Gaiotto, Davide; Vidal, Guifre

2015-03-01

In a system with chiral topological order, there is a remarkable correspondence between the edge and entanglement spectra: the low-energy spectrum of the system in the presence of a physical edge coincides with the lowest part of the entanglement spectrum (ES) across a virtual cut of the system into two parts, up to rescaling and shifting. This correspondence is believed to be due to the existence of protected gapless edge modes. In this paper, we explore whether the edge-entanglement spectrum correspondence extends to nonchiral topological phases, where there are no protected gapless edge modes. Specifically, we consider the Wen-plaquette model, which is equivalent to the Kitaev toric code model and has Z2 topological order (quantum double of Z2) . The unperturbed Wen-plaquette model displays an exact correspondence: both the edge and entanglement spectra within each topological sector a (a =1 ,⋯,4 ) are flat and equally degenerate. Here, we show, through a detailed microscopic calculation, that in the presence of generic local perturbations: (i) the effective degrees of freedom for both the physical edge and the entanglement cut consist of a (spin-1 /2 ) spin chain, with effective Hamiltonians Hedgea and Henta, respectively, both of which have a Z2 symmetry enforced by the bulk topological order; (ii) there is in general no match between the low-energy spectra of Hedgea and Henta, that is, there is no edge-ES correspondence. However, if supplement the Z2 topological order with a global symmetry (translational invariance along the edge/entanglement cut), i.e., by considering the Wen-plaquette model as a symmetry-enriched topological phase (SET), then there is a finite domain in Hamiltonian space in which both Hedgea and Henta realize the critical Ising model, whose low-energy effective theory is the c =1 /2 Ising CFT. This is achieved because the presence of the global symmetry implies that the effective degrees of freedom of both the edge and entanglement

Experimental and theoretical study of the structural environment of magnesium in minerals and silicate glasses using X-ray absorption near-edge structure

NASA Astrophysics Data System (ADS)

Trcera, Nicolas; Cabaret, Delphine; Rossano, Stéphanie; Farges, François; Flank, Anne-Marie; Lagarde, Pierre

2009-05-01

X-ray absorption spectroscopy at the Mg K-edge is used to obtain information on magnesium environment in minerals, silicate and alumino-silicate glasses. First-principles XANES calculations are performed for minerals using a plane-wave density functional formalism with core-hole effects treated in a supercell approach. The good agreement obtained between experimental and theoretical spectra provides useful information to interpret the spectral features. With the help of calculation, the position of the first peak of XANES spectra is related to both coordination and polyhedron distortion changes. In alumino-silicate glasses, magnesium is found to be mainly 5-fold coordinated to oxygen whatever the aluminum saturation index value. In silicate glasses, magnesium coordination increases from 4 in Cs-, Rb- and K-bearing glasses to 5 in Na- and Li-bearing glasses but remains equal as the polymerization degree of the glass varies. The variation of the C feature (position and intensity) is strongly related to the alkali type providing information on the medium range order.

Resonant inelastic X-ray scattering spectrometer with 25meV resolution at the Cu K -edge

DOE PAGES

Ketenoglu, Didem; Harder, Manuel; Klementiev, Konstantin; ...

2015-06-27

An unparalleled resolution is reported with an inelastic X-ray scattering instrument at the CuK-edge. Based on a segmented concave analyzer, featuring single-crystal quartz (SiO 2) pixels, the spectrometer delivers a resolution near 25meV (FWHM) at 8981eV. Besides the quartz analyzer, the performance of the spectrometer relies on a four-bounce Si(553) high-resolution monochromator and focusing Kirkpatrick–Baez optics. The measured resolution agrees with the ray-tracing simulation of an ideal spectrometer. The performance of the spectrometer is demonstrated by reproducing the phonon dispersion curve of a beryllium single-crystal.

Low-Dose-Rate Computed Tomography System Utilizing 25 mm/s-Scan Silicon X-ray Diode and Its Application to Iodine K-Edge Imaging Using Filtered Bremsstrahlung Photons

NASA Astrophysics Data System (ADS)

Matsushita, Ryo; Sato, Eiichi; Yanbe, Yutaka; Chiba, Hiraku; Maeda, Tomoko; Hagiwara, Osahiko; Matsukiyo, Hiroshi; Osawa, Akihiro; Enomoto, Toshiyuki; Watanabe, Manabu; Kusachi, Shinya; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

2013-03-01

A low-dose-rate X-ray computed tomography (CT) system is useful for reducing absorbed dose for patients. The CT system with a tube current of sub-mA was developed using a silicon X-ray diode (Si-XD). The Si-XD is a high-sensitivity Si photodiode (PD) selected for detecting X-ray photons, and the X-ray sensitivity of the Si-XD was twice as high as that of Si-PD cerium-doped yttrium aluminum perovskite [YAP(Ce)]. X-ray photons are directly detected using the Si-XD without a scintillator, and the photocurrent from the diode is amplified using current-voltage and voltage-voltage amplifiers. The output voltage is converted into logical pulses using a voltage-frequency converter with a maximum frequency of 500 kHz, and the frequency is proportional to the voltage. The pulses from the converter are sent to the differentiator with a time constant of 500 ns to generate short positive pulses for counting, and the pulses are counted using a counter card. Tomography is accomplished by repeated linear scans and rotations of an object, and projection curves of the object are obtained by the linear scan. The exposure time for obtaining a tomogram was 5 min at a scan step of 0.5 mm and a rotation step of 3.0°. The tube current and voltage were 0.55 mA and 60 kV, respectively, and iodine K-edge CT was carried out using filtered bremsstrahlung X-ray spectra with a peak energy of 38 keV.

Electrochemical and in situ spectroscopic studies of materials of relevance to energy storage and electrocatalysis

NASA Astrophysics Data System (ADS)

Mo, Yibo

In situ X-ray absorption (XAS), surface enhanced Raman spectroscopy (SERS) and rotating ring disk electrode techniques have been employed for the characterization of materials of relevance to electrochemical energy storage and electrocatalysis. In particular, analysis of in situ Ir LIII-edge extended X-ray absorption fine structure (EXAFS) of IrO2 films electrodeposited on Au substrates yielded Ir-O bond lengths decreasing in the sequence 2.02, 1.97 and 1.93 A, for Ir3+, Ir4+ and Ir5+ sites, respectively. Although features consistent with the presence of crystalline IrO2 in the highly hydrated films were found from in situ SERS, the lack of intense shells in the FT of the EXAFS function beyond the nearest oxygen neighbors indicates that the films by and large do not display long range order. In similar studies, the Fourier transform of the k3-weighted Ru K-edge EXAFS of electrodeposited RuO2 films recorded in situ were characterized by two shells attributed to Ru-O and Ru-Ru interactions at 1.94(1) and 3.12(2) A, in agreement with results obtained ex situ for Ru4+ in hydrous RuO2, whereas films in the reduced state yielded a single Ru-O interaction shell at 2.02(1) A. Extensions of these in situ XAS to the study of electrocatalysts for the nitrite reduction made it possible to identify and characterize the electronic and structural properties of a nitrosyl iron porphyrin adduct adsorbed on an electrode surface via the analysis of Fe K-edge XAS data. The effects of Se and S ad-atoms on the electrocatalytic activity of Pt electrodes have been examined using RRDE techniques. In acid, within a rather narrow range of coverages, both S- and Se-modified Pt surfaces promote the 2-electron reduction of dioxygen to hydrogen peroxide at ca. 100% faradaic efficiency over a wide potential region. Also developed were methods for immobilizing unsupported dispersed high area Pt particles a glassy carbon (GC) disk of a rotating Pt(ring)/GC(disk) electrode assembly allowing

Photoionization of Ne Atoms and Ne + Ions Near the K Edge: PrecisionSpectroscopy and Absolute Cross-sections

DOE PAGES

Müller, Alfred; Bernhardt, Dietrich; Borovik, Alexander; ...

2017-02-17

Single, double, and triple photoionization of Ne + ions by single photons have been investigated at the synchrotron radiation source PETRA III in Hamburg, Germany. Absolute cross-sections were measured by employing the photon-ion merged-beams technique. Photon energies were between about 840 and 930 eV, covering the range from the lowest-energy resonances associated with the excitation of one single K-shell electron up to double excitations involving one K- and one L-shell electron, well beyond the K-shell ionization threshold. Also, photoionization of neutral Ne was investigated just below the K edge. The chosen photon energy bandwidths were between 32 and 500 meV,more » facilitating the determination of natural line widths. The uncertainty of the energy scale is estimated to be 0.2 eV. For comparison with existing theoretical calculations, astrophysically relevant photoabsorption cross-sections were inferred by summing the measured partial ionization channels. Discussion of the observed resonances in the different final ionization channels reveals the presence of complex Auger-decay mechanisms. The ejection of three electrons from the lowest K-shell-excited Ne + (1s2s 2p 6 2S 1/2) level, for example, requires cooperative interaction of at least four electrons.« less

Characterization of Sb-doped Bi(2)UO(6) solid solutions by X-ray diffraction and X-ray absorption spectroscopy.

PubMed

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

2013-01-01

The preparation and characterization of Sb-doped Bi(2)UO(6) solid solutions, in a limited composition range, is reported for the first time. The solid solutions were prepared by solid-state reactions of Bi(2)O(3), Sb(2)O(3) and U(3)O(8) in the required stoichiometry. The reaction products were characterized by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements at the Bi and U L(3) edges. The XRD patterns indicate the precipitation of additional phases in the samples when Sb doping exceeds 4 at%. The chemical shifts of the Bi absorption edges in the samples, determined from the XANES spectra, show a systematic variation only up to 4 at% of Sb doping and support the results of XRD measurements. These observations are further supported by the local structure parameters obtained by analysis of the EXAFS spectra. The local structure of U is found to remain unchanged upon Sb doping indicating that Sb(+3) ions replace Bi(+3) during the doping of Bi(2)UO(6) by Sb.

Minimizing the Diameter of a Network Using Shortcut Edges

NASA Astrophysics Data System (ADS)

Demaine, Erik D.; Zadimoghaddam, Morteza

We study the problem of minimizing the diameter of a graph by adding k shortcut edges, for speeding up communication in an existing network design. We develop constant-factor approximation algorithms for different variations of this problem. We also show how to improve the approximation ratios using resource augmentation to allow more than k shortcut edges. We observe a close relation between the single-source version of the problem, where we want to minimize the largest distance from a given source vertex, and the well-known k-median problem. First we show that our constant-factor approximation algorithms for the general case solve the single-source problem within a constant factor. Then, using a linear-programming formulation for the single-source version, we find a (1 + ɛ)-approximation using O(klogn) shortcut edges. To show the tightness of our result, we prove that any ({3 over 2}-ɛ)-approximation for the single-source version must use Ω(klogn) shortcut edges assuming P ≠ NP.

Polarization-dependent DANES study on vertically-aligned ZnO nanorods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Chengjun; Park, Chang-In; Jin, Zhenlan

2016-05-01

The local structural and local density of states of vertically-aligned ZnO nanorods were examined by using a polarization-dependent diffraction anomalous near edge structure (DANES) measurements from c-oriented ZnO nanorods at the Zn K edge with the incident x-ray electric field parallel and perpendicular to the x-ray momentum transfer direction. Orientation-dependent local structures determined by DANES were comparable with polarization-dependent EXAFS results. Unlike other techniques, polarization-dependent DANES can uniquely describe the orientation-dependent local structural properties and the local density of states of a selected element in selected-phased crystals of compounds or mixed-phased structures.

Detection of significant differences between absorption spectra of neutral helium and low temperature photoionized helium plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bartnik, A.; Wachulak, P.; Fiedorowicz, H.

2013-11-15

In this work, spectral investigations of photoionized He plasmas were performed. The photoionized plasmas were created by irradiation of helium stream, with intense pulses from laser-plasma extreme ultraviolet (EUV) source. The EUV source was based on a double-stream Xe/Ne gas-puff target irradiated with 10 ns/10 J Nd:YAG laser pulses. The most intense emission from the source spanned a relatively narrow spectral region below 20 nm, however, spectrally integrated intensity at longer wavelengths was also significant. The EUV radiation was focused onto a gas stream, injected into a vacuum chamber synchronously with the EUV pulse. The long-wavelength part of the EUVmore » radiation was used for backlighting of the photoionized plasmas to obtain absorption spectra. Both emission and absorption spectra in the EUV range were investigated. Significant differences between absorption spectra acquired for neutral helium and low temperature photoionized plasmas were demonstrated for the first time. Strong increase of intensities and spectral widths of absorption lines, together with a red shift of the K-edge, was shown.« less

Infrared Spectra of M^+(2-AMINO-1-PHENYL ETHANOL)(H_2O)_{n=0-2}Ar (M=Na, K)

NASA Astrophysics Data System (ADS)

Nicely, Amy L.; Lisy, James M.

2009-06-01

A balance of competing electrostatic and hydrogen bonding interactions directs the structure of hydrated gas-phase cluster ions. Because of this, a biologically relevant model of cluster structures should include the effects of surrounding water molecules and metal ions such as sodium and potassium, which are found in high concentrations in the bloodstream. The molecule 2-amino-1-phenyl ethanol (APE) serves as a model for the neurotransmitters ephedrine and adrenaline. The neutral APE molecule contains an internal hydrogen bond between the amino and hydroxyl groups. In the M^+(APE) complex, the cation can either interrupt the internal hydrogen bond or position itself above the phenyl group, leaving the internal hydrogen bond intact. The former is preferred based on DFT calculations (B3LYP/6-31+G*) for both K^+ and Na^+ across the entire range from 0-400K, but infrared photodissociation (IRPD) spectra indicate a preference for the latter configuration at low temperatures. The IRPD spectra of M^+(H_2O)_{n=1-2} and M^+(H_2O)_{n=0-2}Ar (M=Na, K) will be presented along with parallel DFT and thermodynamics calculations to assist with the identification of the isomers present in each experiment.

The variation in frequency locations in Doppler ultrasound spectra for maximum blood flow velocities in narrowed vessels.

PubMed

Zhang, Yingyun; Zhang, Yufeng; Gao, Lian; Deng, Li; Hu, Xiao; Zhang, Kexin; Li, Haiyan

2017-11-01

This study assessed the variation in the frequency locations in the Doppler ultrasound spectra for the maximum blood flow velocities of in vessels with different degrees of bilaterally axisymmetric stenosis. This was done by comparing the relationship between the velocity distributions and corresponding Doppler power spectra. First, a geometric vessel model with axisymmetric stenosis was established. This made it possible to obtain the blood flow velocity distributions for different degrees of stenosis from the solutions of the Navier-Stokes equations. Then, the Doppler spectra were calculated for the entire segment of the vessel that was covered by the sound field. Finally, the maximum frequency locations for the spectra were determined based on the intersections of the maximum values chosen from the calculated blood flow velocity distributions and their corresponding spectra. The computational analysis showed that the maximum frequencies, which corresponded to the maximum blood flow velocities for different degrees of stenosis, were located at different positions along the spectral falling edges. The location for a normal (stenosis free) vessel was in the middle of the falling edge. For vessels with increasing degrees of stenosis, this location shifted approximately linearly downward along the falling edge. For 40% stenosis, the location reached a position at the falling edge of 0.32. Results obtained using the Field II simulation tool demonstrated the validity of the theoretical analysis and calculations, and may help to improve the maximum velocity estimation accuracy for Doppler blood flow spectra in stenosed vessels. Copyright © 2017 IPEM. Published by Elsevier Ltd. All rights reserved.

K-Shell Photoabsorption and Photoionisation of Trace Elements I. Isoelectronic Sequences With Electron Number 3< or = N < or = 11

NASA Technical Reports Server (NTRS)

Palmeri, P.; Quinet, P.; Mendoza, C.; Bautista, M. A.; Witthoeft, M. C.; Kallman, T. R.

2016-01-01