Sample records for absorption near-edge structure

  1. 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

  2. Studies on absorption coefficient near edge of multi elements

    NASA Astrophysics Data System (ADS)

    Eisa, M. H.; Shen, H.; Yao, H. Y.; Mi, Y.; Zhou, Z. Y.; Hu, T. D.; Xie, Y. N.

    2005-12-01

    X-ray absorption near edge structure (XANES) was used to study the near edge mass-absorption coefficients of seven elements, such as, Ti, V, Fe, Co, Ni, Cu and Zn. It is well known that, on the near edge absorption of element, when incident X-ray a few eV change can make the absorption coefficient an order magnitude alteration. So that, there are only a few points mass-absorption coefficient at the near edge absorption and that always average value in published table. Our results showed a wide range of data, the total measured data of mass-absorption coefficient of the seven elements was about 505. The investigation confirmed that XANES is useful technique for multi-element absorption coefficient measurement. Details of experimental methods and results are given and discussed. The experimental work has been performed at Beijing Synchrotron Radiation Facility. The measured values were compared with the published data. Good agreement between experimental results and published data is obtained.

  3. X-Ray Absorption near Edge Structure Spectroscopy of Nanodiamonds from the Allende Meteorite

    NASA Technical Reports Server (NTRS)

    Flynn, G. J.; Keller, L. P.; Hill, H.; Jacobsen, C.; Wirick, S.

    2000-01-01

    Carbon X-ray Absorption Near Edge Structure Spectroscopy shows Allende DM nanodiamonds have two pre-edge peaks, consistent with other small diamonds, but fail to show a diamond exciton which is seen in 3.6 nm diamond thin films.

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

    NASA Astrophysics Data System (ADS)

    Ching, Wai-Yim; Rulis, Paul

    2009-03-01

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

  5. 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.

  6. 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

  7. 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

  8. Near-edge X-ray absorption spectra for metallic Cu and Mn

    NASA Astrophysics Data System (ADS)

    Greaves, G. N.; Durham, P. J.; Diakun, G.; Quinn, P.

    1981-11-01

    The measurement of X-ray absorption fine structure of metals- both in the extended region (EXAFS) as well as in the near edge region (XANES)-has been widely discussed (see refs 1-6 for Cu and refs 7-9 for Mn). The recent availability of intense X-ray fluxes from storage rings has usually been exploited for EXAFS leaving the XANES often with poorer resolution than earlier work performed on conventional sources (for example, compare the near edge structure for copper in ref. 1 with refs 3 or 6). In addition, whilst the theory and analysis of EXAFS is relatively well-established2,10, a theory for the strong scattering regime near to the absorption edge has only recently been developed11. We report here the first high resolution XANES spectra for Cu and Mn which were performed at the SRS storage ring at Daresbury. Although both metals have close-packed structures consisting of atoms of similar size their local atomic structure is different in detail. Significant differences are found in their respective XANES reflecting the senstivity of this region of the X-ray absorption fine structure to the local atomic structure. Spectra for the two metals have been analysed using the new multiple scattering formalism. This is a real space calculation and unlike a conventional band structure approach it does not require structural periodicity but works from the local arrangement of atoms.

  9. 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.

  10. Identification of F impurities in F-doped ZnO by synchrotron X-ray absorption near edge structures

    NASA Astrophysics Data System (ADS)

    Na-Phattalung, Sutassana; Limpijumnong, Sukit; Min, Chul-Hee; Cho, Deok-Yong; Lee, Seung-Ran; Char, Kookrin; Yu, Jaejun

    2018-04-01

    Synchrotron X-ray absorption near edge structure (XANES) measurements of F K-edge in conjunction with first-principles calculations are used to identify the local structure of the fluorine (F) atom in F-doped ZnO. The ZnO film was grown by pulsed laser deposition with an Nd:YAG laser, and an oxyfluoridation method was used to introduce F ions into the ZnO films. The measured XANES spectrum of the sample was compared against the first-principles XANES calculations based on various models for local atomic structures surrounding F atoms. The observed spectral features are attributed to ZnF2 and FO defects in wurtzite bulk ZnO.

  11. 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

  12. Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

  13. 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.

  14. Electronic structure of Cr doped Fe3O4 thin films by X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Chi-Liang; Dong, Chung-Li; Asokan, Kandasami; Chern, G.; Chang, C. L.

    2018-04-01

    Present study reports the electronic structures of Cr doped Fe3O4 (Fe3-xCrxO4 (0 ≤ x ≤ 3) grown on MgO (100) substrates in the form of thin films fabricated by a plasma-oxygen assisted Molecular Beam Epitaxy (MBE). X-ray absorption near-edge structure (XANES) spectra at Cr & Fe L-, and O K-edges were used to understand the electronic structure: changes in the bonding nature, valence states, and site occupancies. Cr doping in Fe3O4 results in the change of charge transfer, crystal structure, and selective occupation of ions in octahedral and tetrahedral sites. Such change modifies the electrical and magnetic properties due to the covalency of Cr ions. The physical and chemical properties of ferrites are strongly dependent on the lattice site, ion size of dopant, and magnetic nature present at different structural symmetry of the spinel structure.

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

    DOE PAGES

    Timoshenko, J.; Shivhare, A.; Scott, R. W.; ...

    2016-06-30

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

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  17. Structural evolution of fluorinated graphene upon molten-alkali treatment probed by X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Liang, Xianqing; Pan, Deyou; Lao, Ming; Liang, Shuiying; Huang, Dan; Zhou, Wenzheng; Guo, Jin

    2017-05-01

    The structural evolution of fluorinated graphene (FG) nanosheets upon molten-alkali treatment has been systematically investigated utilizing X-ray absorption near-edge structure (XANES) spectroscopy. It is found that the hydroxyl groups can progressively displace fluorine atoms to form covalent bonds to the graphene sheets under designed molten-alkali condition. The XANES spectra also reveal the formation of epoxide groups through intramolecular dehydration of neighbouring hydroxyl groups after substitution reaction. At high alkali-FG weight ratio, the restoration of the π-conjugated structure in graphene sheets can be observed due to the gradual decomposition of epoxide groups. Our experimental results indicate that the surface chemistry and electronic structure of hydroxyl-functionalized FG (HFG) can be readily tuned by varying the ratio of reactants.

  18. The use of C-near edge X-ray absorption fine structure spectroscopy for the elaboration of chemistry in lignocellulosics

    Treesearch

    Lucian A. Lucia; Hiroki Nanko; Alan W. Rudie; Doug G. Mancosky; Sue Wirick

    2006-01-01

    The research presented elucidates the oxidation chemistry occurring in hydrogen peroxide bleached kraft pulp fibers by employing carbon near edge x-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft x-ray technique that selectively interrogates atomic moieties using photoelectrons (Xrays) of variable energies. The X1A beam line at the National...

  19. Novel visualization studies of lignocellulosic oxidation chemistry by application of C-near edge X-ray absorption fine structure spectroscopy

    Treesearch

    Douglas G. Mancosky; Lucian A. Lucia; Hiroki Nanko; Sue Wirick; Alan W. Rudie; Robert Braun

    2005-01-01

    The research presented herein is the first attempt to probe the chemical nature of lignocellulosic samples by the application of carbon near edge X-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft X-ray technique that principally provides selective interrogation of discrete atomic moieties using photoelectrons of variable energies. The X1A beam...

  20. 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

  1. The P K-near edge absorption spectra of phosphates

    NASA Astrophysics Data System (ADS)

    Franke, R.; Hormes, J.

    1995-12-01

    The X-ray absorption near edge structure (XANES) at the P K-edge in several orthophosphates with various cations, in condensed, and in substituted sodium phosphates have been measured using synchrotron radiation from the ELSA storage ring at the University of Bonn. The measured spectra demonstrate that chemical changes beyond the PO 4- tetrahedra are reflected by energy shifts of the pre-edge and continuum resonances, by the presence of characteristic shoulders and new peaks and by differences in the intensity of the white line. We discuss the energy differences between the white line positions and the corresponding P ls binding energies as a measure of half of the energy gap. The corresponding values correlate with the valence of the cations and the intensity of the white lines. The energy positions of the continuum resonances are discussed on the basis of an empirical bond-length correlation supporting a 1/ r2 - dependence.

  2. Near-edge x-ray absorption fine structure spectroscopy at atmospheric pressure with a table-top laser-induced soft x-ray source

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

    Kühl, Frank-Christian, E-mail: Frank-christian.kuehl@mail.de; Müller, Matthias, E-mail: matthias.mueller@llg-ev.de; Schellhorn, Meike

    2016-07-15

    The authors present a table-top soft x-ray absorption spectrometer, accomplishing investigations of the near-edge x-ray absorption fine structure (NEXAFS) in a laboratory environment. The system is based on a low debris plasma ignited by a picosecond laser in a pulsed krypton gas jet, emitting soft x-ray radiation in the range from 1 to 5 nm. For absorption spectroscopy in and around the “water window” (2.3–4.4 nm), a compact helium purged sample compartment for experiments at atmospheric pressure has been constructed and tested. NEXAFS measurements on CaCl{sub 2} and KMnO{sub 4} samples were conducted at the calcium and manganese L-edges, as well asmore » at the oxygen K-edge in air, atmospheric helium, and under vacuum, respectively. The results indicate the importance of atmospheric conditions for an investigation of sample hydration processes.« less

  3. Electronic structure and optical properties of CdSxSe1-x solid solution nanostructures from X-ray absorption near edge structure, X-ray excited optical luminescence, and density functional theory investigations

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

    The electronic structure and optical properties of a series of iso-electronic and iso-structural CdSxSe1-x solid solution nanostructures have been investigated using X-ray absorption near edge structure, extended X-ray absorption fine structure, and X-ray excited optical luminescence at various absorption edges of Cd, S, and Se. It is found that the system exhibits compositions, with variable local structure in-between that of CdS and CdSe accompanied by tunable optical band gap between that of CdS and CdSe. Theoretical calculation using density functional theory has been carried out to elucidate the observations. It is also found that luminescence induced by X-ray excitation shows new optical channels not observed previously with laser excitation. The implications of these observations are discussed.

  4. Application toward Confocal Full-Field Microscopic X-ray Absorption Near Edge Structure Spectroscopy.

    PubMed

    Tack, Pieter; Vekemans, Bart; Laforce, Brecht; Rudloff-Grund, Jennifer; Hernández, Willinton Y; Garrevoet, Jan; Falkenberg, Gerald; Brenker, Frank; Van Der Voort, Pascal; Vincze, Laszlo

    2017-02-07

    Using X-ray absorption near edge structure (XANES) spectroscopy, information on the local chemical structure and oxidation state of an element of interest can be acquired. Conventionally, this information can be obtained in a spatially resolved manner by scanning a sample through a focused X-ray beam. Recently, full-field methods have been developed to obtain direct 2D chemical state information by imaging a large sample area. These methods are usually in transmission mode, thus restricting the use to thin and transmitting samples. Here, a fluorescence method is displayed using an energy-dispersive pnCCD detector, the SLcam, characterized by measurement times far superior to what is generally applicable. Additionally, this method operates in confocal mode, thus providing direct 3D spatially resolved chemical state information from a selected subvolume of a sample, without the need of rotating a sample. The method is applied to two samples: a gold-supported magnesia catalyst (Au/MgO) and a natural diamond containing Fe-rich inclusions. Both samples provide XANES spectra that can be overlapped with reference XANES spectra, allowing this method to be used for fingerprinting and linear combination analysis of known XANES reference compounds.

  5. Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

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

    Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

    2016-04-04

    This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

  6. 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.

  7. Near-Edge X-ray Absorption Fine Structure Studies of Electrospun Poly(dimethylsiloxane)/Poly (methyl methacrylate)/Multiwall Carbon Nanotube Composites

    PubMed Central

    Winter, A. Douglas; Larios, Eduardo; Alamgir, Faisal M.; Jaye, Cherno; Fischer, Daniel; Campo, Eva M.

    2014-01-01

    This work describes the near conduction band edge structure of electrospun mats of MWCNT-PDMS-PMMA by near edge X-Ray absorption fine structure (NEXAFS) spectroscopy. Effects of adding nanofillers of different sizes were addressed. Despite observed morphological variations and inhomogeneous carbon nanotube distribution, spun mats appeared homogeneous under NEXAFS analysis. Spectra revealed differences in emissions from glancing and normal spectra; which may evidence phase separation within the bulk of the micron-size fibers. Further, dichroic ratios show polymer chains did not align, even in the presence of nanofillers. Addition of nanofillers affected emissions in the C-H, C=O and C-C regimes, suggesting their involvement in interfacial matrix-carbon nanotube bonding. Spectral differences at glancing angles between pristine and composite mats suggest that geometric conformational configurations are taking place between polymeric chains and carbon nanotubes. These differences appear to be carbon nanotube-dimension dependent, and are promoted upon room temperature mixing and shear flow during electrospinning. CH-π bonding between polymer chains and graphitic walls, as well as H-bonds between impurities in the as-grown CNTs and polymer pendant groups are proposed bonding mechanisms promoting matrix conformation. PMID:24308286

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

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

    McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.

    2010-12-03

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

  9. 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.

  10. Near Edge X-Ray Absorption and X-Ray Photoelectron Diffraction Studies of the Structural Environment of Ge-Si Systems

    NASA Astrophysics Data System (ADS)

    Castrucci, P.; Gunnella, R.; Pinto, N.; Bernardini, R.; de Crescenzi, M.; Sacchi, M.

    Near edge X-ray absorption spectroscopy (XAS), X-ray photoelectron diffraction (XPD) and Auger electron diffraction (AED) are powerful techniques for the qualitative study of the structural and electronic properties of several systems. The recent development of a multiple scattering approach to simulating experimental spectra opened a friendly way to the study of structural environments of solids and surfaces. This article reviews recent X-ray absorption experiments using synchrotron radiation which were performed at Ge L edges and core level electron diffraction measurements obtained using a traditional X-ray source from Ge core levels for ultrathin Ge films deposited on silicon substrates. Thermodynamics and surface reconstruction have been found to play a crucial role in the first stages of Ge growth on Si(001) and Si(111) surfaces. Both techniques show the occurrence of intermixing processes even for room-temperature-grown Ge/Si(001) samples and give a straightforward measurement of the overlayer tetragonal distortion. The effects of Sb as a surfactant on the Ge/Si(001) interface have also been investigated. In this case, evidence of layer-by-layer growth of the fully strained Ge overlayer with a reduced intermixing is obtained when one monolayer of Sb is predeposited on the surface.

  11. 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.

  12. Changes in the near edge X-ray absorption fine structure of hybrid organic-inorganic resists upon exposure.

    PubMed

    Fallica, Roberto; Watts, Benjamin; Roesner, Benedikt; Della Giustina, Gioia; Brigo, Laura; Brusatin, Giovanna; Ekinci, Yasin

    2018-06-14

    We report on the near edge X-ray absorption fine structure (NEXAFS) spectroscopy of hybrid organic-inorganic resists. These materials are nonchemically amplified systems based on Si, Zr, and Ti oxides, synthesized from organically modified precursors and transition metal alkoxides by a sol-gel route and designed for ultraviolet, extreme ultraviolet and electron beam lithography. The experiments were conducted using a scanning transmission X-ray microscope (STXM) which combines high spatial-resolution microscopy and NEXAFS spectroscopy. The absorption spectra were collected in the proximity of the carbon edge (~ 290 eV) before and after in situ exposure, enabling the measurement of a significant photo-induced degradation of the organic group (phenyl or methyl methacrylate, respectively), the degree of which depends on the configuration of the ligand. Photo-induced degradation was more efficient in the resist synthesized with pendant phenyl substituents than it was in the case of systems based on bridging phenyl groups. The degradation of the methyl methacrylate group was relatively efficient, with about half of the initial ligands dissociated upon exposure. Our data reveal that the such dissociation can produce different outcomes, depending on the structural configuration. While all the organic groups were expected to detach and desorb from the resist in their entirety, a sizeable amount of them remain and form undesired byproducts such as alkene chains. In the framework of the materials synthesis and engineering through specific building blocks, these results provide a deeper insight into the photochemistry of resists, in particular for extreme ultraviolet lithography. © 2018 IOP Publishing Ltd.

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

    PubMed

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

    2015-09-01

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

  14. 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

  15. Orientational behavior of thin films of poly(3-methylthiophene) on platinium: A FTIR and near edge x-ray absorption fine structure (NEXAFS) study

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

    Yang, X.Q.; Chen, J.; Hale, P.D.

    1988-01-01

    Near edge x-ray absorption fine structure (NEXAFS) and infrared reflection-absorption spectroscopy (IRRAS) have been used to study the orientational behavior of thin films of poly(3-methylthiophene) electrochemically polymerized on a platinum surface. Clear orientational effects, with the thiophene rings predominantly oriented parallel to the platinum surface, were observed when the thickness of the polymer films were within a few hundred /angstrom/A. It was found that more highly ordered films were produced at lower polymerization potential (1.4V vs SCE) than at higher potential (1.8V vs SCE). 5 refs., 4 figs., 2 tabs.

  16. Structure formation in organic thin films observed in real time by energy dispersive near-edge x-ray absorption fine-structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Scholz, M.; Sauer, C.; Wiessner, M.; Nguyen, N.; Schöll, A.; Reinert, F.

    2013-08-01

    We study the structure formation of 1,4,5,8-naphthalene-tetracarboxylicacid-dianhydride (NTCDA) multilayer films on Ag(111) surfaces by energy dispersive near-edge x-ray absorption fine-structure spectroscopy (NEXAFS) and photoelectron spectroscopy. The time resolution of seconds of the method allows us to identify several sub-processes, which occur during the post-growth three-dimensional structural ordering, as well as their characteristic time scales. After deposition at low temperature the NTCDA molecules are preferentially flat lying and the films exhibit no long-range order. Upon annealing the molecules flip into an upright orientation followed by an aggregation in a transient phase which exists for several minutes. Finally, three-dimensional islands are established with bulk-crystalline structure involving substantial mass transport on the surface and morphological roughening. By applying the Kolmogorov-Johnson-Mehl-Avrami model the activation energies of the temperature-driven sub-processes can be derived from the time evolution of the NEXAFS signal.

  17. The origin of luminescence from di[4-(4-diphenylaminophenyl)phenyl]sulfone (DAPSF), a blue light emitter: an X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) study.

    PubMed

    Zhang, Duo; Zhang, Hui; Zhang, Xiaohong; Sham, Tsun-Kong; Hu, Yongfeng; Sun, Xuhui

    2016-03-07

    The electronic structure and optical properties of di[4-(4-diphenylaminophenyl)phenyl]sulfone (denoted as DAPSF), a highly efficient fluorophor, have been investigated using X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) spectroscopy at excitation energies across the C, N, O K-edges and the sulfur K-edge. The results indicate that the blue luminescence is mainly related to the sulfur functional group.

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. Approximating the near-edge mass absorption coefficients for Ni using an ultra-thin bimetal foil

    DOE PAGES

    Alkire, Randall W.

    2016-11-01

    In an effort to improve the characteristics of a fluorescing metal-foil-based beam position monitor, a new bimetal ultra-thin (0.98/0.67 µm) Ti–Ni foil was introduced to replace an existing single-element ultra-thin 0.5 µm thick Cr foil. During characterization it was determined that absorption measurements on the bimetal foil could be used to fit the Ni mass absorption coefficients accurately in the vicinity of the NiKedge. Comparison with experimental results from the literature demonstrated that the fitting procedure produced coefficients with uncertainties of the order of ±1%. Once determined, these fit coefficients allowed the thickness of an independently mounted 8 µm thickmore » Ni foil to be computed from absorption measurements instead of relying on a tool-based measurement of the foil thickness. Using the 8 µm thick foil, a continuous map of Ni mass absorption coefficients was produced at 1 eV resolution throughout the near-edge region. Lastly, this high-resolution map marks a significant improvement over the existing NIST XCOM or FFAST database mass absorption coefficients, which have estimated errors of 10–20% for the near-edge region.« less

  3. 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1989-11-01

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

  6. Near- and Extended-Edge X-Ray-Absorption Fine-Structure Spectroscopy Using Ultrafast Coherent High-Order Harmonic Supercontinua

    NASA Astrophysics Data System (ADS)

    Popmintchev, Dimitar; Galloway, Benjamin R.; Chen, Ming-Chang; Dollar, Franklin; Mancuso, Christopher A.; Hankla, Amelia; Miaja-Avila, Luis; O'Neil, Galen; Shaw, Justin M.; Fan, Guangyu; Ališauskas, Skirmantas; Andriukaitis, Giedrius; Balčiunas, Tadas; Mücke, Oliver D.; Pugzlys, Audrius; Baltuška, Andrius; Kapteyn, Henry C.; Popmintchev, Tenio; Murnane, Margaret M.

    2018-03-01

    Recent advances in high-order harmonic generation have made it possible to use a tabletop-scale setup to produce spatially and temporally coherent beams of light with bandwidth spanning 12 octaves, from the ultraviolet up to x-ray photon energies >1.6 keV . Here we demonstrate the use of this light for x-ray-absorption spectroscopy at the K - and L -absorption edges of solids at photon energies near 1 keV. We also report x-ray-absorption spectroscopy in the water window spectral region (284-543 eV) using a high flux high-order harmonic generation x-ray supercontinuum with 109 photons/s in 1% bandwidth, 3 orders of magnitude larger than has previously been possible using tabletop sources. Since this x-ray radiation emerges as a single attosecond-to-femtosecond pulse with peak brightness exceeding 1026 photons/s /mrad2/mm2/1 % bandwidth, these novel coherent x-ray sources are ideal for probing the fastest molecular and materials processes on femtosecond-to-attosecond time scales and picometer length scales.

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

    NASA Astrophysics Data System (ADS)

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

    1999-11-01

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

  8. Effects of strain relaxation in Pr 0.67Sr 0.33MnO 3 films probed by polarization dependent X-ray absorption near edge structure

    DOE PAGES

    zhang, Bangmin; Chen, Jingsheng; Venkatesan, T.; ...

    2016-01-28

    In this study, the Mn K edge X-ray absorption near edge structure (XANES) of Pr 0.67Sr 0.33MnO 3 films with different thicknesses on (001) LaAlO 3 substrate were measured, and the effects of strain relaxation on film properties were investigated. The films experienced in-plane compressive strain and out-of-plane tensile strain. Strain relaxation evolved with the film thickness. In the polarization dependent XANES measurements, the in-plane (parallel) and out-of-plane (perpendicular) XANES spectrocopies were anisotropic with different absorption energy E r. The resonance energy Er along two directions shifted towards each other with increasing film thickness. Based on the X-ray diffraction results,more » it was suggested that the strain relaxation weakened the difference of the local environment and probability of electronic charge transfer (between Mn 3d and O 2p orbitals) along the in-plane and out-of-plane directions, which was responsible for the change of E r. XANES is a useful tool to probe the electronic structures, of which the effects on magnetic properties with the strain relaxation was also been studied.« less

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

    NASA Astrophysics Data System (ADS)

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

    1997-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    USGS Publications Warehouse

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

    2016-01-01

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

  12. Fundamental absorption edge of NiO nanocrystals

    NASA Astrophysics Data System (ADS)

    Sokolov, V. I.; Druzhinin, A. V.; Kim, G. A.; Gruzdev, N. B.; Yermakov, A. Ye.; Uimin, M. A.; Byzov, I. V.; Shchegoleva, N. N.; Vykhodets, V. B.; Kurennykh, T. E.

    2013-12-01

    NiO nanocrystals with the average size of 5, 10 and 25 nm were synthesized by gas-condensation method. The well-defined increase of the optical density D near the fundamental absorption edge of NiO nanocrystals in the range of 3.5-4.0 eV observed after the annealing in air is caused by the oxygen content growth. It is the direct experimental evidence of the fact that p-d charge transfer transitions form the fundamental absorption edge.

  13. Direct determination of oxidation state of gold deposits in metal-reducing bacterium Shewanella algae using X-ray absorption near-edge structure spectroscopy (XANES).

    PubMed

    Konishi, Yasuhiro; Tsukiyama, Takeshi; Saitoh, Norizoh; Nomura, Toshiyuki; Nagamine, Shinsuke; Takahashi, Yoshio; Uruga, Tomoya

    2007-06-01

    X-ray absorption near-edge structure spectroscopy (XANES) was successfully employed to determine the gold valence in the metal-reducing bacterium Shewanella algae after exposure to a 1 mM aqueous HAuCl4 solution for 10-120 min. XANES spectra revealed the oxidation state of gold in the bacterial cells to be Au(0) without any contribution from Au(III), demonstrating that S. algae cells can reduce AuCl4- ions to elemental gold. Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis confirmed that gold nanoparticles 5-15 nm in size were deposited in the periplasmic space of the bacterial cells; a preferable, cell surface location for the easy recovery of biogenic nanoparticles.

  14. 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.

  15. Minerals discovered in paleolithic black pigments by transmission electron microscopy and micro-X-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Chalmin, E.; Vignaud, C.; Salomon, H.; Farges, F.; Susini, J.; Menu, M.

    2006-05-01

    Analysis of archeological materials aims to rediscover the know-how of prehistoric men by determining the nature of the painting matter, its preparation mode, and the geographic origin of its raw materials. The preparation mode of the painting matter of the paleolithic rock art apparently consisted of mixing, grinding, and also heat-treatment. In this study, we focus on black pigments and more particularly manganese oxides. Using the combined approach of transmission electron microscopy (TEM) and Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy, we analyzed a variety of archeological black painted samples. The studied pigments arise from the caves of Ekain (Basque country, Spain), Labastide and Gargas (Hautes-Pyrénées, France). In addition, a black “crayon” (i.e., a “pen”) from the cave of Combe Saunière (Dordogne, France) was also investigated. From the analysis of these painting matters, several unusual minerals have been identified as black pigment, such as manganite, groutite, todorokite and birnessite. These conclusions enable us to estimate the technical level of paleolithic artists: they didn’t use heat-treatment to prepare black painting matter. Consequently, the unusual mineralogy found in some of these pigments suggests that some of the manganese ores are coming from geological settings that are sometimes relatively far away from the Dordogne and Basque region such as in Ariège (central-oriental Pyrénées).

  16. 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

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

    PubMed

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

    2008-08-05

    The process of implanting oxygen in polystyrene (PS) via exposure to ultraviolet-ozone (UV-O) was systematically investigated using the characterization technique of near-edge X-ray absorption fine structure (NEXAFS). Samples of PS exposed to UV-O for 10-300 s and washed with isopropanol were analyzed using the carbon and oxygen K-edge NEXAFS partial electron yields, using various retarding bias voltages to depth-profile the oxygen penetration into the surface. Evaluation of reference polymers provided a scale to quantify the oxygen concentration implanted by UV-O treatment. We find that ozone initially reacts with the double bonds on the phenyl rings, forming carbonyl groups, but within 1 min of exposure, the ratio of double to single oxygen bonds stabilizes at a lower value. Oxygen penetrates the film with relative ease, creating a fairly uniform distribution of oxygen within at least the first 4 nm (the effective depth probed by NEXAFS here). Before oxygen accumulates in large concentrations, however, it preferentially degrades the uppermost layer of the film by removing oxygenated low-molecular-weight oligomers. The failure to accumulate high concentrations of oxygen is seen in the nearly constant carbon edge jump, the low concentration of oxygen even at 5 min exposure (58% of that in poly(4-acetoxystyrene), the polymer with the most similarities to UV-O-treated PS), and the relatively high contact angles. At 5 min exposure the oxygen concentration contains ca. 7 atomic % oxygen. The oxygen species that are implanted consist predominantly of single O-C bonds and double O=C bonds but also include a small fraction of O-H. UV-O treatment leads a plateau after 2 min exposure in the water contact angle hysteresis, at a value of 67 +/- 2 degrees , due primarily to chemical heterogeneity. Annealing above T(g) allows oxygenated species to move short distances away from the surface but not diffuse further than 1-2 nm.

  18. Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene/Guanine Interface - A Proposal for High Mobility, Organic Graphene Field Effect Transistors

    DTIC Science & Technology

    2015-07-01

    AFRL-AFOSR-UK-TR-2015-0034 Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine...Interface – A Proposal for High Mobility, Organic Graphene Field Effect Transistors Eva Campo BANGOR UNIVERSITY COLLEGE ROAD BANGOR...April 2015 4. TITLE AND SUBTITLE Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine Interface - A

  19. Time dependent density functional theory study of the near-edge x-ray absorption fine structure of benzene in gas phase and on metal surfaces.

    PubMed

    Asmuruf, Frans A; Besley, Nicholas A

    2008-08-14

    The near-edge x-ray absorption fine structure of benzene in the gas phase and adsorbed on the Au(111) and Pt(111) surfaces is studied with time dependent density functional theory. Excitation energies computed with hybrid exchange-correlation functionals are too low compared to experiment. However, after applying a constant shift the spectra are in good agreement with experiment. For benzene on the Au(111) surface, two bands arising from excitation to the e(2u)(pi(*)) and b(2g)(pi(*)) orbitals of benzene are observed for photon incidence parallel to the surface. On Pt(111) surface, a broader band arises from excitation to benzene orbitals that are mixed with the surface and have both sigma(*)(Pt-C) and pi(*) characters.

  20. 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

  1. X-ray Absorption Near Edge Structure Spectroscopy to Resolve the in Vivo Chemistry of the Redox-Active Indazolium trans-[Tetrachlorobis(1H-indazole)ruthenate(III)] (KP1019)

    PubMed Central

    2013-01-01

    Indazolium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (1, KP1019) and its analogue sodium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (2, KP1339) are promising redox-active anticancer drug candidates that were investigated with X-ray absorption near edge structure spectroscopy. The analysis was based on the concept of the coordination charge and ruthenium model compounds representing possible coordinations and oxidation states in vivo. 1 was investigated in citrate saline buffer (pH 3.5) and in carbonate buffer (pH 7.4) at 37 °C for different time intervals. Interaction studies on 1 with glutathione in saline buffer and apo-transferrin in carbonate buffer were undertaken, and the coordination of 1 and 2 in tumor tissues was studied too. The most likely coordinations and oxidation states of the compound under the above mentioned conditions were assigned. Microprobe X-ray fluorescence of tumor thin sections showed the strong penetration of ruthenium into the tumor tissue, with the highest concentrations near blood vessels and in the edge regions of the tissue samples. PMID:23282017

  2. 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

  3. Influence of point defects on the near edge structure of hexagonal boron nitride

    NASA Astrophysics Data System (ADS)

    McDougall, Nicholas L.; Partridge, Jim G.; Nicholls, Rebecca J.; Russo, Salvy P.; McCulloch, Dougal G.

    2017-10-01

    Hexagonal boron nitride (hBN) is a wide-band-gap semiconductor with applications including gate insulation layers in graphene transistors, far-ultraviolet light emitting devices and as hydrogen storage media. Due to its complex microstructure, defects in hBN are challenging to identify. Here, we combine x-ray absorption near edge structure (XANES) spectroscopy with ab initio theoretical modeling to identify energetically favorable defects. Following annealing of hBN samples in vacuum and oxygen, the B and N K edges exhibited angular-dependent peak modifications consistent with in-plane defects. Theoretical calculations showed that the energetically favorable defects all produce signature features in XANES. Comparing these calculations with experiments, the principle defects were attributed to substitutional oxygen at the nitrogen site, substitutional carbon at the boron site, and hydrogen passivated boron vacancies. Hydrogen passivation of defects was found to significantly affect the formation energies, electronic states, and XANES. In the B K edge, multiple peaks above the major 1 s to π* peak occur as a result of these defects and the hydrogen passivated boron vacancy produces the frequently observed doublet in the 1 s to σ* transition. While the N K edge is less sensitive to defects, features attributable to substitutional C at the B site were observed. This defect was also calculated to have mid-gap states in its band structure that may be responsible for the 4.1-eV ultraviolet emission frequently observed from this material.

  4. 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

  5. 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.

  6. Speciation of sulfur from filamentous microbial mats from sulfidic cave springs using X-ray absorption near-edge spectroscopy.

    PubMed

    Engel, Annette Summers; Lichtenberg, Henning; Prange, Alexander; Hormes, Josef

    2007-04-01

    Most transformations within the sulfur cycle are controlled by the biosphere, and deciphering the abiotic and biotic nature and turnover of sulfur is critical to understand the geochemical and ecological changes that have occurred throughout the Earth's history. Here, synchrotron radiation-based sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy is used to examine sulfur speciation in natural microbial mats from two aphotic (cave) settings. Habitat geochemistry, microbial community compositions, and sulfur isotope systematics were also evaluated. Microorganisms associated with sulfur metabolism dominated the mats, including members of the Epsilonproteobacteria and Gammaproteobacteria. These groups have not been examined previously by sulfur K-edge XANES. All of the mats consisted of elemental sulfur, with greater contributions of cyclo-octasulfur (S8) compared with polymeric sulfur (Smicro). While this could be a biological fingerprint for some bacteria, the signature may also indicate preferential oxidation of Smicro and S8 accumulation. Higher sulfate content correlated to less S8 in the presence of Epsilonproteobacteria. Sulfur isotope compositions confirmed that sulfur content and sulfur speciation may not correlate to microbial metabolic processes in natural samples, thereby complicating the interpretation of modern and ancient sulfur records.

  7. 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.

  8. 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.

  9. Local structure in LaMnO3 and CaMnO3 perovskites: A quantitative structural refinement of Mn K -edge XANES data

    NASA Astrophysics Data System (ADS)

    Monesi, C.; Meneghini, C.; Bardelli, F.; Benfatto, M.; Mobilio, S.; Manju, U.; Sarma, D. D.

    2005-11-01

    Hole-doped perovskites such as La1-xCaxMnO3 present special magnetic and magnetotransport properties, and it is commonly accepted that the local atomic structure around Mn ions plays a crucial role in determining these peculiar features. Therefore experimental techniques directly probing the local atomic structure, like x-ray absorption spectroscopy (XAS), have been widely exploited to deeply understand the physics of these compounds. Quantitative XAS analysis usually concerns the extended region [extended x-ray absorption fine structure (EXAFS)] of the absorption spectra. The near-edge region [x-ray absorption near-edge spectroscopy (XANES)] of XAS spectra can provide detailed complementary information on the electronic structure and local atomic topology around the absorber. However, the complexity of the XANES analysis usually prevents a quantitative understanding of the data. This work exploits the recently developed MXAN code to achieve a quantitative structural refinement of the Mn K -edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1-xMnO3 . The results derived from the EXAFS and XANES analyses are in good agreement, demonstrating that a quantitative picture of the local structure can be obtained from XANES in these crystalline compounds. Moreover, the quantitative XANES analysis provides topological information not directly achievable from EXAFS data analysis. This work demonstrates that combining the analysis of extended and near-edge regions of Mn K -edge XAS spectra could provide a complete and accurate description of Mn local atomic environment in these compounds.

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

    PubMed

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

    2009-11-01

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

  11. Composition analysis of a polymer electrolyte membrane fuel cell microporous layer using scanning transmission X-ray microscopy and near edge X-ray absorption fine structure analysis

    NASA Astrophysics Data System (ADS)

    George, Michael G.; Wang, Jian; Banerjee, Rupak; Bazylak, Aimy

    2016-03-01

    The novel application of scanning transmission X-ray microscopy (STXM) to the microporous layer (MPL) of a polymer electrolyte membrane fuel cell is investigated. A spatially resolved chemical component distribution map is obtained for the MPL of a commercially available SGL 25 BC sample. This is achieved with near edge X-ray absorption fine structure spectroscopic analysis. Prior to analysis the sample is embedded in non-reactive epoxy and ultra-microtomed to a thickness of 100 nm. Polytetrafluoroethylene (PTFE), carbon particle agglomerates, and supporting epoxy resin distributions are identified and reconstructed for a scanning area of 6 μm × 6 μm. It is observed that the spatial distribution of PTFE is strongly correlated to the carbon particle agglomerations. Additionally, agglomerate structures of PTFE are identified, possibly indicating the presence of a unique mesostructure in the MPL. STXM analysis is presented as a useful technique for the investigation of chemical species distributions in the MPL.

  12. 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.

  13. [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

  14. 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

  15. Analysis of sulfidic linkages formed in natural rubber latex medical gloves by using X-ray absorption near edge structure

    NASA Astrophysics Data System (ADS)

    Chankrachang, M.; Limphirat, W.; Yongyingsakthavorn, P.; Nontakaew, U.; Tohsan, A.

    2017-09-01

    A study of sulfidic linkages formed in natural rubber (NR) latex medical gloves by using X-ray Absorption Near Edge Structure (XANES) is presented in this paper. The NR latex compound was prepared by using prevulcanization method, that is, it was prevulcanized at room temperature for 24 hrs before utilization. After the 24 hrs of prevulcanization, the latex film samples were obtained by dipping process. The dipped films were subjected to vulcanize at 110°C for 5 to 25 min. It was observed that after the compound was prevulcanized for 24 hrs, polysulfidic linkages were mainly formed in the sample. It was however found that after curing at 110°C for 5-25 min, the polysulfidic linkages are tended to change into disulfide linkages. Especially, in the case of 25 minutes cured sample, disulfide linkages are found to be the main linkages. In term of tensile strength, it was observed that when cure time increased from 5 - 10 min, tensile strengths were also increased. But when the cure time of the film is 25 minutes, tensile strength was slightly dropped. The dropped of tensile strength when cure time is longer than 10 minutes can be ascribed to a degradation of polysulfidic and disulfidic linkages during curing. Therefore, by using XANES analysis, it was found to be very useful to understand the cure characteristic, thus it can be very helpful to optimize cure time and tensile properties of the product.

  16. Optical absorption edge of ZnO thin films: The effect of substrate

    NASA Astrophysics Data System (ADS)

    Srikant, V.; Clarke, D. R.

    1997-05-01

    The optical absorption edge and the near-absorption edge characteristics of undoped ZnO films grown by laser ablation on various substrates have been investigated. The band edge of films on C [(0001)] and R-plane [(1102)] sapphire, 3.29 and 3.32 eV, respectively, are found to be very close to the single crystal value of ZnO (3.3 eV) with the differences being accounted for in terms of the thermal mismatch strain using the known deformation potentials of ZnO. In contrast, films grown on fused silica consistently exhibit a band edge ˜0.1 eV lower than that predicted using the known deformation potential and the thermal mismatch strains. This behavior is attributed to the small grain size (50 nm) realized in these films and the effect of electrostatic potentials that exist at the grain boundaries. Additionally, the spread in the tail (E0) of the band edge for the different films is found to be very sensitive to the defect structure in the films. For films grown on sapphire substrates, values of E0 as low as 30 meV can be achieved on annealing in air, whereas films on fused silica always show a value >100 meV. We attribute this difference to the substantially higher density of high-angle grain boundaries in the films on fused silica.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  18. Electronic structure of transition metal-cysteine complexes from X-ray absorption spectroscopy.

    PubMed

    Leung, Bonnie O; Jalilehvand, Farideh; Szilagyi, Robert K

    2008-04-17

    The electronic structures of HgII, NiII, CrIII, and MoV complexes with cysteine were investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory. The covalency in the metal-sulfur bond was determined by analyzing the intensities of the electric-dipole allowed pre-edge features appearing in the XANES spectra below the ionization threshold. Because of the well-defined structures of the selected cysteine complexes, the current work provides a reference set for further sulfur K-edge XAS studies of bioinorganic active sites with transition metal-sulfur bonds from cysteine residues as well as more complex coordination compounds with thiolate ligands.

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

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

  1. Electronic structure of nickel silicide in subhalf-micron lines and blanket films: An x-ray absorption fine structures study at the Ni and Si L3,2 edge

    NASA Astrophysics Data System (ADS)

    Naftel, S. J.; Coulthard, I.; Sham, T. K.; Xu, D.-X.; Erickson, L.; Das, S. R.

    1999-05-01

    We report a Ni and Si L3,2-edge x-ray absorption near edge structures (XANES) study of nickel-silicon interaction in submicron (0.15 and 0.2 μm) lines on a n-Si(100) wafer as well as a series of well characterized Ni-Si blanket films. XANES measurements recorded in both total electron yield and soft x-ray fluorescence yield indicate that under the selected silicidation conditions, the more desirable low resistivity phase, NiSi, is indeed the dominant phase in the subhalf-micron lines although the formation of this phase is less complete as the line becomes narrower and this is accompanied by a Ni rich surface.

  2. 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

  3. 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

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

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

    Antalek, Matthew; Hedman, Britt; Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu

    2016-07-28

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

  5. Soft X-ray Absorption Edges in LMXBs

    NASA Technical Reports Server (NTRS)

    2004-01-01

    The XMM observation of LMC X-2 is part of our program to study X-ray absorption in the interstellar medium (ISM). This program includes a variety of bright X-ray binaries in the Galaxy as well as the Magellanic Clouds (LMC and SMC). LMC X-2 is located near the heart of the LMC. Its very soft X-ray spectrum is used to determine abundance and ionization fractions of neutral and lowly ionized oxygen of the ISM in the LMC. The RGS spectrum so far allowed us to determine the O-edge value to be for atomic O, the EW of O-I in the ls-2p resonance absorption line, and the same for O-II. The current study is still ongoing in conjunction with other low absorption sources like Sco X-1 and the recently observed X-ray binary 4U 1957+11.

  6. Characterization of Unsteady Flow Structures Near Leading-Edge Slat. Part 1; PIV Measurements

    NASA Technical Reports Server (NTRS)

    Jenkins, Luther N.; Khorrami, Mehdi R.; Choudhari, Meelan

    2004-01-01

    A comprehensive computational and experimental study has been performed at the NASA Langley Research Center as part of the Quiet Aircraft Technology (QAT) Program to investigate the unsteady flow near a leading-edge slat of a two-dimensional, high-lift system. This paper focuses on the experimental effort conducted in the NASA Langley Basic Aerodynamics Research Tunnel (BART) where Particle Image Velocimetry (PIV) data was acquired in the slat cove and at the slat trailing edge of a three-element, high-lift model at 4, 6, and 8 degrees angle of attack and a freestream Mach Number of 0.17. Instantaneous velocities obtained from PIV images are used to obtain mean and fluctuating components of velocity and vorticity. The data show the recirculation in the cove, reattachment of the shear layer on the slat lower surface, and discrete vortical structures within the shear layer emanating from the slat cusp and slat trailing edge. Detailed measurements are used to examine the shear layer formation at the slat cusp, vortex shedding at the slat trailing edge, and convection of vortical structures through the slat gap. Selected results are discussed and compared with unsteady, Reynolds-Averaged Navier-Stokes (URANS) computations for the same configuration in a companion paper by Khorrami, Choudhari, and Jenkins (2004). The experimental dataset provides essential flow-field information for the validation of near-field inputs to noise prediction tools.

  7. Enhancement of broadband optical absorption in photovoltaic devices by band-edge effect of photonic crystals.

    PubMed

    Tanaka, Yoshinori; Kawamoto, Yosuke; Fujita, Masayuki; Noda, Susumu

    2013-08-26

    We numerically investigate broadband optical absorption enhancement in thin, 400-nm thick microcrystalline silicon (µc-Si) photovoltaic devices by photonic crystals (PCs). We realize absorption enhancement by coupling the light from the free space to the large area resonant modes at the photonic band-edge induced by the photonic crystals. We show that multiple photonic band-edge modes can be produced by higher order modes in the vertical direction of the Si photovoltaic layer, which can enhance the absorption on multiple wavelengths. Moreover, we reveal that the photonic superlattice structure can produce more photonic band-edge modes that lead to further optical absorption. The absorption average in wavelengths of 500-1000 nm weighted to the solar spectrum (AM 1.5) increases almost twice: from 33% without photonic crystal to 58% with a 4 × 4 period superlattice photonic crystal; our result outperforms the Lambertian textured structure.

  8. 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.

  9. On the Electronic Structure of Cu Chlorophyllin and Its Breakdown Products: A Carbon K-Edge X-ray Absorption Spectroscopy Study.

    PubMed

    Witte, Katharina; Mantouvalou, Ioanna; Sánchez-de-Armas, Rocío; Lokstein, Heiko; Lebendig-Kuhla, Janina; Jonas, Adrian; Roth, Friedrich; Kanngießer, Birgit; Stiel, Holger

    2018-02-15

    Using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, the carbon backbone of sodium copper chlorophyllin (SCC), a widely used chlorophyll derivative, and its breakdown products are analyzed to elucidate their electronic structure and physicochemical properties. Using various sample preparation methods and complementary spectroscopic methods (including UV/Vis, X-ray photoelectron spectroscopy), a comprehensive insight into the SCC breakdown process is presented. The experimental results are supported by density functional theory calculations, allowing a detailed assignment of characteristic NEXAFS features to specific C bonds. SCC can be seen as a model system for the large group of porphyrins; thus, this work provides a novel and detailed description of the electronic structure of the carbon backbone of those molecules and their breakdown products. The achieved results also promise prospective optical pump/X-ray probe investigations of dynamic processes in chlorophyll-containing photosynthetic complexes to be analyzed more precisely.

  10. 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

  11. 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.

  12. 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.

  13. [Distribution and speciation of Pb in Arabidopsis thaliana shoot and rhizosphere soil by in situ synchrotron radiation micro X-ray fluorescence and X-ray absorption near edge structure].

    PubMed

    Shen, Ya-Ting

    2014-03-01

    In order to investigate plant reacting mechanism with heavy metal stress in organ and tissue level, synchrotron radiation micro X-ray fluorescence (micro-SRXRF) was used to determine element distribution characteristics of K, Ca, Mn, Fe, Cu, Zn, Pb in an Arabidopsis thaliana seedling grown in tailing dam soil taken from a lead-zinc mine exploration area. The results showed a regular distribution characters of K, Ca, Fe, Cu and Zn, while Pb appeared not only in root, but also in a leaf bud which was beyond previously understanding that Pb mainly appeared in plant root. Pb competed with Mn in the distribution of the whole seedling. Pb may cause the increase of oxidative stress in root and leaf bud, and restrict Mn absorption and utilization which explained the phenomenon of seedling death in this tailing damp soil. Speciation of Pb in Arabidopsis thaliana and tailing damp rhizosphere soil were also presented after using PbL3 micro X-ray absorption near edge structure (micro-XANES). By comparison of PbL3 XANES peak shape and peak position between standard samples and rhizosphere soil sample, it was demonstrated that the tailing damp soil was mainly formed by amorphous forms like PbO (64.2%), Pb (OH)2 (28.8%) and Pb3O4 (6.3%) rather than mineral or organic Pb speciations. The low plant bioavailability of Pb demonstrated a further research focusing on Pb absorption and speciation conversion is needed, especially the role of dissolve organic matter in soil which may enhance Pb bioavailability.

  14. The aquatic hyphomycete Heliscus lugdunensis protects its hyphae tip cells from cadmium: A micro X-ray fluorescence and X-ray absorption near edge structure spectroscopy study

    NASA Astrophysics Data System (ADS)

    Isaure, Marie-Pierre; Leyh, Benjamin; Salomé, Murielle; Krauss, Gerd-Joachim; Schaumlöffel, Dirk; Dobritzsch, Dirk

    2017-11-01

    Aquatic fungi can be used to evaluate the functioning of natural ecosystems. Heliscus lugdunensis is an early colonizer of allochthone leafs. Since this aquatic hyphomycete is able to develop in metal contaminated habitats and tolerates cadmium, it appears to be a good candidate to investigate adaptation to metal pollution. This study aimed at examining the sequestration of Cd in the hyphae of H. lugdunensis, and particularly the role of the tip cells. For that, H. lugdunensis growth was evaluated under various Cd concentrations, and a combination of synchrotron micro X-ray fluorescence and X-ray absorption near edge structure spectroscopy was carried out to determine the compartments of Cd accumulation and the Cd chemical species, respectively. Results showed that the hyphal tip cells were depleted in Cd, and that the metal was stored in older cells. Cd was mainly associated with sulfur ligands and to a lesser extent bound to phosphates and carboxyl/hydroxyl groups from cell wall and/or organic acids. Finally, the aquatic fungus was able to maintain the tip cell as a functional system, thus allowing the colonization of contaminated environments.

  15. Chlorine levels and species in fine and size resolved atmospheric particles by X-ray absorption near-edge structure spectroscopy analysis in Beijing, China.

    PubMed

    Ouyang, Jie; Yang, Guo-Sheng; Ma, Ling-Ling; Luo, Min; Zheng, Lei; Huo, Qing; Zhao, Yi-Dong; Hu, Tian-Dou; Cai, Zhen-Feng; Xu, Dian-Dou

    2018-04-01

    An understanding of the species of chlorine is crucial in the metropolis-Beijing, which is suffering serious haze pollution with high frequency. Particulate Matters (PMs) with five different sizes were collected in Beijing from July 2009 to March 2016, and characterized non-destructively by X-ray absorption near edge structure spectroscopy. PM <0.2 , PM 0.2-0.5 and PM >2.5 contributed for the major PMs mass in spring and summer, PM 0.5-1.0 and PM 1.0-2.5 contributed for the major PMs mass in autumn and winter. The concentrations of the three chlorine species were in the order of inorganic chlorine (Cl inorg ) > aliphatic chlorine (Cl ali ) > aromatic chlorine (Cl aro ), indicating that Cl inorg constituted the primary chlorine fraction and less toxic Cl ali constituted the primary total organic chlorine (Cl ali  + Cl aro , abbreviated as Cl org ) in the PMs in Beijing. In addition, these three chlorine species exhibited identical seasonal variation in PM 2.5 : winter > autumn > spring > summer. Wet precipitation is an important factor to result in the lower mass concentrations of these three chlorine species in summer. The temporal variations of both size resolved PM mass concentrations and chlorine species concentrations suggested that the air pollution prevention and control in Beijing has just won initial success. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Nanoindentation near the edge

    Treesearch

    J.E. Jakes; C.R. Frihart; J.F. Beecher; R.J. Moon; P.J. Resto; Z.H. Melgarejo; O.M. Saurez; H. Baumgart; A.A. Elmustafa; D.S. Stone

    2009-01-01

    Whenever a nanoindent is placed near an edge, such as the free edge of the specimen or heterophase interface intersecting the surface, the elastic discontinuity associated with the edge produces artifacts in the load-depth data. Unless properly handled in the data analysis, the artifacts can produce spurious results that obscure any real trends in properties as...

  17. Role of defects in BiFeO₃ multiferroic films and their local electronic structure by x-ray absorption spectroscopy

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

    Ravalia, Ashish; Vagadia, Megha; Solanki, P. S.

    2014-10-21

    Present study reports the role of defects in the electrical transport in BiFeO₃ (BFO) multiferroic films and its local electronic structure investigated by near-edge X-ray absorption fine structure. Defects created by high energy 200 MeV Ag⁺¹⁵ ion irradiation with a fluence of ∼5 × 10¹¹ ions/cm² results in the increase in structural strain and reduction in the mobility of charge carriers and enhancement in resistive (I-V) and polarization (P-E) switching behaviour. At higher fluence of ∼5 × 10¹² ions/cm², there is a release in the structural strain due to local annealing effect, resulting in an increase in the mobility of charge carriers, which are releasedmore » from oxygen vacancies and hence suppression in resistive and polarization switching. Near-edge X-ray absorption fine structure studies at Fe L₃,₂- and O K-edges show a significant change in the spectral features suggesting the modifications in the local electronic structure responsible for changes in the intrinsic magnetic moment and electrical transport properties of BFO.« less

  18. Band-edge absorption coefficients from photoluminescence in semiconductor multiple quantum wells

    NASA Technical Reports Server (NTRS)

    Kost, Alan; Zou, Yao; Dapkus, P. D.; Garmire, Elsa; Lee, H. C.

    1989-01-01

    A novel approach to determining absorption coefficients in thin films using luminescence is described. The technique avoids many of the difficulties typically encountered in measurements of thin samples, Fabry-Perot effects, for example, and can be applied to a variety of materials. The absorption edge for GaAs/AlGaAs multiple quantum well structures, with quantum well widths ranging from 54 to 193 A is examined. Urbach (1953) parameters and excitonic linewidths are tabulated.

  19. 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

  20. Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems

    NASA Astrophysics Data System (ADS)

    Ildefonse, Ph.; Calas, G.; Flank, A. M.; Lagarde, P.

    1995-05-01

    Soft X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy have been performed at the Mg-, Al- and Si-K edges in order to establish the ability of this spectroscopy to derive structural information in disordered solids such as glasses and gels. Mg- and Al-K XANES are good structural probes to determine the coordination state of these elements in important minerals, glasses and gels. In a CaOsbnd MgOsbnd 2SiO2 glass Mg XANES spectra differ from that found in the crystalline equivalent, with a significant shift of the edge maxima to lower energy, consistent with a CN lower than 6. Mg-EXAFS on the same sample are in agreement and indicate the presence of 5-coordinated Mg with Mgsbnd O distances of 2.01Å. In aluminosilicate gels, Alsbnd K XANES has been used to investigate the [4]Al/Altotal ratios. These ratios increase as the Al/Si ratios decrease. Aluminosilicate and ferric-silicate gels were studied by using Sisbnd K edge XANES. XANES spectra differ significantly among the samples studied. Aluminosilicate gels with Al/Si= 1 present a different Al and Si local environment from that known in clay minerals with the same Al/Si ratio. The gel-to-mineral transformation thus implies a dissolution-recrystallization mechanism. On the contrary, ferric-silicate gel presents a Si local environment close to that found in nontronite which may be formed by a long range ordering of the initial gels.

  1. 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

  2. Simulation studies of structure and edge tension of lipid bilayer edges: effects of tail structure and force-field.

    PubMed

    West, Ana; Ma, Kevin; Chung, Jonathan L; Kindt, James T

    2013-08-15

    Molecular dynamics simulations of lipid bilayer ribbons have been performed to investigate the structures and line tensions associated with free bilayer edges. Simulations carried out for dioleoyl phosphatidylcholine with three different force-field parameter sets yielded edge line tensions of 45 ± 2 pN, over 50% greater than the most recently reported experimentally determined value for this lipid. Edge tensions obtained from simulations of a series of phosphatidylcholine lipid bilayer ribbons with saturated acyl tails of length 12-16 carbons and with monounsaturated acyl tails of length 14-18 carbons could be correlated with the excess area associated with forming the edge, through a two-parameter fit. Saturated-tail lipids underwent local thickening near the edge, producing denser packing that correlated with lower line tensions, while unsaturated-tail lipids showed little or no local thickening. In a dipalmitoyl phosphatidylcholine ribbon initiated in a tilted gel-phase structure, lipid headgroups tended to tilt toward the nearer edge producing a herringbone pattern, an accommodation that may account for the reported edge-induced stabilization of an ordered structure at temperatures near a lipid gel-fluid phase transition.

  3. Analysis of buried interfaces in multilayer mirrors using grazing incidence extreme ultraviolet reflectometry near resonance edges.

    PubMed

    Sertsu, M G; Nardello, M; Giglia, A; Corso, A J; Maurizio, C; Juschkin, L; Nicolosi, P

    2015-12-10

    Accurate measurements of optical properties of multilayer (ML) mirrors and chemical compositions of interdiffusion layers are particularly challenging to date. In this work, an innovative and nondestructive experimental characterization method for multilayers is discussed. The method is based on extreme ultraviolet (EUV) reflectivity measurements performed on a wide grazing incidence angular range at an energy near the absorption resonance edge of low-Z elements in the ML components. This experimental method combined with the underlying physical phenomenon of abrupt changes of optical constants near EUV resonance edges enables us to characterize optical and structural properties of multilayers with high sensitivity. A major advantage of the method is to perform detailed quantitative analysis of buried interfaces of multilayer structures in a nondestructive and nonimaging setup. Coatings of Si/Mo multilayers on a Si substrate with period d=16.4  nm, number of bilayers N=25, and different capping structures are investigated. Stoichiometric compositions of Si-on-Mo and Mo-on-Si interface diffusion layers are derived. Effects of surface oxidation reactions and carbon contaminations on the optical constants of capping layers and the impact of neighboring atoms' interactions on optical responses of Si and Mo layers are discussed.

  4. 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.

  5. Near-edge X-ray refraction fine structure microscopy

    DOE PAGES

    Farmand, Maryam; Celestre, Richard; Denes, Peter; ...

    2017-02-06

    We demonstrate a method for obtaining increased spatial resolution and specificity in nanoscale chemical composition maps through the use of full refractive reference spectra in soft x-ray spectro-microscopy. Using soft x-ray ptychography, we measure both the absorption and refraction of x-rays through pristine reference materials as a function of photon energy and use these reference spectra as the basis for decomposing spatially resolved spectra from a heterogeneous sample, thereby quantifying the composition at high resolution. While conventional instruments are limited to absorption contrast, our novel refraction based method takes advantage of the strongly energy dependent scattering cross-section and can seemore » nearly five-fold improved spatial resolution on resonance.« less

  6. 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.

  7. Accurate and facile determination of the index of refraction of organic thin films near the carbon 1s absorption edge.

    PubMed

    Yan, Hongping; Wang, Cheng; McCarn, Allison R; Ade, Harald

    2013-04-26

    A practical and accurate method to obtain the index of refraction, especially the decrement δ, across the carbon 1s absorption edge is demonstrated. The combination of absorption spectra scaled to the Henke atomic scattering factor database, the use of the doubly subtractive Kramers-Kronig relations, and high precision specular reflectivity measurements from thin films allow the notoriously difficult-to-measure δ to be determined with high accuracy. No independent knowledge of the film thickness or density is required. High confidence interpolation between relatively sparse measurements of δ across an absorption edge is achieved. Accurate optical constants determined by this method are expected to greatly improve the simulation and interpretation of resonant soft x-ray scattering and reflectivity data. The method is demonstrated using poly(methyl methacrylate) and should be extendable to all organic materials.

  8. Spin and orbital states in single-layered La2-xCaxCoO4 studied by doping- and temperature-dependent near-edge x-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Merz, M.; Fuchs, D.; Assmann, A.; Uebe, S.; v. Löhneysen, H.; Nagel, P.; Schuppler, S.

    2011-07-01

    The doping-dependent valence, orbital, and spin-state configurations of single-layered La2-xCaxCoO4 (x=0, 0.5, 1, and 1.5) were investigated with temperature-dependent near-edge x-ray absorption fine structure at the Co L2,3 and O K edges. The spectra show that in La2CoO4, the superexchange between neighboring Co2+ HS states is responsible for the strong antiferromagnetism. With increasing hole doping, the superexchange interactions between Co2+ HS ions are rapidly reduced by interlaced nonmagnetic Co3+ LS. For La1.5Ca0.5CoO4, the low Néel temperature of the samples together with the 50% Co2+ HS and 50% Co3+ LS configuration suggests a checkerboard arrangement of these ions. The spin blockade resulting from this arrangement naturally explains the high resistivity of La1.5Ca0.5CoO4. Upon further doping, Co2+ HS ions are replaced by Co3+ HS, and for LaCaCoO4 a mixture of Co3+ LS and Co3+ HS occurs. Superexchange via configuration fluctuation processes between these two species seems to induce long-range ferromagnetism, while the superexchange between adjacent Co3+ HS neighbors may lead to a competing antiferromagnetic exchange. For a doping content beyond x=1, Co4+ HS is introduced to the system at the expense of Co3+ LS, and a t2g double exchange between Co3+ HS and Co4+ HS is established, which further enhances ferromagnetic interactions and reduces resistivity. No indications for a Co3+ IS state are found throughout the La2-xCaxCoO4 doping series.

  9. Interstellar X-Ray Absorption Spectroscopy of the Crab Pulsar with the LETGS

    NASA Technical Reports Server (NTRS)

    Paerels, Frits; Weisskopf, Martin C.; Tennant, Allyn F.; ODell, Stephen L.; Swartz, Douglas A.; Kahn, Steven M.; Behar, Ehud; Becker, Werner; Whitaker, Ann F. (Technical Monitor)

    2001-01-01

    We study the interstellar X-ray absorption along the line of sight to the Crab Pulsar. The Crab was observed with the Low Energy Transmission Grating Spectrometer on the Chandra X-ray Observatory, and the pulsar, a point source, produces a full resolution spectrum. The continuum spectrum appears smooth, and we compare its parameters with other measurements of the pulsar spectrum. The spectrum clearly shows absorption edges due to interstellar Ne, Fe, and O. The O edge shows spectral structure that is probably due to O bound in molecules or dust. We search for near-edge structure (EXAFS) in the O absorption spectrum. The Fe L absorption spectrum is largely due to a set of unresolved discrete n=2-3 transitions in neutral or near-neutral Fe, and we analyze it using a new set of dedicated atomic structure calculations, which provide absolute cross sections. In addition to being interesting in its own right, the ISM absorption needs to be understood in quantitative detail in order to derive spectroscopic constraints on possible soft thermal radiation from the pulsar.

  10. Ca 3d unoccupied states in Bi2Sr2CaCu2O8 investigated by Ca L2,3 x-ray-absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Borg, A.; King, P. L.; Pianetta, P.; Lindau, I.; Mitzi, D. B.; Kapitulnik, A.; Soldatov, A. V.; della Longa, S.; Bianconi, A.

    1992-10-01

    The high-resolution Ca L2,3 x-ray-absorption near-edge-structure (XANES) spectrum of a Bi2Sr2CaCu2O8 single crystal has been measured by use of a magnetic-projection x-ray microscope probing a surface area of 200×200 μm2. The Ca L2,3 XANES spectrum is analyzed by performing a multiple-scattering XANES calculation in real space and comparing the results with the spectrum of CaF2. Good agreement between the calculated and experimental crystal-field splitting Δf of the Ca 3d final states is found and the splitting is shown to be smaller by 0.5 eV than in the initial state. The Ca 3d partial density of states is found to be close to the Fermi level in the initial state. The Ca-O(in plane) distance is shown to be a critical parameter associated with the shift of the Ca 3d states relative to the Fermi level; in particular, we have studied the effect of the out-of-plane dimpling mode of the in-plane oxygen atoms O(in plane) that will move the Ca 3d states on or off the Fermi level. This mode can therefore play a role in modulating the charge transfer between the two CuO2 planes separated by the Ca ions.

  11. Time-dependent mean-field theory for x-ray near-edge spectroscopy

    NASA Astrophysics Data System (ADS)

    Bertsch, G. F.; Lee, A. J.

    2014-02-01

    We derive equations of motion for calculating the near-edge x-ray absorption spectrum in molecules and condensed matter, based on a two-determinant approximation and Dirac's variational principle. The theory provides an exact solution for the linear response when the Hamiltonian or energy functional has only diagonal interactions in some basis. We numerically solve the equations to compare with the Mahan-Nozières-De Dominicis theory of the edge singularity in metallic conductors. Our extracted power-law exponents are similar to those of the analytic theory, but are not in quantitative agreement. The calculational method can be readily generalized to treat Kohn-Sham Hamiltonians with electron-electron interactions derived from correlation-exchange potentials.

  12. Sulfur K-edge extended X-ray absorption fine structure spectroscopy of homoleptic thiolato complexes with Zn(II) and Cd(II).

    PubMed

    Matsunaga, Yuki; Fujisawa, Kiyoshi; Ibi, Naoko; Fujita, Mitsuharu; Ohashi, Tetuya; Amir, Nagina; Miyashita, Yoshitaro; Aika, Ken-Ichi; Izumi, Yasuo; Okamoto, Ken-Ichi

    2006-02-01

    The sulfur K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy is applied to homoleptic thiolato complexes with Zn(II) and Cd(II), (Et(4)N)[Zn(SAd)(3)] (1), (Et(4)N)(2)[{Zn(ScHex)(2)}(2)(mu-ScHex)(2)] (2), (Et(4)N)(2)[{Cd(ScHex)(2)}(2)(mu-ScHex)(2)] (3), (Et(4)N)(2)[{Cd(ScHex)}(4)(mu-ScHex)(6)] (4), [Zn(mu-SAd)(2)](n) (5), and [Cd(mu-SAd)(2)](n) (6) (HSAd=1-adamantanethiol, HScHex=cyclohexanethiol). The EXAFS results are consistent with the X-ray crystal data of 1-4. The structures of 5 and 6, which have not been determined by X-ray crystallography, are proposed to be polynuclear structures on the basis of the sulfur K-edge EXAFS, far-IR spectra, and elemental analysis. Clear evidences of the S...S interactions (between bridging atoms or neighboring sulfur atoms) and the S...C(far) interactions (in which C(far) atom is next to carbon atom directly bonded to sulfur atom) were observed in the EXAFS data for all complexes and thus lead to the reliable determination of the structures of 5 and 6 in combination with conventional zinc K-edge EXAFS analysis for 5. This new methodology, sulfur K-edge EXAFS, could be applied for the structural determination of in vivo metalloproteins as well as inorganic compounds.

  13. 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.

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

    PubMed

    Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

    2015-11-01

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

  15. Silicon K-edge XANES spectra of silicate minerals

    NASA Astrophysics Data System (ADS)

    Li, Dien; Bancroft, G. M.; Fleet, M. E.; Feng, X. H.

    1995-03-01

    Silicon K-edge x-ray absorption near-edge structure (XANES) spectra of a selection of silicate and aluminosilicate minerals have been measured using synchrotron radiation (SR). The spectra are qualitatively interpreted based on MO calculation of the tetrahedral SiO{4/4-}cluster. The Si K-edge generally shifts to higher energy with increased polymerization of silicates by about 1.3 eV, but with considerable overlap for silicates of different polymerization types. The substitution of Al for Si shifts the Si K-edge to lower energy. The chemical shift of Si K-edge is also sensitive to cations in more distant atom shells; for example, the Si K-edge shifts to lower energy with the substitution of Al for Mg in octahedral sites. The shifts of the Si K-edge show weak correlation with average Si-O bond distance (dSi-O), Si-O bond valence (sSi-O) and distortion of SiO4 tetrahedra, due to the crystal structure complexity of silicate minerals and multiple factors effecting the x-ray absorption processes.

  16. 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.

  17. Origin of improved scintillation efficiency in (Lu,Gd)3(Ga,Al)5O12:Ce multicomponent garnets: An X-ray absorption near edge spectroscopy study

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    In the recent successful improvement of scintillation efficiency in Lu3Al5O12:Ce driven by Ga3+ and Gd3+ admixture, the "band-gap engineering" and energy level positioning have been considered the valid strategies so far. This study revealed that this improvement was also associated with the cerium valence instability along with the changes of chemical composition. By utilizing X-ray absorption near edge spectroscopy technique, tuning the Ce3+/Ce4+ ratio by Ga3+ admixture was evidenced, while it was kept nearly stable with the Gd3+ admixture. Ce valence instability and Ce3+/Ce4+ ratio in multicomponent garnets can be driven by the energy separation between 4f ground state of Ce3+ and Fermi level.

  18. Substitution behavior of x(Na0.5K0.5)NbO3-(1 - x)BaTiO3 ceramics for multilayer ceramic capacitors by a near edge x-ray absorption fine structure analysis

    NASA Astrophysics Data System (ADS)

    Ha, Jooyeon; Ryu, Jiseung; Lee, Heesoo

    2014-06-01

    The doping effect of (Na0.5K0.5)NbO3 (NKN) as alternatives for rare-earth elements on the electrical properties of BaTiO3 has been investigated, in terms of their substitution behavior. The dielectric constant of a specimen with x = 0.05 was about 79% higher than that of pure BaTiO3, and the temperature coefficient of capacitance was satisfied by the X7R specification. The specimen with x = 0.05 showed the lowest tetragonality among the four compositions and had a fine grain size of <2 μm. Although the addition of NKN decreased the specimen's tetragonality, the electrical properties were enhanced by the formation of defect dipoles and conduction electrons, which resulted from an acceptor and donor substitution behavior. Through O K-edge near edge x-ray absorption fine structure spectroscopy, the practical substitution behavior was defined by the change in Ti 3d orbital states. The energy separation of the Ti 3d orbitals was more apparent with the specimen of x = 0.05, which is related to the donor level from the donor substitution of Nb5+ ion for Ti-sites. Therefore, the simultaneous substitution of Na+/K+ and Nb5+ ions into BaTiO3 can improve dielectric properties, based on the charge-transfer process.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. Optically Unraveling the Edge Chirality-Dependent Band Structure and Plasmon Damping in Graphene Edges.

    PubMed

    Duan, Jiahua; Chen, Runkun; Cheng, Yuan; Yang, Tianzhong; Zhai, Feng; Dai, Qing; Chen, Jianing

    2018-05-01

    The nontrivial topological origin and pseudospinorial character of electron wavefunctions make edge states possess unusual electronic properties. Twenty years ago, the tight-binding model calculation predicted that zigzag termination of 2D sheets of carbon atoms have peculiar edge states, which show potential application in spintronics and modern information technologies. Although scanning probe microscopy is employed to capture this phenomenon, the experimental demonstration of its optical response remains challenging. Here, the propagating graphene plasmon provides an edge-selective polaritonic probe to directly detect and control the electronic edge state at ambient condition. Compared with armchair, the edge-band structure in the bandgap gives rise to additional optical absorption and strongly absorbed rim at zigzag edge. Furthermore, the optical conductivity is reconstructed and the anisotropic plasmon damping in graphene systems is revealed. The reported approach paves the way for detecting edge-specific phenomena in other van der Waals materials and topological insulators. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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

  6. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  8. 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

  9. Mass attenuation coefficient of chromium and manganese compounds around absorption edge.

    PubMed

    Sharanabasappa; Kaginelli, S B; Kerur, B R; Anilkumar, S; Hanumaiah, B

    2009-01-01

    The total mass attenuation coefficient for Potassium dichromate, Potassium chromate and Manganese acetate compounds are measured at different photon energies 5.895, 6.404, 6.490, 7.058, 8.041 and 14.390 keV using Fe-55, Co-57 and 241Am source with Copper target, radioactive sources. The photon intensity is analyzed using a high resolution HPGe detector system coupled to MCA under good geometrical arrangement. The obtained values of mass attenuation coefficient values are compared with theoretical values. This study suggests that measured mass attenuation coefficient values at and near absorption edges differ from the theoretical value by about 5-28%.

  10. Emission and absorption x-ray edges of Li

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

    Callcott, T A; Arakawa, E T; Ederer, D L

    1977-01-01

    Measurements of the K X-ray absorption and emission edges of Li are reported. They were made with the same spectrometer at the NBS storage ring and serve to establish a 0.1 eV separation between the edges with no possibility of instrument calibration error. These results are compared with recent theories of Almbladh and Mahan describing the effects of incomplete phonon relaxation about the core hole. It is concluded that these theories give a satisfactory explanation of the data.

  11. 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

  12. 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

  13. 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

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

    PubMed Central

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

    2014-01-01

    The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called “molecular movie” within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes. PMID:24740172

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

    DOE PAGES

    Gaudin, J.; Fourment, C.; Cho, B. I.; ...

    2014-04-17

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

  16. Infrared study of the absorption edge of {beta}-InN films grown on GaN/MgO structures

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

    Perez-Caro, M.; Rodriguez, A. G.; Vidal, M. A.

    2010-07-15

    Infrared optical studies were carried out in a group of cubic InN samples grown by gas source molecular beam epitaxy on MgO (001) substrates. Room temperature (RT) reflectance and low-temperature (LT) transmittance measurements were performed by using fast Fourier transform infrared spectrometry. Reflectance fittings allowed to establish that {beta}-InN films have large free-carrier concentrations present (>10{sup 19} cm{sup -3}), a result that is corroborated by Hall effect measurements. Each sample explored exhibited a different optical absorption edge. The Varshni parameters that describe adequately the optical absorption edge responses with temperature are obtained for the set of samples studied. The observedmore » temperatures changes, from LT to RT, are the lowest reported for III-V semiconductor binary compounds. The temperature coefficient of the conduction band depends on the strength of the electron-phonon interaction (e-ph-i), as well as on the thermal expansion. It has been predicted that cubic InN has one of the smallest e-ph-i of all III-V compounds, which is corroborated by these results. The variation in values of absorption edges is clearly consistent with the Burstein-Moss and band renormalization effects, produced by high free electron concentrations. It is shown that the conduction band in {beta}-InN, analogous to wurtzite InN, follows a nonparabolic behavior.« less

  17. Infrared study of the absorption edge of β-InN films grown on GaN/MgO structures

    NASA Astrophysics Data System (ADS)

    Pérez-Caro, M.; Rodríguez, A. G.; Vidal, M. A.; Navarro-Contreras, H.

    2010-07-01

    Infrared optical studies were carried out in a group of cubic InN samples grown by gas source molecular beam epitaxy on MgO (001) substrates. Room temperature (RT) reflectance and low-temperature (LT) transmittance measurements were performed by using fast Fourier transform infrared spectrometry. Reflectance fittings allowed to establish that β-InN films have large free-carrier concentrations present (>1019 cm-3), a result that is corroborated by Hall effect measurements. Each sample explored exhibited a different optical absorption edge. The Varshni parameters that describe adequately the optical absorption edge responses with temperature are obtained for the set of samples studied. The observed temperatures changes, from LT to RT, are the lowest reported for III-V semiconductor binary compounds. The temperature coefficient of the conduction band depends on the strength of the electron-phonon interaction (e-ph-i), as well as on the thermal expansion. It has been predicted that cubic InN has one of the smallest e-ph-i of all III-V compounds, which is corroborated by these results. The variation in values of absorption edges is clearly consistent with the Burstein-Moss and band renormalization effects, produced by high free electron concentrations. It is shown that the conduction band in β-InN, analogous to wurtzite InN, follows a nonparabolic behavior.

  18. Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite.

    PubMed

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

    2016-08-01

    Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

  19. Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

  20. 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.

  1. Absorption edge parameters of the LIII edge for compounds of Hg, Tl, Pb and Bi using EDXRF technique

    NASA Astrophysics Data System (ADS)

    Singh, Gurinderjeet; Singh, Amrit; Gupta, Manoj Kumar; Dhaliwal, A. S.; Kahlon, K. S.

    2018-03-01

    The measurement of Absorption edge parameters of the LIII edge of pure elements Hg, Tl, Pb and Bi along with their compounds HgCl2, HgO, HgF2, TlCl, Tl2O3, PbCl2, PbF2, Pb3O4, BiF3, BiCl3 and Bi2O3 has been done using EDXRF technique. In the present measurements 241Am (59.54 keV) radioactive source of activity 100 mCi along with CANBERRA make cryo-cooled Si (Li) detector is used. The measured results are compared with theoretically calculated values from FFAST version 2.1 (Chantler et al., 2005) and shows good agreement with each other within experimental uncertainties within 3.5%. It is observed that the values of absorption edge parameters of the LIII edge depends slightly on the chemical environment and shows almost constant behaviour with effective atomic number (Zeff)

  2. Mechanism of Pressure-Induced Phase Transitions, Amorphization, and Absorption-Edge Shift in Photovoltaic Methylammonium Lead Iodide.

    PubMed

    Szafrański, Marek; Katrusiak, Andrzej

    2016-09-01

    Our single-crystal X-ray diffraction study of methylammonium lead triiodide, MAPbI3, provides the first comprehensive structural information on the tetragonal phase II in the pressure range to 0.35 GPa, on the cubic phase IV stable between 0.35 and 2.5 GPa, and on the isostructural cubic phase V observed above 2.5 GPa, which undergoes a gradual amorphization. The optical absorption study confirms that up to 0.35 GPa, the absorption edge of MAPbI3 is red-shifted, allowing an extension of spectral absorption. The transitions to phases IV and V are associated with the abrupt blue shifts of the absorption edge. The strong increase of the energy gap in phase V result in a spectacular color change of the crystal from black to red around 3.5 GPa. The optical changes have been correlated with the pressure-induced strain of the MAPbI3 inorganic framework and its frustration, triggered by methylammonium cations trapped at random orientations in the squeezed voids.

  3. Effects of acoustic- and optical-phonon sidebands on the fundamental optical-absorption edge in crystals and disordered semiconductors

    NASA Astrophysics Data System (ADS)

    Grein, C. H.; John, Sajeev

    1990-04-01

    We present the results of a parameter-free first-principles theory for the fine structure of the Urbach optical-absorption edge in crystalline and disordered semiconductors. The dominant features are recaptured by means of a simple physical argument based on the most probable potential-well analogy. At finite temperatures, the overall linear exponential Urbach behavior of the subgap optical-absorption coefficient is a consequence of multiple LA-phonon emission and absorption sidebands that accompany the electronic transition. The fine structure of subgap absorption spectra observed in some materials is accounted for by multiple TO-, LO-, and TA-phonon absorption and emission sidebands. Good agreement is found with experimental data on crystalline silicon. The effects of nonadiabaticity in the electron-phonon interaction are calculated.

  4. 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.

  5. Effects of Edge Directions on the Structural Controllability of Complex Networks.

    PubMed

    Xiao, Yandong; Lao, Songyang; Hou, Lvlin; Small, Michael; Bai, Liang

    2015-01-01

    Recent advances indicate that assigning or reversing edge direction can significantly improve the structural controllability of complex networks. For directed networks, approaching the optimal structural controllability can be achieved by detecting and reversing certain "inappropriate" edge directions. However, the existence of multiple sets of "inappropriate" edge directions suggests that different edges have different effects on optimal controllability-that is, different combinations of edges can be reversed to achieve the same structural controllability. Therefore, we classify edges into three categories based on their direction: critical, redundant and intermittent. We then investigate the effects of changing these edge directions on network controllability, and demonstrate that the existence of more critical edge directions implies not only a lower cost of modifying inappropriate edges but also better controllability. Motivated by this finding, we present a simple edge orientation method aimed at producing more critical edge directions-utilizing only local information-which achieves near optimal controllability. Furthermore, we explore the effects of edge direction on the controllability of several real networks.

  6. Strength evaluation of butt joint by stress intensity factor of small edge crack near interface edge

    NASA Astrophysics Data System (ADS)

    Sato, T.; Oda, K.; Tsutsumi, N.

    2018-06-01

    Failure of the bonded dissimilar materials generally initiates near the interface, or just from the interface edge due to the stress singularity at the interface edge. In this study, the stress intensity factor of an edge crack close to the interface between the dissimilar materials is analyzed. The small edge crack is strongly dominated by the singular stress field near the interface edge. The analysis of stress intensity factor of small edge crack near the interface in bi-material and butt joint plates is carried out by changing the length and the location of the crack and the region dominated by the interface edge is examined. It is found that the dimensionless stress intensity factor of small crack, normalized by the singular stress at the crack tip point in the bonded plate without the crack, is equal to 1.12, independent of the material combination and adhesive layer thickness, when the relative crack length with respect to the crack location is less than 0.01. The adhesive strength of the bonded plate with various adhesive layer thicknesses can be expressed as the constant critical stress intensity factor of the small edge crack.

  7. First principles pseudopotential calculation of electron energy loss near edge structures of lattice imperfections.

    PubMed

    Mizoguchi, Teruyasu; Matsunaga, Katsuyuki; Tochigi, Eita; Ikuhara, Yuichi

    2012-01-01

    Theoretical calculations of electron energy loss near edge structures (ELNES) of lattice imperfections, particularly a Ni(111)/ZrO₂(111) heterointerface and an Al₂O₃ stacking fault on the {1100} plane, are performed using a first principles pseudopotential method. The present calculation can qualitatively reproduce spectral features as well as chemical shifts in experiment by employing a special pseudopotential designed for the excited atom with a core-hole. From the calculation, spectral changes observed in O-K ELNES from a Ni/ZrO₂ interface can be attributable to interfacial oxygen-Ni interactions. In the O-K ELNES of Al₂O₃ stacking faults, theoretical calculation suggests that the spectral feature reflects coordination environment and chemical bonding. Powerful combinations of ELNES with a pseudopotential method used to investigate the atomic and electronic structures of lattice imperfections are demonstrated. Copyright © 2011 Elsevier Ltd. All rights reserved.

  8. 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.

  9. Optical absorption of Mg-doped layers and InGaN quantum wells on c-plane and semipolar GaN structures

    NASA Astrophysics Data System (ADS)

    Sizov, Dmitry; Bhat, Rajaram; Zah, Chung-en

    2013-05-01

    We studied optical absorption of Mg-doped AlInGaN layers using excitation-position dependent and polarization resolved photoluminescence from the slab-waveguide edge of a laser structure. The major absorption in the Mg-doped layers was found only when p-doping is activated. It increases with the removal of residual hydrogen, which in case of Mg doping is a p-type passivation impurity, and reversibly disappears after passivation by hydrogen. This absorption is weakly wavelength and temperature dependent, and isotropic. This can be attributed to acceptor-bound hole absorption, because those holes concentration is nearly equal to that of activated acceptors and weakly temperature dependent (unlike the free hole concentration, which is much lower and is an exponential function of temperature due to high ionization energy). The cross section of photon absorption on such activated acceptor was quantified to be in the order of 10-17 cm-2. The absorption cross section of free electrons was found to be at least one order of magnitude lower and below detection limit. The same technique was used to experimentally quantify band structure polarization components along basis directions for green InGaN quantum wells (QWs) grown on c- and semipolar planes. The A1 and B1 valence subbands of c-plane QW were found to comprise mostly |X⟩ and |Y⟩ states. There was rather minor amount of |Z⟩ states with average square fraction of only 0.02. In (20-21) plane, due to small band anticrossing near gamma-point, we observed highly polarized absorption edges of A1- and B1-subbands consisting mainly of |Y⟩ and |X⟩ states, respectively, and found their energy splitting to be ˜40 meV. For (11-22) plane with smaller band splitting and polarization, we observed polarization switching with indium (In) concentration greater than 30% in the QW (or photon energy less than 2.3 eV). We confirmed our study of valence band structures by optical gain measurements.

  10. 4d Electronic structure analysis of ruthenium in the perovskite oxides by Ru K- and L-edge XAS.

    PubMed

    Kim, J Y; Hwang, S H; Kim, S J; Demazeau, G; Choy, J H; Shimada, H

    2001-03-01

    The 4d electronic structure of ruthenium in the perovskite oxides, La2MRuIVO6 (M = Zn, Mg, and Li) and Ba2YRuVO6, has been investigated by the Ru K-and L-edge XANES and EXAFS analyses. Such X-ray absorption spectroscopic results clarify that the RuIV (d4) and RuV (d3) ions are stabilized in nearly regular Oh site. Comparing the Ru L-edge XANES spectra of perovskites containing isovalent ruthenium, it has been found that the t2g state is mainly influenced by A site cation, whereas the eg is mainly affected by neighboring B site cation. The experimental EXAFS spectra in the range of R < or = approximately 4.5 A are well reproduced by ab-initio calculation based on crystallographic data, which supports the long-range structure presented by Rietveld refinement.

  11. 2D Radiative Processes Near Cloud Edges

    NASA Technical Reports Server (NTRS)

    Varnai, T.

    2012-01-01

    Because of the importance and complexity of dynamical, microphysical, and radiative processes taking place near cloud edges, the transition zone between clouds and cloud free air has been the subject of intense research both in the ASR program and in the wider community. One challenge in this research is that the one-dimensional (1D) radiative models widely used in both remote sensing and dynamical simulations become less accurate near cloud edges: The large horizontal gradients in particle concentrations imply that accurate radiative calculations need to consider multi-dimensional radiative interactions among areas that have widely different optical properties. This study examines the way the importance of multidimensional shortwave radiative interactions changes as we approach cloud edges. For this, the study relies on radiative simulations performed for a multiyear dataset of clouds observed over the NSA, SGP, and TWP sites. This dataset is based on Microbase cloud profiles as well as wind measurements and ARM cloud classification products. The study analyzes the way the difference between 1D and 2D simulation results increases near cloud edges. It considers both monochromatic radiances and broadband radiative heating, and it also examines the influence of factors such as cloud type and height, and solar elevation. The results provide insights into the workings of radiative processes and may help better interpret radiance measurements and better estimate the radiative impacts of this critical region.

  12. Intrinsic defect oriented visible region absorption in zinc oxide films

    NASA Astrophysics Data System (ADS)

    Rakhesh, V.; Shankar, Balakrishnan

    2018-05-01

    Zinc Oxide films were deposited on the glass substrate using vacuum arc sputtering technology. Films were prepared in oxygen ambience for 10mA and 15 mA deposition current separately. The UV-Visible spectroscopy of the samples showed that both samples possess sharp absorption near 3.5eV which is the characteristic band gap absorption energy of ZnO films. The absorption coefficient were calculated for the samples and the (αℎϑ)2 vs energy plot is drawn. The plot suggested that in addition to the sharp band edge absorption, the sample prepared at 10mA deposition current showed sharp absorption edge near 1.51eV and that at 15 mA showed absorption edge near 1.47eV. This refers to the presence of an intrinsic defect level which is likely to be deep in the band gap.

  13. Abnormal blueshift of the absorption edge in graphene nanodots

    NASA Astrophysics Data System (ADS)

    Sheng, Weidong

    2018-06-01

    In a conventional semiconductor, when the dielectric screening effect is suppressed, the exciton binding energy increases and the corresponding excitonic transition would exhibit a redshift in the spectrum. In this work, I study the optical properties of hexagonal graphene nanodots by using a configuration interaction approach and reveal that the edge of the absorption spectrum shows an abnormal blueshift as the environmental dielectric constant ɛr decreases. The two dominant many-body effects in the nanodot: the quasiparticle and excitonic effects are both found to scale almost linearly with ɛr-1. The former is shown to have a larger proportionality constant and thus accounts for the blueshift of the absorption edge. In contrast to the long-range Coulomb interaction, the on-site Coulomb energy is found to have a negative impact on the bright excitonic states. In the presence of a strong dielectric screening effect, a strong short-range Coulomb interaction is revealed to be responsible for the disintegration of the bright exciton.

  14. Effects of Edge Directions on the Structural Controllability of Complex Networks

    PubMed Central

    Xiao, Yandong; Lao, Songyang; Hou, Lvlin; Small, Michael; Bai, Liang

    2015-01-01

    Recent advances indicate that assigning or reversing edge direction can significantly improve the structural controllability of complex networks. For directed networks, approaching the optimal structural controllability can be achieved by detecting and reversing certain “inappropriate” edge directions. However, the existence of multiple sets of “inappropriate” edge directions suggests that different edges have different effects on optimal controllability—that is, different combinations of edges can be reversed to achieve the same structural controllability. Therefore, we classify edges into three categories based on their direction: critical, redundant and intermittent. We then investigate the effects of changing these edge directions on network controllability, and demonstrate that the existence of more critical edge directions implies not only a lower cost of modifying inappropriate edges but also better controllability. Motivated by this finding, we present a simple edge orientation method aimed at producing more critical edge directions—utilizing only local information—which achieves near optimal controllability. Furthermore, we explore the effects of edge direction on the controllability of several real networks. PMID:26281042

  15. Understanding the shrinkage of optical absorption edges of nanostructured Cd-Zn sulphide films for photothermal applications

    NASA Astrophysics Data System (ADS)

    Hossain, Md. Sohrab; Kabir, Humayun; Rahman, M. Mahbubur; Hasan, Kamrul; Bashar, Muhammad Shahriar; Rahman, Mashudur; Gafur, Md. Abdul; Islam, Shariful; Amri, Amun; Jiang, Zhong-Tao; Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.

    2017-01-01

    In this article Cd-Zn sulphide thin films deposited onto soda lime glass substrates via chemical bath deposition (CBD) technique were investigated for photovoltaic applications. The synthesized films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet visible (UV-vis) spectroscopic methodologies. A higher degree of crystallinity of the films was attained with the increase of film thicknesses. SEM micrographs exhibited a partial crystalline structure with a particulate appearance surrounded by the amorphous grain boundaries. The optical absorbance and absorption coefficient of the films were also enhanced significantly with the increase in film thicknesses. Optical band-gap analysis indicated a monotonic decrease in direct and indirect band-gaps with the increase of thicknesses of the films. The presence of direct and indirect transitional energies due to the exponential falling edges of the absorption curves may either be due to the lack of long-range order or to the existence of defects in the films. The declination of the optical absorption edges was also confirmed via Urbach energy and steepness parameters studies.

  16. X-ray absorption spectroscopy investigations on oxidized Ni/Au contacts to p-GaN.

    PubMed

    Jan, J C; Asokan, K; Chiou, J W; Pong, W F; Tseng, P K; Chen, L C; Chen, F R; Lee, J F; Wu, J S; Lin, H J; Chen, C T

    2001-03-01

    X-ray absorption spectroscopy was used to investigate the electronic structure of as-deposited and oxidized Ni/Au contacts to p-GaN and to elucidate the mechanism responsible for low impedance. X-ray absorption near edge spectra of Ni K- and L3,2-edges clearly indicate formation of NiO on the sample surface after annealing. The reason for low impedance may be attributed to increase in hole concentration and existence of p-NiO layer on the surface.

  17. 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).

  18. California gull chicks raised near colony edges have elevated stress levels

    USGS Publications Warehouse

    Herring, Garth; Ackerman, Joshua T.

    2011-01-01

    Coloniality in nesting birds represents an important life history strategy for maximizing reproductive success. Birds nesting near the edge of colonies tend to have lower reproductive success than individuals nesting near colony centers, and offspring of edge-nesting parents may be impaired relative to those of central-nesting parents. We used fecal corticosterone metabolites in California gull chicks (Larus californicus) to examine whether colony size or location within the colony influenced a chick's physiological condition. We found that chicks being raised near colony edges had higher fecal corticosterone metabolite concentrations than chicks raised near colony centers, but that colony size (ranging from 150 to 11,554 nests) had no influence on fecal corticosterone levels. Fecal corticosterone metabolite concentrations also increased with chick age. Our results suggest that similarly aged California gull chicks raised near colony edges may be more physiologically stressed, as indicated by corticosterone metabolites, than chicks raised near colony centers.

  19. Multispectral selective near-perfect light absorption by graphene monolayer using aperiodic multilayer microstructures

    NASA Astrophysics Data System (ADS)

    Zand, Iman; Dalir, Hamed; Chen, Ray T.; Dowling, Jonathan P.

    2018-03-01

    We investigate one-dimensional aperiodic multilayer microstructures in order to achieve near-total absorptions at preselected wavelengths in a graphene monolayer. The proposed structures are designed using a genetic optimization algorithm coupled to a transfer matrix code. Coupled-mode-theory analysis, consistent with transfer matrix method results, indicates the existence of a critical coupling in the graphene monolayer for perfect absorptions. Our findings show that the near-total-absorption peaks are highly tunable and can be controlled simultaneously or independently in a wide range of wavelengths in the near-infrared and visible ranges. The proposed approach is metal-free, does not require surface texturing or patterning, and can be also applied for other two-dimensional materials.

  20. Extremely asymmetric diffraction as a method of determining magneto-optical constants for X-rays near absorption edges

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

    Andreeva, M. A., E-mail: Mandreeva1@yandex.ru; Repchenko, Yu. L., E-mail: kent160@mail.ru; Smekhova, A. G.

    2015-06-15

    The spectral dependence of the Bragg peak position under conditions of extremely asymmetric diffraction has been analyzed in the kinematical and dynamical approximations of the diffraction theory. Simulations have been performed for the L{sub 3} absorption edge of yttrium in a single-crystal YFe{sub 2} film; they have shown that the magneto-optical constants (or, equivalently, the dispersion corrections to the atomic scattering factor) for hard X-rays can be determined from this dependence. Comparison with the experimental data obtained for a Nb(4 nm)/YFe{sub 2}(40 nm〈110〉)/Fe(1.5 nm)/Nb(50 nm)/sapphire sample at the European Synchrotron Radiation Facility has been made.

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

    PubMed Central

    2015-01-01

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

  2. Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires

    NASA Astrophysics Data System (ADS)

    Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P.; Schaller, Richard D.; Gosztola, David J.; Stroscio, Michael A.; Dutta, Mitra

    2018-04-01

    We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor-liquid-solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy ({V}{{O}}) defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of {V}{{O}} defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.

  3. Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In 2 O 3 nanowires

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

    Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P.

    We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor–liquid–solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy (VO) defects as confirmed using Raman spectroscopy. A combination of highmore » resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of VO defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.« less

  4. Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires.

    PubMed

    Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P; Schaller, Richard D; Gosztola, David J; Stroscio, Michael A; Dutta, Mitra

    2018-04-27

    We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In 2 O 3 ) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In 2 O 3 nanostructure based device characteristics for potential optoelectronic applications. In 2 O 3 nanowires with cubic crystal structure (c-In 2 O 3 ) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor-liquid-solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy [Formula: see text] defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of [Formula: see text] defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  6. Electronic structure and electric polarity of edge-functionalized graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Taira, Remi; Yamanaka, Ayaka; Okada, Susumu

    2017-08-01

    On the basis of the density functional theory combined with the effective screening medium method, we studied the electronic structure of graphene nanoribbons with zigzag edges, which are terminated by functional groups. The work function of the nanoribbons is sensitive to the functional groups. The edge state inherent in the zigzag edges is robust against edge functionalization. OH termination causes the injection of electrons into the nearly free electron states situated alongside the nanoribbons, resulting in the formation of free electron channels outside the nanoribbons. We also demonstrated that the polarity of zigzag graphene nanoribbons is controllable by the asymmetrical functionalization of their edges.

  7. Nanoscale infrared absorption spectroscopy of individual nanoparticles enabled by scattering-type near-field microscopy.

    PubMed

    Stiegler, Johannes M; Abate, Yohannes; Cvitkovic, Antonija; Romanyuk, Yaroslav E; Huber, Andreas J; Leone, Stephen R; Hillenbrand, Rainer

    2011-08-23

    Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption. © 2011 American Chemical Society

  8. Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

    DOE PAGES

    Riddle, Catherine; Czerwinski, Kenneth; Kim, Eunja; ...

    2016-01-18

    We studied the speciation of pentavalent and hexavalent americium (Am) complexes in nitric acidicby X-ray absorption fine structure spectroscopy (XAFS), UV-visible spectroscopy, and density functional theory (DFT). Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results were consistent with the presence of a mixture of AmO 2 + and AmO 2 2+ with only a small amount AmO 2 present. The resulting average bond distances we found were 1.71 Å for Am=O and 2.44 Å for Am-O. All-electron scalar relativistic calculations were also carried out using DFT to predict the equilibrium geometries and properties ofmore » the AmO 2 + and AmO 2 2+ aquo complexes. Calculated bond distances for the Am(VI) complex are in reasonable agreement with EXAFS data and the computed energy gaps between frontier molecular orbitals suggest a slightly higher kinetic stability and chemical hardness of Am(VI) compared to Am(V).« less

  9. Collision mechanics and the structure of planetary ring edges

    NASA Technical Reports Server (NTRS)

    Spaute, Dominique; Greenberg, Richard

    1987-01-01

    The present numerical simulation of collisional evolution, in the case of a hypothetical ring whose parameters are modeled after those of Saturn's rings, gives attention to changes in radial structure near the ring edges and notes that when random motion is in equilibrium, the rings tend to spread in order to conserve angular momentum while energy is dissipated in collisions. As long as random motion is damped, ring edges may contract rather than spread, producing a concentration of material at the ring edges. For isotropic scattering, damping dominates for a coefficient of restitution of velocity value of up to 0.83.

  10. Edge-functionalization of armchair graphene nanoribbons with pentagonal-hexagonal edge structures.

    PubMed

    Ryou, Junga; Park, Jinwoo; Kim, Gunn; Hong, Suklyun

    2017-06-21

    Using density functional theory calculations, we have studied the edge-functionalization of armchair graphene nanoribbons (AGNRs) with pentagonal-hexagonal edge structures. While the AGNRs with pentagonal-hexagonal edge structures (labeled (5,6)-AGNRs) are metallic, the edge-functionalized (5,6)-AGNRs with substitutional atoms opens a band gap. We find that the band structures of edge-functionalized (5,6)-N-AGNRs by substitution resemble those of defect-free (N-1)-AGNR at the Γ point, whereas those at the X point show the original ones of the defect-free N-AGNR. The overall electronic structures of edge-functionalized (5,6)-AGNRs depend on the number of electrons, supplied by substitutional atoms, at the edges of functionalized (5,6)-AGNRs.

  11. Dynamical tuning between nearly perfect reflection, absorption, and transmission of light via graphene/dielectric structures

    PubMed Central

    Linder, Jacob; Halterman, Klaus

    2016-01-01

    Exerting well-defined control over the reflection (R), absorption (A), and transmission (T) of electromagnetic waves is a key objective in quantum optics. To this end, one often utilizes hybrid structures comprised of elements with different optical properties in order to achieve features such as high R or high A for incident light. A desirable goal would be the possibility to tune between all three regimes of nearly perfect reflection, absorption, and transmission within the same device, thus swapping between the cases R → 1, A → 1, and T → 1 dynamically. We here show that a dielectric interfaced with a graphene layer on each side allows for precisely this: by tuning only the Fermi level of graphene, all three regimes can be reached in the THz regime and below. Moreover, we show that the inclusion of cylindrical defects in the system offers a different type of control of the scattering of electromagnetic waves by means of the graphene layers. PMID:27917886

  12. Femtosecond time-resolved X-ray absorption spectroscopy of anatase TiO2 nanoparticles using XFEL

    PubMed Central

    Obara, Yuki; Ito, Hironori; Ito, Terumasa; Kurahashi, Naoya; Thürmer, Stephan; Tanaka, Hiroki; Katayama, Tetsuo; Togashi, Tadashi; Owada, Shigeki; Yamamoto, Yo-ichi; Karashima, Shutaro; Nishitani, Junichi; Yabashi, Makina; Suzuki, Toshinori; Misawa, Kazuhiko

    2017-01-01

    The charge-carrier dynamics of anatase TiO2 nanoparticles in an aqueous solution were studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser in combination with a synchronized ultraviolet femtosecond laser (268 nm). Using an arrival time monitor for the X-ray pulses, we obtained a temporal resolution of 170 fs. The transient X-ray absorption spectra revealed an ultrafast Ti K-edge shift and a subsequent growth of a pre-edge structure. The edge shift occurred in ca. 100 fs and is ascribed to reduction of Ti by localization of generated conduction band electrons into shallow traps of self-trapped polarons or deep traps at penta-coordinate Ti sites. Growth of the pre-edge feature and reduction of the above-edge peak intensity occur with similar time constants of 300–400 fs, which we assign to the structural distortion dynamics near the surface. PMID:28713842

  13. Structural and Dynamical Properties of 2:1 Phyllosilicates Edges and Nanoparticles

    NASA Astrophysics Data System (ADS)

    Newton, A. G.; Sposito, G.

    2012-12-01

    and dynamical properties of the phyllosilicate edge interface differ from those of the 2:1 phyllosilicate basal surface. The non-planar surface structure and abundant oxygen atoms and hydroxyl groups at the edge order the water layers such that a steep gradient in the water self-diffusion coefficient exists near the surface. Isolated phyllosilicate nanoparticles maintain the original crystal habit; disordered edge structures emerge upon stacking of the particles. These simulations validate CLAYFF as a general forcefield for 2:1 phyllosilicate edges and nanoparticles and demonstrate a powerful method for future investigations of geologic media at the mesoscale.

  14. 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.

  15. 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

  16. 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.

  17. Near Field Trailing Edge Tone Noise Computation

    NASA Technical Reports Server (NTRS)

    Loh, Ching Y.

    2002-01-01

    Blunt trailing edges in a flow often generate tone noise due to wall-jet shear layer and vortex shedding. In this paper, the space-time conservation element (CE/SE) method is employed to numerically study the near-field noise of blunt trailing edges. Two typical cases, namely, flow past a circular cylinder (aeolian noise problem) and flow past a flat plate of finite thickness are considered. The computed frequencies compare well with experimental data. For the aeolian noise problem, comparisons with the results of other numerical approaches are also presented.

  18. Implications of New Methane Absorption Coefficients on Uranus Vertical Structure Derived from Near-IR Spectra

    NASA Astrophysics Data System (ADS)

    Fry, Patrick M.; Sromovsky, L. A.

    2009-09-01

    Using new methane absorption coefficients from Karkoschka and Tomasko (2009, submitted to Icarus, "Methane Absorption Coefficients for the Jovian Planets from Laboratory, Huygens, and HST Data"), we fit Uranus near-IR spectra previously analyzed in Sromovsky et al. (2006, Icarus 182, 577-593, Fink and Larson, 1979 J- and H-band), Sromovsky and Fry (2008, Icarus 193, 252-266, 2006 NIRC2 J- and H-band, 2006 SpeX) using Irwin et al. (2006, Icarus 181, 309-319) methane absorption coefficients. Because the new absorption coefficients usually result in higher opacities at the low temperatures seen in Uranus' upper troposphere, our previously derived cloud altitudes are expected to generally rise to higher altitudes. For example, using Lindal et al. (1987, JGR 92, 14987-15001) model D temperature and methane abundance profiles, we are better able to fit the J-band 43-deg. south bright band with the new coefficients (chi-square=205, vs. 315 for Irwin), with the pressure of the upper tropospheric cloud decreasing to 1.6 bars (from 2.4 bars using Irwin coefficients). Improvements in fitting H-band spectra from the same latitude are not as readily obtained. Derived upper tropospheric cloud pressures are very similar using the two absorption datasets (1.6-1.7 bars), but the character of the fits differs. New Karkoschka and Tomasko coefficients better fit some details in the 1.5-1.58 micron region, but Irwin fits the broad absorption band wing at 1.61-1.62 microns better, and the fit chi-square values are similar (K&T: 243, Irwin: 220). Results for a higher methane concentration (Lindal et al. model F) were similar. Whether the new coefficients will simply raise derived altitudes across the planet or will result in fundamental changes in structure is as yet unclear. This work was suported by NASA planetary astronomy and planetary atmospheres programs.

  19. Electrostatic potential barrier for electron emission at graphene edges induced by the nearly free electron states

    NASA Astrophysics Data System (ADS)

    Gao, Yanlin; Okada, Susumu

    2017-05-01

    Using the density functional theory, we studied the electronic structures of zigzag graphene nanoribbons with hydroxyl, H, ketone, aldehyde, or carboxyl terminations under a lateral electric field. The critical electric field for electron emission is proportional to the work function of the functionalized edges except the hydroxylated edge, which leads to the anomalous electric field outside the edge, owing to the electrons in the nearly free electron (NFE) state in the vacuum region. The strong electric field also causes a potential barrier for the electron emission from the H-terminated edge owing to the downward shift of the NFE state.

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

    PubMed

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

    2014-10-22

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

  1. Dynamical Study of Femtosecond-Laser-Ablated Liquid-Aluminum Nanoparticles Using Spatiotemporally Resolved X-Ray-Absorption Fine-Structure Spectroscopy

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

    Oguri, Katsuya; Okano, Yasuaki; Nishikawa, Tadashi

    2007-10-19

    We study the temperature evolution of aluminum nanoparticles generated by femtosecond laser ablation with spatiotemporally resolved x-ray-absorption fine-structure spectroscopy. We successfully identify the nanoparticles based on the L-edge absorption fine structure of the ablation plume in combination with the dependence of the edge structure on the irradiation intensity and the expansion velocity of the plume. In particular, we show that the lattice temperature of the nanoparticles is estimated from the L-edge slope, and that its spatial dependence reflects the cooling of the nanoparticles during plume expansion. The results reveal that the emitted nanoparticles travel in a vacuum as a condensedmore » liquid phase with a lattice temperature of about 2500 to 4200 K in the early stage of plume expansion.« less

  2. Manganese L-edge X-ray absorption spectroscopy of manganese catalase from Lactobacillus plantarum and mixed valence manganese complexes

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

    Grush, M.M.; Chen, J.; George, S.J.

    1996-01-10

    The first Mn L-edge absorption spectra of a Mn metalloprotein are presented in this paper. Both reduced and superoxidized Mn catalase have been examined by fluorescence-detected soft X-ray absorption spectroscopy, and their Mn L-edge spectra are dramatically different. The spectrum of reduced Mn(II)Mn(II) catalase has been interpreted by ligand field atomic multiplet calculations and by comparison to model compound spectra. The analysis finds a 10 Dq value of nearly 1.1 eV, consistent with coordination by predominately nitrogen and oxygen donor ligands. For interpretation of mixed valence Mn spectra, an empirical simulation procedure based on the addition of homovalent model compoundmore » spectra has been developed and was tested on a variety of Mn complexes and superoxidized Mn catalase. This routine was also used to determine the oxidation state composition of the Mn in [Ba{sub 8}Na{sub 2}ClMn{sub 16}(OH){sub 8}(CO{sub 3}){sub 4}L{sub 8}] .53 H{sub 2}O (L=1,3-diamino-2-hydroxypropane-N,N,N`N`-tetraacetic acid). 27 refs., 6 figs.« less

  3. Degradation in carbon stocks near tropical forest edges.

    PubMed

    Chaplin-Kramer, Rebecca; Ramler, Ivan; Sharp, Richard; Haddad, Nick M; Gerber, James S; West, Paul C; Mandle, Lisa; Engstrom, Peder; Baccini, Alessandro; Sim, Sarah; Mueller, Carina; King, Henry

    2015-12-18

    Carbon stock estimates based on land cover type are critical for informing climate change assessment and landscape management, but field and theoretical evidence indicates that forest fragmentation reduces the amount of carbon stored at forest edges. Here, using remotely sensed pantropical biomass and land cover data sets, we estimate that biomass within the first 500 m of the forest edge is on average 25% lower than in forest interiors and that reductions of 10% extend to 1.5 km from the forest edge. These findings suggest that IPCC Tier 1 methods overestimate carbon stocks in tropical forests by nearly 10%. Proper accounting for degradation at forest edges will inform better landscape and forest management and policies, as well as the assessment of carbon stocks at landscape and national levels.

  4. Degradation in carbon stocks near tropical forest edges

    PubMed Central

    Chaplin-Kramer, Rebecca; Ramler, Ivan; Sharp, Richard; Haddad, Nick M.; Gerber, James S.; West, Paul C.; Mandle, Lisa; Engstrom, Peder; Baccini, Alessandro; Sim, Sarah; Mueller, Carina; King, Henry

    2015-01-01

    Carbon stock estimates based on land cover type are critical for informing climate change assessment and landscape management, but field and theoretical evidence indicates that forest fragmentation reduces the amount of carbon stored at forest edges. Here, using remotely sensed pantropical biomass and land cover data sets, we estimate that biomass within the first 500 m of the forest edge is on average 25% lower than in forest interiors and that reductions of 10% extend to 1.5 km from the forest edge. These findings suggest that IPCC Tier 1 methods overestimate carbon stocks in tropical forests by nearly 10%. Proper accounting for degradation at forest edges will inform better landscape and forest management and policies, as well as the assessment of carbon stocks at landscape and national levels. PMID:26679749

  5. 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.

  6. 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

  7. Edge physics of the quantum spin Hall insulator from a quantum dot excited by optical absorption.

    PubMed

    Vasseur, Romain; Moore, Joel E

    2014-04-11

    The gapless edge modes of the quantum spin Hall insulator form a helical liquid in which the direction of motion along the edge is determined by the spin orientation of the electrons. In order to probe the Luttinger liquid physics of these edge states and their interaction with a magnetic (Kondo) impurity, we consider a setup where the helical liquid is tunnel coupled to a semiconductor quantum dot that is excited by optical absorption, thereby inducing an effective quantum quench of the tunneling. At low energy, the absorption spectrum is dominated by a power-law singularity. The corresponding exponent is directly related to the interaction strength (Luttinger parameter) and can be computed exactly using boundary conformal field theory thanks to the unique nature of the quantum spin Hall edge.

  8. A structural study of bone changes in knee osteoarthritis by synchrotron-based X-ray fluorescence and X-ray absorption spectroscopy techniques

    NASA Astrophysics Data System (ADS)

    Sindhupakorn, Bura; Thienpratharn, Suwittaya; Kidkhunthod, Pinit

    2017-10-01

    Osteoarthritis (OA) is characterized by degeneration of articular cartilage and thickening of subchondral bone. The present study investigated the changing of biochemical components of cartilage and bone compared between normal and OA people. Using Synchrotron-based X-ray fluorescence (SR-XRF) and X-ray absorption spectroscopy (XAS) techniquesincluding X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were employed for the bone changes in kneeosteoarthritisstudies. The bone samples were collected from various osteoarthritis patients with both male and female in the ages range between 20 and 74 years old. SR-XRF results excited at 4240 eV for Ca elements show a majority three main groups, based on their XRF intensities, 20-36 years, 40-60 years and over 70 years, respectively. By employing XAS techniques, XANES features can be used to clearly explain in term of electronic transitions occurring in bone samples which are affected from osteoarthritis symptoms. Moreover, a structural change around Ca ions in bone samples is obviously obtained by EXAFS results indicating an increase of Ca-amorphous phase when the ages increase.

  9. 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

  10. Drift paths of ions composing multiple-nose spectral structures near the inner edge of the plasma sheet

    NASA Astrophysics Data System (ADS)

    Ferradas, C. P.; Zhang, J.-C.; Spence, H. E.; Kistler, L. M.; Larsen, B. A.; Reeves, G.; Skoug, R.; Funsten, H.

    2016-11-01

    We present a case study of the H+, He+, and O+ multiple-nose structures observed by the Helium, Oxygen, Proton, and Electron instrument on board Van Allen Probe A over one complete orbit on 28 September 2013. Nose structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift in the highly dynamic environment of the inner magnetosphere. We find that the multiple noses are intrinsically associated with variations in the solar wind. Backward ion drift path tracings show new details of the drift trajectories of these ions; i.e., multiple noses are formed by ions with a short drift time from the assumed source location to the inner region and whose trajectories (1) encircle the Earth different number of times or (2) encircle the Earth equal number of times but with different drift time, before reaching the observation site.

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

    PubMed

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

    2015-11-01

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

  12. Imaging at an x-ray absorption edge using free electron laser pulses for interface dynamics in high energy density systems [Resonant phase contrast imaging for interface physics

    DOE PAGES

    Beckwith, M. A.; Jiang, S.; Schropp, A.; ...

    2017-05-01

    Tuning the energy of an x-ray probe to an absorption line or edge can provide material-specific measurements that are particularly useful for interfaces. Simulated hard x-ray images above the Fe K-edge are presented to examine ion diffusion across an interface between Fe 2O 3 and SiO 2 aerogel foam materials. The simulations demonstrate the feasibility of such a technique for measurements of density scale lengths near the interface with submicron spatial resolution. A proof-of-principle experiment is designed and performed at the Linac coherent light source facility. Preliminary data show the change of the interface after shock compression and heating withmore » simultaneous fluorescence spectra for temperature determination. Here, the results provide the first demonstration of using x-ray imaging at an absorption edge as a diagnostic to detect ultrafast phenomena for interface physics in high-energy-density systems.« less

  13. 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.

  14. A search for the iron absorption edge in the tail of an X-ray burst from X1636 - 53

    NASA Astrophysics Data System (ADS)

    Day, C. S. R.; Fabian, A. C.; Ross, R. R.

    1992-08-01

    Model atmosphere calculations of the spectrum of a neutron star cooling after an X-ray burst show that the photoelectric edge of iron should be prominent. No clear evidence for such a redshifted feature in the spectrum of a burst from X1636 - 53 is found, and it is concluded that the iron abundance there must be less than 0.3 solar. Unless the iron abundance of the surface matter on the neutron star is highly time-dependent, the present result argues against the 4.1-keV absorption line seen in some bursts from X1636 - 53 by Waki et al. (1984) being due to iron. The iron edge will be a powerful diagnostic of the surface redshift of the neutron star in burst sources where the iron abundance is more nearly solar.

  15. A search for the iron absorption edge in the tail of an X-ray burst from X1636 - 53

    NASA Technical Reports Server (NTRS)

    Day, C. S. R.; Fabian, A. C.; Ross, R. R.

    1992-01-01

    Model atmosphere calculations of the spectrum of a neutron star cooling after an X-ray burst show that the photoelectric edge of iron should be prominent. No clear evidence for such a redshifted feature in the spectrum of a burst from X1636 - 53 is found, and it is concluded that the iron abundance there must be less than 0.3 solar. Unless the iron abundance of the surface matter on the neutron star is highly time-dependent, the present result argues against the 4.1-keV absorption line seen in some bursts from X1636 - 53 by Waki et al. (1984) being due to iron. The iron edge will be a powerful diagnostic of the surface redshift of the neutron star in burst sources where the iron abundance is more nearly solar.

  16. 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.

  17. Drift paths of ions composing multiple-nose spectral structures near the inner edge of the plasma sheet

    DOE PAGES

    Ferradas, C. P.; Zhang, J. -C.; Spence, H. E.; ...

    2016-11-05

    Here in this paper, we present a case study of the H +, He +, and O + multiple-nose structures observed by the Helium, Oxygen, Proton, and Electron instrument on board Van Allen Probe A over one complete orbit on 28 September 2013. Nose structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift in the highly dynamic environment of the inner magnetosphere. We find that the multiple noses are intrinsically associated with variations in the solar wind. Backward ion drift path tracings show new details of the drift trajectories of thesemore » ions; i.e., multiple noses are formed by ions with a short drift time from the assumed source location to the inner region and whose trajectories (1) encircle the Earth different number of times or (2) encircle the Earth equal number of times but with different drift time, before reaching the observation site.« less

  18. Drift paths of ions composing multiple-nose spectral structures near the inner edge of the plasma sheet

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

    Ferradas, C. P.; Zhang, J. -C.; Spence, H. E.

    Here in this paper, we present a case study of the H +, He +, and O + multiple-nose structures observed by the Helium, Oxygen, Proton, and Electron instrument on board Van Allen Probe A over one complete orbit on 28 September 2013. Nose structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift in the highly dynamic environment of the inner magnetosphere. We find that the multiple noses are intrinsically associated with variations in the solar wind. Backward ion drift path tracings show new details of the drift trajectories of thesemore » ions; i.e., multiple noses are formed by ions with a short drift time from the assumed source location to the inner region and whose trajectories (1) encircle the Earth different number of times or (2) encircle the Earth equal number of times but with different drift time, before reaching the observation site.« less

  19. Specimen charging in X-ray absorption spectroscopy: correction of total electron yield data from stabilized zirconia in the energy range 250-915 eV.

    PubMed

    Vlachos, Dimitrios; Craven, Alan J; McComb, David W

    2005-03-01

    The effects of specimen charging on X-ray absorption spectroscopy using total electron yield have been investigated using powder samples of zirconia stabilized by a range of oxides. The stabilized zirconia powder was mixed with graphite to minimize the charging but significant modifications of the intensities of features in the X-ray absorption near-edge fine structure (XANES) still occurred. The time dependence of the charging was measured experimentally using a time scan, and an algorithm was developed to use this measured time dependence to correct the effects of the charging. The algorithm assumes that the system approaches the equilibrium state by an exponential decay. The corrected XANES show improved agreement with the electron energy-loss near-edge fine structure obtained from the same samples.

  20. Characterization of local atomic structure in Co/Zn based ZIFs by XAFS

    NASA Astrophysics Data System (ADS)

    Podkovyrina, Yulia; Butova, Vera; Bulanova, Elena; Budnyk, Andriy; Kremennaya, Maria; Soldatov, Alexander; Lamberti, Carlo

    2018-03-01

    The local atomic structure in bimetallic Co/Zn zeolitic imidazolate frameworks (ZIFs) was studied using X-ray Absorption Fine Structure (XAFS) spectroscopy and theoretical calculations. The experimental Co K-edge and Zn K-edge XANES (X-ray Absorption Near Edge Structure) spectra of Zn1-xCoxC8H10N4 samples (x = 0.05, 0.25, 0.75) synthesized by microwave synthesis were compared with the data for the ZIF-67 (x=1) and ZIF-8 (x=0). Theoretical XANES spectra for the bimetallic ZIFs were calculated. It was shown that in bimetallic ZIFs the Co and Zn atoms have the similar local environment.

  1. Thin structured rigid body for acoustic absorption

    NASA Astrophysics Data System (ADS)

    Starkey, T. A.; Smith, J. D.; Hibbins, A. P.; Sambles, J. R.; Rance, H. J.

    2017-01-01

    We present a thin acoustic metamaterial absorber, comprised of only rigid metal and air, that gives rise to near unity absorption of airborne sound on resonance. This simple, easily fabricated, robust structure comprising a perforated metal plate separated from a rigid wall by a deeply subwavelength channel of air is an ideal candidate for a sound absorbing panel. The strong absorption in the system is attributed to the thermo-viscous losses arising from a sound wave guided between the plate and the wall, defining the subwavelength channel.

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

    PubMed

    Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

    2014-08-14

    The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

  3. Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic-Inorganic Lead Halide Perovskites.

    PubMed

    Vorwerk, Christian; Hartmann, Claudia; Cocchi, Caterina; Sadoughi, Golnaz; Habisreutinger, Severin N; Félix, Roberto; Wilks, Regan G; Snaith, Henry J; Bär, Marcus; Draxl, Claudia

    2018-04-19

    In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L 3 and the Pb M 5 edges of the methylammonium lead iodide (MAPbI 3 ) hybrid inorganic-organic perovskite and its binary phase PbI 2 . The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI 3 are essentially given by its inorganic component, with negligible influence from the organic groups. The theoretical analysis complementing experimental observations provides the conceptual insights required for a full characterization of this complex material.

  4. Tunable dual-band nearly perfect absorption based on a compound metallic grating

    NASA Astrophysics Data System (ADS)

    Gao, Hua; Zheng, Zhi-Yuan; Feng, Juan

    2017-02-01

    Traditional metallic gratings and novel metamaterials are two basic kinds of candidates for perfect absorption. Comparatively speaking, metallic grating is the preferred choice for the same absorption effect because it is structurally simpler and more convenient to fabricate. However, to date, most of the perfect absorption effects achieved based on metamaterials are also available using an metallic grating except the tunable dual(multi)-band perfect absorption. To fill this gap, in this paper, by adding subgrooves on the rear surface as well as inside the grating slits to a free-standing metallic grating, tunable dual-band perfect absorption is also obtained for the first time. The grooves inside the slits is to tune the frequency of the Cavity Mode(CM) resonance which enhances the transmission and suppresses the reflectance simultaneously. The grooves on the rear surface give rise to the phase resonance which not only suppresses the transmission but also reinforces the reflectance depression effect. Thus, when the phase resonance and the frequency tunable CM resonance occur together, transmission and reflection can be suppressed simultaneously, dual-band nearly perfect absorption with tunable frequencies is obtained. To our knowledge, this perfect absorption phenomenon is achieved for the first time in a designed metallic grating structure.

  5. 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

  6. Nonlinear refraction at the absorption edge in InAs.

    PubMed

    Poole, C D; Garmire, E

    1984-08-01

    The results of measurements of nonlinear refraction at the absorption edge in InAs between 68 and 90 K taken with an HF laser are compared with those of a band-gap resonant model in which the contribution of the light-hole band is included and found to account for more than 40% of the observed nonlinear refraction. A generalized expression for the nonlinear index is derived by using the complete Fermi-Dirac distribution function. Good agreement between theory and experiment is obtained, with no free parameters.

  7. Optimal perturbations of a finite-width mixing layer near the trailing edge

    NASA Astrophysics Data System (ADS)

    Gumbart, James C.; Rabchuk, James

    2002-03-01

    The trailing edge of a surface separating two fluid flows can act as an efficient receptor for acoustic or other disturbances. The incident wave energy is converted by a linear mechanism into incipient flow instabilities which lead further downstream to the transition to turbulence. Understanding this process is essential for analyzing feedback loops and other resonances which can cause unwanted structural vibrations in the surface material or directed acoustic emissions from the mixing region. Previously, the modes of instability in a finite-width mixing layer near the trailing edge were studied as a function of frequency by assuming that vorticity was continually being introduced into the flow at the trailing edge by the forcing field. It was found that the initial amplitude of the growing instability mode was a sharply decreasing function of forcing frequency, and that the initial amplitude was a minimum for the frequency at which the rate of instability growth was a maximum^1. This result has led to a study of the adjoint equation for the perturbation stream function, whose eigensolutions are known to be associated with the optimal perturbation field for the frequency of forcing leading to the greatest instability growth downstream. We have obtained these solutions for a piecewise linear velocity profile near the trailing edge using group-theoretic techniques and have shown that they are indeed optimal. We have also analyzed the nature of the physical forcing field that might produce these optimal perturbations. ^1 Rabchuk, J.A., July 2000, Physics of Fluids.

  8. A nearly on-axis spectroscopic system for simultaneously measuring UV-visible absorption and X-ray diffraction in the SPring-8 structural genomics beamline.

    PubMed

    Sakaguchi, Miyuki; Kimura, Tetsunari; Nishida, Takuma; Tosha, Takehiko; Sugimoto, Hiroshi; Yamaguchi, Yoshihiro; Yanagisawa, Sachiko; Ueno, Go; Murakami, Hironori; Ago, Hideo; Yamamoto, Masaki; Ogura, Takashi; Shiro, Yoshitsugu; Kubo, Minoru

    2016-01-01

    UV-visible absorption spectroscopy is useful for probing the electronic and structural changes of protein active sites, and thus the on-line combination of X-ray diffraction and spectroscopic analysis is increasingly being applied. Herein, a novel absorption spectrometer was developed at SPring-8 BL26B2 with a nearly on-axis geometry between the X-ray and optical axes. A small prism mirror was placed near the X-ray beamstop to pass the light only 2° off the X-ray beam, enabling spectroscopic analysis of the X-ray-exposed volume of a crystal during X-ray diffraction data collection. The spectrometer was applied to NO reductase, a heme enzyme that catalyzes NO reduction to N2O. Radiation damage to the heme was monitored in real time during X-ray irradiation by evaluating the absorption spectral changes. Moreover, NO binding to the heme was probed via caged NO photolysis with UV light, demonstrating the extended capability of the spectrometer for intermediate analysis.

  9. 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

  10. Development of XAFS Into a Structure Determination Technique

    NASA Astrophysics Data System (ADS)

    Stern, E. A.

    After the detection of diffraction of x-rays by M. Laue in 1912, the technique was soon applied to structure determination by Bragg within a year. On the other hand, although the edge steps in X-Ray absorption were discovered even earlier by Barkla and both the near edge (XANES) and extended X-Ray fine structure (EXAFS) past the edge were detected by 1929, it still took over 40 years to realize the structure information contained in this X-Ray absorption fine structure (XAFS). To understand this delay a brief historical review of the development of the scientific ideas that transformed XAFS into the premiere technique for local structure determination is given. The development includes both advances in theoretical understanding and calculational capabilities, and in experimental facilities, especially synchrotron radiation sources. The present state of the XAFS technique and its capabilities are summarized.

  11. Brown carbon absorption in the red and near-infrared spectral region

    NASA Astrophysics Data System (ADS)

    Hoffer, András; Tóth, Ádám; Pósfai, Mihály; Eddy Chung, Chul; Gelencsér, András

    2017-06-01

    Black carbon (BC) aerosols have often been assumed to be the only light-absorbing carbonaceous particles in the red and near-infrared spectral regions of solar radiation in the atmosphere. Here we report that tar balls (a specific type of organic aerosol particles from biomass burning) do absorb red and near-infrared radiation significantly. Tar balls were produced in a laboratory experiment, and their chemical and optical properties were measured. The absorption of these particles in the range between 470 and 950 nm was measured with an aethalometer, which is widely used to measure atmospheric aerosol absorption. We find that the absorption coefficient of tar balls at 880 nm is more than 10 % of that at 470 nm. The considerable absorption of red and infrared light by tar balls also follows from their relatively low absorption Ångström coefficient (and significant mass absorption coefficient) in the spectral range between 470 and 950 nm. Our results support the previous finding that tar balls may play an important role in global warming. Due to the non-negligible absorption of tar balls in the near-infrared region, the absorption measured in the field at near-infrared wavelengths cannot solely be due to soot particles.

  12. Near-Unity Absorption in van der Waals Semiconductors for Ultrathin Optoelectronics.

    PubMed

    Jariwala, Deep; Davoyan, Artur R; Tagliabue, Giulia; Sherrott, Michelle C; Wong, Joeson; Atwater, Harry A

    2016-09-14

    We demonstrate near-unity, broadband absorbing optoelectronic devices using sub-15 nm thick transition metal dichalcogenides (TMDCs) of molybdenum and tungsten as van der Waals semiconductor active layers. Specifically, we report that near-unity light absorption is possible in extremely thin (<15 nm) van der Waals semiconductor structures by coupling to strongly damped optical modes of semiconductor/metal heterostructures. We further fabricate Schottky junction devices using these highly absorbing heterostructures and characterize their optoelectronic performance. Our work addresses one of the key criteria to enable TMDCs as potential candidates to achieve high optoelectronic efficiency.

  13. Near band edge photoluminescence of ZnO nanowires: Optimization via surface engineering

    NASA Astrophysics Data System (ADS)

    Yan, Danhua; Zhang, Wenrui; Cen, Jiajie; Stavitski, Eli; Sadowski, Jerzy T.; Vescovo, Elio; Walter, Andrew; Attenkofer, Klaus; Stacchiola, Darío J.; Liu, Mingzhao

    2017-12-01

    Zinc oxide (ZnO) nanowire arrays have potential applications for various devices such as ultra-violet light emitting diodes and lasers, where photoluminescence of intense near band edge emission without defect emissions is usually desired. Here, we demonstrate, counter-intuitively, that the near band edge emission may become dominant by introducing certain surface defects to ZnO nanowires via surface engineering. Specifically, near band edge emission (NBE) is effectively enhanced after a low pressure O2 plasma treatment that sputters off surface oxygen species to produce a reduced and oxygen vacancy-rich surface. The effect is attributed to the lowered surface valence band maximum of the reduced ZnO surface that creates an accumulative band bending, which screens the photo-generated minority carriers (holes) from reaching or being trapped by the surface defects.

  14. 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.

  15. Near-infrared absorption spectroscopy of interstellar hydrocarbon grains

    NASA Astrophysics Data System (ADS)

    Pendleton, Y. J.; Sandford, S. A.; Allamandola, L. J.; Tielens, A. G. G. M.; Sellgren, K.

    1994-12-01

    We present new 3600 - 2700/cm (2.8 - 3.7 micrometer) spectra of objects whose extinction is dominated by dust in the diffuse interstellar medium. The observations presented here augment an ongoing study of the organic component of the diffuse interstellar medium. These spectra contain a broad feature centered near 3300/cm (3.0 micrometers) and/or a feature with a more complex profile near 2950/cm (3.4 micrometers), the latter of which is attributed to saturated aliphatic hydrocarbons in interstellar grains and is the primary interest of this paper. As in our earlier work, the similarity of the absorption bands near 2950/cm (3.4 micrometers) along different lines of sight and the correlation of these features with interstellar extinction reveal that the carrier of this band lies in the dust in the diffuse interstellar medium (DISM). At least 2.5% of the cosmic carbon in the local interstellar medium and 4% toward the Galactic center is tied up in the carrier of the 2950/cm (3.4 micrometer) band. The spectral structure of the diffuse dust hydrocarbon C-H stretch absorption features is reasonably similar to UV photolyzed laboratory ice residues and is quite similar to the carbonaceous component of the Murchison meteorite. The similarity between the DISM and the meteoritic spectrum suggests that some of the interstellar material originally incorporated into the solar nebula may have survived relatively untouched in primitive solar system bodies. Comparisons of the DISM spectrum to hydrogenated amorphous carbon and quenched carbonaceous composite are also presented. The AV/tau ratio for the 2950/cm (3.4 micrometer) feature is lower toward the Galactic center than toward sources in the local solar neighborhood (approximately 150 for the Galactic center sources vs. approximately 250 for the local ISM sources). A similar trend has been observed previously for silicates in the diffuse medium by Roche & Aitken, suggesting that (1) the silicate and carbonaceous materials in

  16. Near-infrared absorption spectroscopy of interstellar hydrocarbon grains

    NASA Technical Reports Server (NTRS)

    Pendleton, Y. J.; Sandford, S. A.; Allamandola, L. J.; Tielens, A. G. G. M.; Sellgren, K.

    1994-01-01

    We present new 3600 - 2700/cm (2.8 - 3.7 micrometer) spectra of objects whose extinction is dominated by dust in the diffuse interstellar medium. The observations presented here augment an ongoing study of the organic component of the diffuse interstellar medium. These spectra contain a broad feature centered near 3300/cm (3.0 micrometers) and/or a feature with a more complex profile near 2950/cm (3.4 micrometers), the latter of which is attributed to saturated aliphatic hydrocarbons in interstellar grains and is the primary interest of this paper. As in our earlier work, the similarity of the absorption bands near 2950/cm (3.4 micrometers) along different lines of sight and the correlation of these features with interstellar extinction reveal that the carrier of this band lies in the dust in the diffuse interstellar medium (DISM). At least 2.5% of the cosmic carbon in the local interstellar medium and 4% toward the Galactic center is tied up in the carrier of the 2950/cm (3.4 micrometer) band. The spectral structure of the diffuse dust hydrocarbon C-H stretch absorption features is reasonably similar to UV photolyzed laboratory ice residues and is quite similar to the carbonaceous component of the Murchison meteorite. The similarity between the DISM and the meteoritic spectrum suggests that some of the interstellar material originally incorporated into the solar nebula may have survived relatively untouched in primitive solar system bodies. Comparisons of the DISM spectrum to hydrogenated amorphous carbon and quenched carbonaceous composite are also presented. The A(sub V)/tau ratio for the 2950/cm (3.4 micrometer) feature is lower toward the Galactic center than toward sources in the local solar neighborhood (approximately 150 for the Galactic center sources vs. approximately 250 for the local ISM sources). A similar trend has been observed previously for silicates in the diffuse medium by Roche & Aitken, suggesting that (1) the silicate and carbonaceous

  17. 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).

  18. Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic–Inorganic Lead Halide Perovskites

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

    Vorwerk, Christian; Hartmann, Claudia; Cocchi, Caterina

    In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L 3 and the Pb M 5 edges of the methylammonium lead iodide (MAPbI 3) hybrid inorganic-organic perovskite and its binary phase PbI 2. The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI 3 are essentially given by its inorganic component, with negligible influence from the organic groups. Furthermore, the theoretical analysis complementing experimental observationsmore » provides the conceptual insights required for a full characterization of this complex material.« less

  19. Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic–Inorganic Lead Halide Perovskites

    DOE PAGES

    Vorwerk, Christian; Hartmann, Claudia; Cocchi, Caterina; ...

    2018-03-23

    In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L 3 and the Pb M 5 edges of the methylammonium lead iodide (MAPbI 3) hybrid inorganic-organic perovskite and its binary phase PbI 2. The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI 3 are essentially given by its inorganic component, with negligible influence from the organic groups. Furthermore, the theoretical analysis complementing experimental observationsmore » provides the conceptual insights required for a full characterization of this complex material.« less

  20. Near band edge photoluminescence of ZnO nanowires: Optimization via surface engineering

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

    Yan, Danhua; Zhang, Wenrui; Cen, Jiajie

    Zinc oxide (ZnO) nanowire arrays have potential applications for various devices including ultra-violet light emitting diodes and lasers, where photoluminescence of intense near band edge emission without defect emissions is usually desired. Here, we demonstrate, counter-intuitively, that the near band edge emission may become dominant by introducing certain surface defects to ZnO nanowires via surface engineering. Specifically, near band edge emission (NBE) is effectively enhanced after a low pressure O 2 plasma treatment that sputters off surface oxygen species to produce a reduced and oxygen vacancy-rich surface. The effect is attributed to the lowered surface valence band maximum of themore » reduced ZnO surface that creates an accumulative band bending, which screens the photo-generated minority carriers (holes) from reaching or being trapped by the surface defects.« less

  1. Near band edge photoluminescence of ZnO nanowires: Optimization via surface engineering

    DOE PAGES

    Yan, Danhua; Zhang, Wenrui; Cen, Jiajie; ...

    2017-12-04

    Zinc oxide (ZnO) nanowire arrays have potential applications for various devices including ultra-violet light emitting diodes and lasers, where photoluminescence of intense near band edge emission without defect emissions is usually desired. Here, we demonstrate, counter-intuitively, that the near band edge emission may become dominant by introducing certain surface defects to ZnO nanowires via surface engineering. Specifically, near band edge emission (NBE) is effectively enhanced after a low pressure O 2 plasma treatment that sputters off surface oxygen species to produce a reduced and oxygen vacancy-rich surface. The effect is attributed to the lowered surface valence band maximum of themore » reduced ZnO surface that creates an accumulative band bending, which screens the photo-generated minority carriers (holes) from reaching or being trapped by the surface defects.« less

  2. L-Edge X-ray Absorption Spectroscopic Investigation of {FeNO} 6: Delocalization vs Antiferromagnetic Coupling

    DOE PAGES

    Yan, James J.; Gonzales, Margarita A.; Mascharak, Pradip K.; ...

    2016-12-22

    NO is a classic non-innocent ligand, and iron nitrosyls can have different electronic structure descriptions depending on their spin state and coordination environment. These highly covalent ligands are found in metalloproteins and are also used as models for Fe–O 2 systems. Here, this study utilizes iron L-edge X-ray absorption spectroscopy (XAS), interpreted using a valence bond configuration interaction multiplet model, to directly experimentally probe the electronic structure of the S = 0 {FeNO} 6 compound [Fe(PaPy 3)NO] 2+ (PaPy 3 = N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-pyridine-2-carboxamide) and the S = 0 [Fe(PaPy 3)CO] + reference compound. This method allows separation of the σ-donation andmore » π-acceptor interactions of the ligand through ligand-to-metal and metal-to-ligand charge-transfer mixing pathways. The analysis shows that the {FeNO} 6 electronic structure is best described as Fe III–NO(neutral), with no localized electron in an NO π* orbital or electron hole in an Fe dπ orbital. This delocalization comes from the large energy gap between the Fe–NO π-bonding and antibonding molecular orbitals relative to the exchange interactions between electrons in these orbitals. This study demonstrates the utility of L-edge XAS in experimentally defining highly delocalized electronic structures.« less

  3. Electronic Structure of Ytterbium-Doped Strontium Fluoroapatite: Photoemission and Photoabsorption Investigation

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

    Nelson, Art J.; Van Buuren, Tony W.; Bostedt, C

    X-ray photoemission and x-ray photoabsorption were used to study the composition and the electronic structure of ytterbium-doped strontium fluoroapatite (Yb:S-FAP). High resolution photoemission measurements on the valence band electronic structure and Sr 3d, P 2p and 2s, Yb 4d and 4p, F 1s and O 1s core lines were used to evaluate the surface and near surface chemistry of this fluoroapatite. Element specific density of unoccupied electronic states in Yb:S-FAP were probed by x-ray absorption spectroscopy (XAS) at the Yb 4d (N4,5-edge), Sr 3d (M4,5-edge), P 2p (L2,3-edge), F 1s and O 1s (K-edges) absorption edges. These results provide themore » first measurements of the electronic structure and surface chemistry of this material.« less

  4. 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

  5. On the aeroacoustic and flow structures developed on a flat plate with a serrated sawtooth trailing edge

    NASA Astrophysics Data System (ADS)

    Chong, Tze Pei; Vathylakis, Alexandros

    2015-10-01

    Results of an experimental study on turbulent flow over a flat plate with a serrated sawtooth trailing edge are presented in this paper. After tripping the boundary layer to become turbulent, the broadband noise sources at the sawtooth serrated trailing edge is studied by several experimental techniques. Broadband noise reduction by the serrated sawtooth trailing edge can be realistically achieved in the flat plate configuration. The variations of wall pressure power spectral density and the spanwise coherence (which relates to the spanwise correlation length) in a sawtooth trailing edge play a minor role in the mechanisms underpinning the reduction of self noise radiation. Conditional-averaging technique was applied in the boundary layer data where a pair of pressure-driven oblique vortical structures near the sawtooth side edges is identified. In the current flat plate configuration, the interaction between the vortical structures and the local turbulent boundary layer results in a redistribution of the momentum transport and turbulent shear stress near the sawtooth side edges as well as the sawtooth tip, thus affecting the efficiency of self noise radiation.

  6. Near-infrared light absorption by brown carbon in the ambient atmosphere

    NASA Astrophysics Data System (ADS)

    Chung, C.; Hoffer, A.; Beres, N. D.; Moosmüller, H.; Liu, C.; Green, M.; Kim, S. W.; Engelbrecht, J. P.; Gelencser, A.

    2017-12-01

    Organic aerosols have been assumed to have little-to-no absorption in the red and near-infrared spectral regions of solar radiation, even though a class of organic aerosols were shown to absorb significantly in these spectral regions. Here, we show that ambient atmospheric data from commonly-used 7-wavelength aethalometers contain evidence of abundant near-infrared light absorption by organic aerosol. This evidence comes from the absorption Ångström exponent over 880 950 nm, which often exceeds values explainable by fresh or coated black carbon, or mineral dust. This evidence is not due to an artifact from the instrument random errors or biases, either. The best explanation for these large 880/950 nm absorption Ångström exponent values in the aethalometer data is near-infrared light absorption by tar balls. Tar balls are among common particles from forest fire.

  7. 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

  8. CNNEDGEPOT: CNN based edge detection of 2D near surface potential field data

    NASA Astrophysics Data System (ADS)

    Aydogan, D.

    2012-09-01

    All anomalies are important in the interpretation of gravity and magnetic data because they indicate some important structural features. One of the advantages of using gravity or magnetic data for searching contacts is to be detected buried structures whose signs could not be seen on the surface. In this paper, a general view of the cellular neural network (CNN) method with a large scale nonlinear circuit is presented focusing on its image processing applications. The proposed CNN model is used consecutively in order to extract body and body edges. The algorithm is a stochastic image processing method based on close neighborhood relationship of the cells and optimization of A, B and I matrices entitled as cloning template operators. Setting up a CNN (continues time cellular neural network (CTCNN) or discrete time cellular neural network (DTCNN)) for a particular task needs a proper selection of cloning templates which determine the dynamics of the method. The proposed algorithm is used for image enhancement and edge detection. The proposed method is applied on synthetic and field data generated for edge detection of near-surface geological bodies that mask each other in various depths and dimensions. The program named as CNNEDGEPOT is a set of functions written in MATLAB software. The GUI helps the user to easily change all the required CNN model parameters. A visual evaluation of the outputs due to DTCNN and CTCNN are carried out and the results are compared with each other. These examples demonstrate that in detecting the geological features the CNN model can be used for visual interpretation of near surface gravity or magnetic anomaly maps.

  9. Near-infrared radiation absorption properties of covellite (CuS) using first-principles calculations

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

    Xiao, Lihua, E-mail: xiaolihua@git.edu.cn; College of Physics and Information Science, Hunan Normal University, Changsha 410081; Guizhou Special Functional Materials 2011 Collaborative Innovation Center, Guizhou Institute of Technology, Guiyang 550003

    2016-08-15

    First-principles density functional theory was used to investigate the electronic structure, optical properties and the origin of the near-infrared (NIR) absorption of covellite (CuS). The calculated lattice constant and optical properties are found to be in reasonable agreement with experimental and theoretical findings. The electronic structure reveals that the valence and conduction bands of covellite are determined by the Cu 3d and S 3p states. By analyzing its optical properties, we can fully understand the potential of covellite (CuS) as a NIR absorbing material. Our results show that covellite (CuS) exhibits NIR absorption due to its metal-like plasma oscillation inmore » the NIR range.« less

  10. Near-field tsunami edge waves and complex earthquake rupture

    USGS Publications Warehouse

    Geist, Eric L.

    2013-01-01

    The effect of distributed coseismic slip on progressive, near-field edge waves is examined for continental shelf tsunamis. Detailed observations of edge waves are difficult to separate from the other tsunami phases that are observed on tide gauge records. In this study, analytic methods are used to compute tsunami edge waves distributed over a finite number of modes and for uniformly sloping bathymetry. Coseismic displacements from static elastic theory are introduced as initial conditions in calculating the evolution of progressive edge-waves. Both simple crack representations (constant stress drop) and stochastic slip models (heterogeneous stress drop) are tested on a fault with geometry similar to that of the M w = 8.8 2010 Chile earthquake. Crack-like ruptures that are beneath or that span the shoreline result in similar longshore patterns of maximum edge-wave amplitude. Ruptures located farther offshore result in reduced edge-wave excitation, consistent with previous studies. Introduction of stress-drop heterogeneity by way of stochastic slip models results in significantly more variability in longshore edge-wave patterns compared to crack-like ruptures for the same offshore source position. In some cases, regions of high slip that are spatially distinct will yield sub-events, in terms of tsunami generation. Constructive interference of both non-trapped and trapped waves can yield significantly larger tsunamis than those that produced by simple earthquake characterizations.

  11. Structural and Visible-Near Infrared Optical Properties of Cr-Doped TiO2 for Colored Cool Pigments

    NASA Astrophysics Data System (ADS)

    Yuan, Le; Weng, Xiaolong; Zhou, Ming; Zhang, Qingyong; Deng, Longjiang

    2017-11-01

    Chromium-doped TiO2 pigments were synthesized via a solid-state reaction method and studied with X-ray diffraction, SEM, XPS, and UV-VIS-NIR reflectance spectroscopy. The incorporation of Cr3+ accelerates the transition from the anatase phase to the rutile phase and compresses the crystal lattice. Moreover, the particle morphology, energy gap, and reflectance spectrum of Cr-doped TiO2 pigments is affected by the crystal structure and doping concentration. For the rutile samples, some of the Cr3+ ions are oxidized to Cr4+ after sintering at a high temperature, which leads to a strong near-infrared absorption band due to the 3A2 → 3 T1 electric dipole-allowed transitions of Cr4+. And the decrease of the band gap causes an obvious redshift of the optical absorption edges as the doping concentration increases. Thus, the VIS and near-infrared average reflectance of the rutile Ti1 - x Cr x O2 sample decrease by 60.2 and 58%, respectively, when the Cr content increases to x = 0.0375. Meanwhile, the color changes to black brown. However, for the anatase Ti1 - x Cr x O2 pigments, only the VIS reflection spectrum is inhibited by forming some characteristic visible light absorption peaks of Cr3+. The morphology, band gap, and NIR reflectance are not significantly affected. Finally, a Cr-doped anatase TiO2 pigment with a brownish-yellow color and 90% near-infrared reflectance can be obtained.

  12. Seismic signatures of carbonate caves affected by near-surface absorptions

    NASA Astrophysics Data System (ADS)

    Rao, Ying; Wang, Yanghua

    2015-12-01

    The near-surface absorption within a low-velocity zone generally has an exponential attenuation effect on seismic waves. But how does this absorption affect seismic signatures of karstic caves in deep carbonate reservoirs? Seismic simulation and analysis reveals that, although this near-surface absorption attenuates the wave energy of a continuous reflection, it does not alter the basic kinematic shape of bead-string reflections, a special seismic characteristic associated with carbonate caves in the Tarim Basin, China. Therefore, the bead-strings in seismic profiles can be utilized, with a great certainty, for interpreting the existence of caves within the deep carbonate reservoirs and for evaluating their pore spaces. Nevertheless, the difference between the central frequency and the peak frequency is increased along with the increment in the absorption. While the wave energy of bead-string reflections remains strong, due to the interference of seismic multiples generated by big impedance contrast between the infill materials of a cave and the surrounding carbonate rocks, the central frequency is shifted linearly with respect to the near-surface absorption. These two features can be exploited simultaneously, for a stable attenuation analysis of field seismic data.

  13. Structural evaluation of reduced graphene oxide in graphene oxide during ion irradiation: X-ray absorption spectroscopy and in-situ sheet resistance studies

    NASA Astrophysics Data System (ADS)

    Saravanan, K.; Jayalakshmi, G.; Suresh, K.; Sundaravel, B.; Panigrahi, B. K.; Phase, D. M.

    2018-03-01

    We report the structural evolution of reduced graphene oxide (rGO) in graphene oxide (GO) flakes during 1 MeV Si+ ion irradiation. In-situ electrical resistivity measurements facilitate monitoring the sheet resistance with the increase in the fluence. The electrical sheet resistance of the GO flake shows the exponential decay behaviour with the increasing ion fluence. Raman spectra of the GO flake reveal the increase in the ID/IG ratio, indicating restoration of the sp2 network upon irradiation. The C/O ratio estimated from resonant Rutherford backscattering spectrometry analysis directly evidenced the reduction of oxygen moieties upon irradiation. C K-edge X-ray absorption near edge structure spectra reveal the restoration of C=C sp2-hybridized carbon atoms and the removal of oxygen-containing functional groups in the GO flake. STM data reveal the higher conductance in the rGO regime in comparison with the regime, where the oxygen functional groups are present. The experimental investigation demonstrates that the ion irradiation can be employed for efficient reduction of GO with tunable electrical and structural properties.

  14. Correction of absorption-edge artifacts in polychromatic X-ray tomography in a scanning electron microscope for 3D microelectronics

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

    Laloum, D., E-mail: david.laloum@cea.fr; CEA, LETI, MINATEC Campus, 17 rue des Martyrs, 38054 Grenoble Cedex 9; STMicroelectronics, 850 rue Jean Monnet, 38926 Crolles

    2015-01-15

    X-ray tomography is widely used in materials science. However, X-ray scanners are often based on polychromatic radiation that creates artifacts such as dark streaks. We show this artifact is not always due to beam hardening. It may appear when scanning samples with high-Z elements inside a low-Z matrix because of the high-Z element absorption edge: X-rays whose energy is above this edge are strongly absorbed, violating the exponential decay assumption for reconstruction algorithms and generating dark streaks. A method is proposed to limit the absorption edge effect and is applied on a microelectronic case to suppress dark streaks between interconnections.

  15. AKARI Near-infrared Spectroscopic Observations of Interstellar Ices in the Edge-on Starburst Galaxy NGC 253

    NASA Astrophysics Data System (ADS)

    Yamagishi, Mitsuyoshi; Kaneda, Hidehiro; Ishihara, Daisuke; Oyabu, Shinki; Onaka, Takashi; Shimonishi, Takashi; Suzuki, Toyoaki

    2011-04-01

    We present the spatially resolved near-infrared (2.5-5.0 μm) spectra of the edge-on starburst galaxy NGC 253 obtained with the Infrared Camera on board AKARI. Near the center of the galaxy, we clearly detect the absorption features of interstellar ices (H2O: 3.05 μm, CO2: 4.27 μm, and XCN: 4.62 μm) and the emission of polycyclic aromatic hydrocarbons (PAHs) at 3.29 μm and the hydrogen recombination line Brα at 4.05 μm. We find that the distributions of the ices differ from those of the PAH and gas. We calculate the column densities of the ices and derive the abundance ratios of N(CO2)/N(H2O) = 0.17 ± 0.05. They are similar to those obtained around the massive young stellar objects in our Galaxy (0.17 ± 0.03), although a much stronger interstellar radiation field and higher dust temperature are expected near the center of NGC 253.

  16. Integrated three-dimensional photonic nanostructures for achieving near-unity solar absorption and superhydrophobicity

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

    Kuang, Ping; Lin, Shawn-Yu, E-mail: sylin@rpi.edu; Hsieh, Mei-Li

    2015-06-07

    In this paper, we proposed and realized 3D photonic nanostructures consisting of ultra-thin graded index antireflective coatings (ARCs) and woodpile photonic crystals. The use of the integrated ARC and photonic crystal structure can achieve broadband, broad-angle near unity solar absorption. The amorphous silicon based photonic nanostructure experimentally shows an average absorption of ∼95% for λ = 400–620 nm over a wide angular acceptance of θ = 0°–60°. Theoretical studies show that a Gallium Arsenide (GaAs) based structure can achieve an average absorption of >95% for λ = 400–870 nm. Furthermore, the use of the slanted SiO{sub 2} nanorod ARC surface layer by glancing angle deposition exhibits Cassie-Baxter statemore » wetting, and superhydrophobic surface is obtained with highest water contact angle θ{sub CB} ∼ 153°. These properties are fundamentally important for achieving maximum solar absorption and surface self-cleaning in thin film solar cell applications.« less

  17. 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.

  18. 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.

  19. Virtual edge illumination and one dimensional beam tracking for absorption, refraction, and scattering retrieval

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

    Vittoria, Fabio A., E-mail: fabio.vittoria.12@ucl.ac.uk; Diemoz, Paul C.; Research Complex at Harwell, Harwell Oxford Campus, OX11 0FA Didcot

    2014-03-31

    We propose two different approaches to retrieve x-ray absorption, refraction, and scattering signals using a one dimensional scan and a high resolution detector. The first method can be easily implemented in existing procedures developed for edge illumination to retrieve absorption and refraction signals, giving comparable image quality while reducing exposure time and delivered dose. The second method tracks the variations of the beam intensity profile on the detector through a multi-Gaussian interpolation, allowing the additional retrieval of the scattering signal.

  20. Edge-closed laminated structures for thin-film heads

    NASA Astrophysics Data System (ADS)

    Herman, D. A.; Argyle, B. E.; Lee, H.-P.; Trouilloud, P. O.; Petek, B.

    1991-04-01

    Magnetic film laminations containing nonmagnetic spacers have been explored with the hope of eliminating domain walls to diminish Barkhausen instabilities. Such laminates have limitations however, which originate in their ``edge-curling walls'' (ECWs).1 We have developed a new structure, free of ECWs, in which flux closure at opposing edges occurs via edge-shorting material added to circulate the easy-axis flux of the flat layers. We show experimentally with Kerr-effect imaging that (1) this edge-closed laminated (ECL) structure can support an (ECW-free) ``easy-axis'' (EA) magnetic state under conditions as modeled recently by Slonczewski,2 and (2) that this EA state is quite robust in the face of imperfect structure fabrication. This is, if the imperfections are not too severe, the resultant states depart minimally from the pure EA state and conduct hard-axis-driven flux nearly as well. Flat-film ECL elements in diamond, stripe, and recording-head-yoke shapes, plus experimental heads with ECL top yokes, were fabricated. Our domain images verify some key predictions from Slonczewski's static equilibrium modeling; additional results taken in applied magnetic fields extend the micromagnetic understanding. The sketch shows a typical domain pattem for a yoke-shaped element. The most stable state in the open portion of the yoke is the single domain shown. This remanent pattern was stable in the face of (slowly varying) external fields up to the 150 Oe that could be applied. The pole tip region contained a few 180° walls as indicated. On close inspection, these walls were seen to end in vestigial, nontouching, closure domains as predicted by the model when only partial flux closure occurs via the edge shorting material. The wall spacing in the tip varied somewhat following saturation-demagnetization cycles. The dynamic stability of this EA state was investigated in the experimental heads having ECL top yokes. The pseudodynamic LAMOM technique3 was applied using ``write

  1. 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

  2. X-ray absorption Studies of Zinc species in Centella asiatica

    NASA Astrophysics Data System (ADS)

    Dehipawala, Sunil; Cheung, Tak; Hogan, Clayton; Agoudavi, Yao; Dehipawala, Sumudu

    2013-03-01

    Zinc is a very important mineral present in a variety of vegetables. It is an essential element in cellular metabolism and several bodily functions. We used X-ray fluorescence, and X-ray Absorption near Edge structure(XANES) to study the amount of zinc present in several leafy vegetables as well as its chemical environment within the plant. Main absorption edge position of XANES is sensitive to the oxidation state of zinc and is useful when comparing the type of zinc present in different vegetables to the standard zinc present in supplements. Normalized main edge height is proportional to the amount of zinc present in the sample. Several leafy greens were used in this study, such as Spinacia oleracea, Basella alba, Brassica oleracea, Cardiospermum halicacabumand Centella asiatica. All of these plant leaves contained approximately the same amount of zinc in the leaf portion of the plant and a slightly lower amount in the stems, except Centella asiatica. Both leaves and stems of the plant Centella asiatica contained nearly two times the zinc compared to other plants. Further investigation of zinc's chemical environment within Centella asiatica could lead to a much more efficient dietary consumption of zinc. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886

  3. Achieving an Accurate Surface Profile of a Photonic Crystal for Near-Unity Solar Absorption in a Super Thin-Film Architecture.

    PubMed

    Kuang, Ping; Eyderman, Sergey; Hsieh, Mei-Li; Post, Anthony; John, Sajeev; Lin, Shawn-Yu

    2016-06-28

    In this work, a teepee-like photonic crystal (PC) structure on crystalline silicon (c-Si) is experimentally demonstrated, which fulfills two critical criteria in solar energy harvesting by (i) its Gaussian-type gradient-index profile for excellent antireflection and (ii) near-orthogonal energy flow and vortex-like field concentration via the parallel-to-interface refraction effect inside the structure for enhanced light trapping. For the PC structure on 500-μm-thick c-Si, the average reflection is only ∼0.7% for λ = 400-1000 nm. For the same structure on a much thinner c-Si ( t = 10 μm), the absorption is near unity (A ∼ 99%) for visible wavelengths, while the absorption in the weakly absorbing range (λ ∼ 1000 nm) is significantly increased to 79%, comparing to only 6% absorption for a 10-μm-thick planar c-Si. In addition, the average absorption (∼94.7%) of the PC structure on 10 μm c-Si for λ = 400-1000 nm is only ∼3.8% less than the average absorption (∼98.5%) of the PC structure on 500 μm c-Si, while the equivalent silicon solid content is reduced by 50 times. Furthermore, the angular dependence measurements show that the high absorption is sustained over a wide angle range (θinc = 0-60°) for teepee-like PC structure on both 500 and 10-μm-thick c-Si.

  4. Temperature dependence of the fundamental optical absorption edge in crystals and disordered semiconductors

    NASA Astrophysics Data System (ADS)

    Grein, C. H.; John, Sajeev

    1989-04-01

    We present a first principles theory of the temperature dependence of the Urbach optical absorption edge in crystals and disordered semiconductors which incorporates the effects of short range correlated static disorder and the non-adiabatic quantum dynamics of the coupled electron-phonon system. At finite temperatures the dominant features of the Urbach tail are accounted for by multiple phonon absorption and emission side bands which accompany the optically induced electronic transition and which provide a dynamic polaronic potential well that localizes the electron. Excellent agreement is found with experimental data on both crystalline and amorphous silicon.

  5. Complete wetting near an edge of a rectangular-shaped substrate

    NASA Astrophysics Data System (ADS)

    Malijevský, Alexandr

    2014-08-01

    We consider fluid adsorption near a rectangular edge of a solid substrate that interacts with the fluid atoms via long range (dispersion) forces. The curved geometry of the liquid-vapour interface dictates that the local height of the interface above the edge ℓE must remain finite at any subcritical temperature, even when a macroscopically thick film is formed far from the edge. Using an interfacial Hamiltonian theory and a more microscopic fundamental measure density functional theory (DFT), we study the complete wetting near a single edge and show that {{\\ell}_{\\text{E}}}\\left(0\\right)-{{\\ell}_{\\text{E}}}\\left(\\delta \\mu \\right)\\sim \\delta {{\\mu}^{\\beta _{\\text{E}}^{\\text{co}}}} , as the chemical potential departure from the bulk coexistence δμ = μs(T) - μ tends to zero. The exponent \\beta _{\\text{E}}^{\\text{co}} depends on the range of the molecular forces and in particular \\beta _{\\text{E}}^{\\text{co}}=2/3 for three-dimensional systems with van der Waals forces. We further show that for a substrate model that is characterised by a finite linear dimension L, the height of the interface deviates from the one at the infinite substrate as δℓE(L) ˜ L-1 in the limit of large L. Both predictions are supported by numerical solutions of the DFT.

  6. 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.

  7. X-ray K-edge absorption spectra of Fe minerals and model compounds: II. EXAFS

    NASA Astrophysics Data System (ADS)

    Waychunas, Glenn A.; Brown, Gordon E.; Apted, Michael J.

    1986-01-01

    K-edge extended X-ray absorption fine structure (EXAFS) spectra of Fe in varying environments in a suite of well-characterized silicate and oxide minerals were collected using synchrotron radiation and analyzed using single scattering approximation theory to yield nearest neighbor Fe-O distances and coordination numbers. The partial inverse character of synthetic hercynite spinal was verified in this way. Comparison of the results from all samples with structural data from X-ray diffraction crystal structure refinements indicates that EXAFS-derived first neighbor distances are generally accurate to ±0.02 Å using only theoretically generated phase information, and may be improved over this if similar model compounds are used to determine EXAFS phase functions. Coordination numbers are accurate to ±20 percent and can be similarly improved using model compound EXAFS amplitude information. However, in particular cases the EXAFS-derived distances may be shortened, and the coordination number reduced, by the effects of static and thermal disorder or by partial overlap of the longer Fe-O first neighbor distances with second neighbor distances in the EXAFS structure function. In the former case the total information available in the EXAFS is limited by the disorder, while in the latter case more accurate results can in principle be obtained by multiple neighbor EXAFS analysis. The EXAFS and XANES spectra of Fe in Nain, Labrador osumulite and Lakeview, Oregon plagioclase are also analyzed as an example of the application of X-ray absorption spectroscopy to metal ion site occupation determination in minerals.

  8. 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.

  9. Dramatic enhancement of near-infrared intersubband absorption in c-plane AlInN/GaN superlattices

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

    Shirazi-HD, M.; Birck Nanotechnology Center, West Lafayette, Indiana 47907; Turkmeneli, K.

    2016-03-21

    We report substantial improvement of near-infrared (2–2.6 μm) intersubband absorption in c-plane AlInN/GaN superlattices grown by molecular beam epitaxy. Progress was obtained through optimization of AlInN growth conditions using an AlInN growth rate of 0.9-nm/min at substrate temperature of 550 °C, as well as by judiciously placing the charge into two delta-doping sheets. Structural characterization suggests that AlInN crystal quality is enhanced and interface roughness is reduced. Importantly, near-infrared absorption data indicate that the optical quality of the AlInN/GaN superlattices is now comparable with that of AlN/GaN superlattices designed to exploit near-infrared intersubband transitions.

  10. Io: Near-Infrared Absorptions Not Attributable to SO2

    NASA Astrophysics Data System (ADS)

    Shirley, J. H.; Clark, R. N.; Soderblom, L. A.; Carlson, R. W.; Kamp, L. W.; Galileo NIMS Team

    2001-11-01

    The Near-Infrared Mapping Spectrometer (NIMS) onboard the Galileo spacecraft imaged the leading side of Jupiter's satellite Io at full spectral resolution and with triple Nyquist spatial sampling during the fifteenth orbital encounter (E15). New despiking and "dejittering" algorithms have been applied to this high S/N observation (15INHRSPEC01A). Spectral absorption features not attributable to SO2 are found between 3.0-3.4 microns and near 4.65 microns. The patterns of the spatial distributions of both absorbers differ from that of the omnipresent SO2. The broad 3.0-3.4 micron absorption is most pronounced in polar regions. Preliminary work suggests that the 4.65 micron feature may be associated with an unidentified sulfate mineral, while the 3.0-3.4 micron feature may result from the presence of more than one absorbing material. Hydrogen-bearing species are likely candidates. For example, H2O ice provides a good match for the absorption near 3.2 microns, but the absorption is shifted to wavelengths longer than that in pure H2O ice. If only one absorber is present, then hydrogen bonding of small numbers of H2O molecules could perhaps account for the shift. The absorption is weak; if H20 related, optical path lengths of a fraction of a micron are indicated. Portions of this research were carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration.

  11. Broadband and wide angle near-unity absorption in graphene-insulator-metal thin film stacks

    NASA Astrophysics Data System (ADS)

    Zhang, H. J.; Zheng, G. G.; Chen, Y. Y.; Xu, L. H.

    2018-05-01

    Broadband unity absorption in graphene-insulator-metal (GIM) structures is demonstrated in the visible (VIS) and near-infrared (NIR) spectra. The spectral characteristics possess broadband absorption peaks, by simply choosing a stack of GIM, while no nanofabrication steps and patterning are required, and thus can be easily fabricated to cover a large area. The electromagnetic (EM) waves can be entirely trapped and the absorption can be greatly enhanced are verified with the finite-difference time-domain (FDTD) and rigorous coupled wave analysis (RCWA) methods. The position and the number of the absorption peak can be totally controlled by adjusting the thickness of the insulator layer. The proposed absorber maintains high absorption (above 90%) for both transverse electric (TE) and transverse magnetic (TM) polarizations, and for angles of incidence up to 80°. This work opens up a promising approach to realize perfect absorption (PA) with ultra-thin film, which could implicate many potential applications in optical detection and optoelectronic devices.

  12. 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.

  13. Atomic-scale distortion of optically activated Sm dopants identified with site-selective X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ishii, Masashi; Crowe, Iain F.; Halsall, Matthew P.; Hamilton, Bruce; Hu, Yongfeng; Sham, Tsun-Kong; Harako, Susumu; Zhao, Xin-Wei; Komuro, Shuji

    2013-10-01

    The local structure of luminescent Sm dopants was investigated using an X-ray absorption fine-structure technique with X-ray-excited optical luminescence. Because this technique evaluates X-ray absorption from luminescence, only optically active sites are analyzed. The Sm L3 near-edge spectrum contains split 5d states and a shake-up transition that are specific to luminescent Sm. Theoretical calculations using cluster models identified an atomic-scale distortion that can reproduce the split 5d states. The model with C4v local symmetry and compressive bond length of Sm-O of a six-fold oxygen (SmO6) cluster is most consistent with the experimental results.

  14. [Near ultraviolet absorption spectral properties of chromophoric dissolved organic matter in the north area of Yellow Sea].

    PubMed

    Wang, Lin; Zhao, Dong-Zhi; Yang, Jian-Hong; Chen, Yan-Long

    2010-12-01

    Chromophoric dissolved organic matter (CDOM) near ultraviolet absorption spectra contains CDOM molecular structure, composition and other important physical and chemical information. Based on the measured data of CDOM absorption coefficient in March 2009 in the north area of Yellow Sea, the present paper analyzed near ultraviolet absorption spectral properties of CDOM. The results showed that due to the impact of near-shore terrigenous input, the composition of CDOM is quite different in the north area of Yellow Sea, and this area is a typical case II water; fitted slope with specific range of spectral band and absorption coefficient at specific band can indicate the relative size of CDOM molecular weight, correlation between spectral slope of the Sg,275-300), Sg,300-350, Sg,350-400 and Sg,250-275 and the relative size of CDOM molecular weight indicative parameter M increases in turn and the highest is up to 0.95. Correlation between a(g)(lambda) and M value increases gradually with the increase in wavelength, and the highest is up to 0.92 at 400 nm; being correlated or not between spectral slope and absorption coefficient is decided by the fitting-band wavelength range for the spectra slope and the wavelength for absorption coefficient. Correlation between Sg,275-300 and a(g)(400) is the largest, up to 0.87.

  15. 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

  16. Activation of an intense near band edge emission from ZnTe/ZnMgTe core/shell nanowires grown on silicon.

    PubMed

    Wojnar, P; Szymura, M; Zaleszczyk, W; Kłopotowski, L; Janik, E; Wiater, M; Baczewski, L T; Kret, S; Karczewski, G; Kossut, J; Wojtowicz, T

    2013-09-13

    The absence of luminescence in the near band edge energy region of Te-anion based semiconductor nanowires grown by gold catalyst assisted molecular beam epitaxy has strongly limited their applications in the field of photonics. In this paper, an enhancement of the near band edge emission intensity from ZnTe/ZnMgTe core/shell nanowires grown on Si substrates is reported. A special role of the use of Si substrates instead of GaAs substrates is emphasized, which results in an increase of the near band edge emission intensity by at least one order of magnitude accompanied by a simultaneous reduction of the defect related luminescence. A possible explanation of this effect relies on the presence of Ga-related deep level defects in structures grown on GaAs substrates, which are absent when Si substrates are used. Monochromatic mapping of the cathodoluminescence clearly confirms that the observed emission originates, indeed, from the ZnTe/ZnMgTe core/shell nanowires, whereas individual objects are studied by means of microphotoluminescence.

  17. Structural and electrical properties of In-implanted Ge

    DOE PAGES

    Feng, R.; Kremer, F.; Sprouster, D. J.; ...

    2015-10-22

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

  18. Multi-epoch Detections of Water Ice Absorption in Edge-on Disks around Herbig Ae Stars: PDS 144N and PDS 453

    NASA Astrophysics Data System (ADS)

    Terada, Hiroshi; Tokunaga, Alan T.

    2017-01-01

    We report the multi-epoch detections of water ice in 2.8-4.2 μ {{m}} spectra of two Herbig Ae stars, PDS 144N (A2 IVe) and PDS 453 (F2 Ve), which have an edge-on circumstellar disk. The detected water ice absorption is found to originate from their protoplanetary disks. The spectra show a relatively shallow absorption of water ice of around 3.1 μ {{m}} for both objects. The optical depths of the water ice absorption are ˜0.1 and ˜0.2 for PDS 144N and PDS 453, respectively. Compared to the water ice previously detected in low-mass young stellar objects with an edge-on disk with a similar inclination angle, these optical depths are significantly lower. It suggests that stronger UV radiation from the central stars effectively decreases the water ice abundance around the Herbig Ae stars through photodesorption. The water ice absorption in PDS 453 shows a possible variation of the feature among the six observing epochs. This variation could be due to a change of absorption materials passing through our line of sight to the central star. The overall profile of the water ice absorption in PDS 453 is quite similar to the absorption previously reported in the edge-on disk object d216-0939, and this unique profile may be seen only at a high inclination angle in the range of 76°-80°.

  19. Unraveling the atomic structure of biogenic silica: evidence of the structural association of Al and Si in diatom frustules

    NASA Astrophysics Data System (ADS)

    Gehlen, M.; Beck, L.; Calas, G.; Flank, A.-M.; Van Bennekom, A. J.; Van Beusekom, J. E. E.

    2002-05-01

    We used X-ray absorption spectroscopy at the Al K-edge to investigate the atomic structure of biogenic silica and to assess the effect of Al on its crystal chemistry. Our study provides the first direct evidence for a structural association of Al and Si in biogenic silica. In samples of cultured diatoms, Al is present exclusively in fourfold coordination. The location and relative intensity of X-ray absorption near-edge structure (XANES) features suggests the structural insertion of tetrahedral Al inside the silica framework synthesized by the organism. In diatom samples collected in the marine environment, Al is present in mixed six- and fourfold coordination. The relative intensity of XANES structures indicates the coexistence of structural Al with a clay component, which most likely reflects sample contamination by adhering mineral particles. Extended X-ray absorption fine structure spectroscopy has been used to get Al-O distances in biogenic silica of cultured diatoms, confirming a tetrahedral coordination. Because of its effect on solubility and reaction kinetics of biogenic silica, the structural association between Al and biogenic silica at the stage of biosynthesis has consequences for the use of sedimentary biogenic silica as an indicator of past environmental conditions.

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

    PubMed Central

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

    2015-01-01

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

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

    DOE PAGES

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

    2015-06-05

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

  2. Strain-Dependent Edge Structures in MoS2 Layers.

    PubMed

    Tinoco, Miguel; Maduro, Luigi; Masaki, Mukai; Okunishi, Eiji; Conesa-Boj, Sonia

    2017-11-08

    Edge structures are low-dimensional defects unavoidable in layered materials of the transition metal dichalcogenides (TMD) family. Among the various types of such structures, the armchair (AC) and zigzag (ZZ) edge types are the most common. It has been predicted that the presence of intrinsic strain localized along these edges structures can have direct implications for the customization of their electronic properties. However, pinning down the relation between local structure and electronic properties at these edges is challenging. Here, we quantify the local strain field that arises at the edges of MoS 2 flakes by combining aberration-corrected transmission electron microscopy (TEM) with the geometrical-phase analysis (GPA) method. We also provide further insight on the possible effects of such edge strain on the resulting electronic behavior by means of electron energy loss spectroscopy (EELS) measurements. Our results reveal that the two-dominant edge structures, ZZ and AC, induce the formation of different amounts of localized strain fields. We also show that by varying the free edge curvature from concave to convex, compressive strain turns into tensile strain. These results pave the way toward the customization of edge structures in MoS 2 , which can be used to engineer the properties of layered materials and thus contribute to the optimization of the next generation of atomic-scale electronic devices built upon them.

  3. X ray absorption fine structure of systems in the anharmonic limit

    NASA Astrophysics Data System (ADS)

    Mustredeleon, J.; Conradson, S. D.; Batistic, I.; Bishop, A. R.; Raistrick, I.; Jackson, W. E.; Brown, G. E.

    A new approach to the analysis of x-ray absorption fine structure (XAFS) data is presented. It is based on the use of radial distribution functions directly calculated from a single-particle ion Hamiltonian containing model potentials. The starting point of this approach is the statistical average of the XAFS for an atomic pair. This average can be computed using a radial distribution function (RDF), which can be expressed in terms of the eigenvalues and wavefunctions associated with the model potential. The pair potential describing the ionic motion is then expressed in terms of parameters that are determined by fitting this statistical average to the experimental XAFS spectrum. This approach allows the use of XAFS as a tool for mapping near-neighbor interatomic potentials, and allows the treatment of systems which exhibit strongly anharmonic potentials which can be treated by perturbative methods. Using this method we have analyzed the high temperature behavior of the oxygen contributions to the Fe K-edge XAFS in the ferrosilicate minerals andradite (Ca3Fe2Si3O12) and magnesiowustite (Mg(0.9)Fe(0.1)O). Using a temperature dependent anharmonic correction derived from these model compounds, we have found evidence for a local structural change in the Fe-O coordination environment upon melting of the geologically important mineral fayalite (Fe2SiO4). We have also employed this method to the study of the axial oxygen contributions to the polarized Cu K-edge XAFS on oriented samples of YBa2Cu3O7 and related compounds. From this study we find evidence for an axial oxygen-centered lattice distortion accompanying the superconducting phase transition and a correlation between this distortion and Tc. The relation of the observed lattice distortion to mechanisms of superconductivity is discussed.

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

    DOE PAGES

    Levantino, M.; Lemke, H. T.; Schirò, G.; ...

    2015-07-01

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

  5. X-ray absorption 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.

  6. 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

  7. Linear instabilities near the DIII-D edge simulated in fluid models

    NASA Astrophysics Data System (ADS)

    Bass, Eric; Holland, Christopher

    2017-10-01

    The linear instability spectrum is reported near the DIII-D edge (within the separatrix) for L-mode and H-mode shots using the new eigenvalue solver FluTES (Fluid Toroidal Eigenvalue Solver). FluTES circumvents difficulties with convergence to clean linear eigenmodes (required for diagnosis of nonlinear simulations in codes such as BOUT++) often encountered with fluid initial-value solvers. FluTES is well-verified in analytic cases and against a BOUT++/ELITE benchmark toroidal case. We report results for both a 3-field, one-fluid model (the well-known ``elm-pb'' model) and a 5-field, two-fluid model. For the peeling-ballooning-dominated H-mode, the two solutions are qualitatively the same. In the driftwave-dominated L-mode edge, only the two-fluid solution gives robust instabilities which occur primarily at n > 50 . FluTES is optimized for this regime (near-flutelike limit, toroidally spectral). Cross-separatrix, coupled fluid and drift instabilities may play a role in explaining the gyrokinetic L-mode edge transport shortfall. Extension of FluTES into the open-field-line region is underway. Prepared by UCSD under Contract Number DE-FG02-06ER54871.

  8. Enhanced absorption of TM waves in conductive nanoparticles structure

    NASA Astrophysics Data System (ADS)

    Mousa, H. M.; Shabat, M. M.; Ouda, A. K.; Schaadt, D. M.

    2018-05-01

    This paper tackles anti-reflection coating structure for silicon solar cell where conductive nanoparticle (CNP) film is sandwiched between a semi-infinite glass cover and a semi-infinite silicon substrate. The transmission and reflection coefficients are derived by the transfer matrix method and simulated for values of unit cell sizes, gab widths in visible and near-infrared radiation. We also illustrated the dependence of the absorption, transmission and reflection coefficients on several angles of incidence of the transverse magnetic polarized (TM) waves. We found out that reflection decreases by the increase of incident angle to 50∘. If nanoparticles are suitably located and sized at gab width of 3.5 nm, unit cell of 250 nm and CNP layer thickness of 150 nm, the absorptivity of the structure achieves 100%.

  9. 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.

  10. Quick-scanning x-ray absorption spectroscopy system with a servo-motor-driven channel-cut monochromator with a temporal resolution of 10 ms.

    PubMed

    Nonaka, T; Dohmae, K; Araki, T; Hayashi, Y; Hirose, Y; Uruga, T; Yamazaki, H; Mochizuki, T; Tanida, H; Goto, S

    2012-08-01

    We have developed a quick-scanning x-ray absorption fine structure (QXAFS) system and installed it at the recently constructed synchrotron radiation beamline BL33XU at the SPring-8. Rapid acquisition of high-quality QXAFS data was realized by combining a servo-motor-driven Si channel-cut monochromator with a tapered undulator. Two tandemly aligned monochromators with channel-cut Si(111) and Si(220) crystals covered energy ranges of 4.0-28.2 keV and 6.6-46.0 keV, respectively. The system allows the users to adjust instantly the energy ranges of scans, the starting angles of oscillations, and the frequencies. The channel-cut crystals are cooled with liquid nitrogen to enable them to withstand the high heat load from the undulator radiation. Deformation of the reflecting planes is reduced by clamping each crystal with two cooling blocks. Performance tests at the Cu K-edge demonstrated sufficiently high data quality for x-ray absorption near-edge structure and extended x-ray absorption fine-structure analyses with temporal resolutions of up to 10 and 25 ms, respectively.

  11. 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.

  12. Intersubband absorption of p-type wurtzite GaN/AlN quantum well for fiber-optics telecommunication

    NASA Astrophysics Data System (ADS)

    Park, Seoung-Hwan; Ahn, Doyeol; Park, Chan-Yong

    2017-11-01

    The intersubband transition of wurtzite (WZ) p-type GaN/AlN quantum well (QW) structures grown on GaN substrate was investigated theoretically using the multiband effective-mass theory. The peak value of the TE-polarization absorption spectrum is found to be similar to that of the TM-polarization absorption spectrum. The absorption coefficients for TE- and TM-polarizations are mainly attributed to the absorption from the ground state (m1 = 1) because holes are mainly confined in ground states near the band-edge in an investigated range of the carrier density. We observe that a transition wavelength of 1.55 μm can be obtained for the QW structure with a relatively thin (˜16 Å) well width. Thus, we expect that a p-type WZ AlN/GaN heterostructure is applicable for a photodetector application for fiber-optic communications with normal incidence of wave.

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    This paper presents the X-ray absorption near edge structure (XANES) studies of Nd doped phosphate glasses before and after gamma irradiation. The intensity and location of LIII edge white line peak of Nd changes depending on its concentration as well as on the ratio of O/Nd in the glass matrix. The decrease in the peak intensity of white line after gamma irradiation indicates towards reduction of Nd3+ to Nd2+ in the glass matrix, which increases with an increase in the doses of gamma irradiation. Similarity in the XANES spectra of Nd doped phosphate glasses and Nd2O3 suggests that coordination geometry around Nd3+ in glass samples may be identical to that of Nd2O3.

  15. Electronic and atomic structures of Ti{sub 1-x}Al{sub x}N thin films related to their damage behavior

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

    Tuilier, M.-H.; Pac, M.-J.; Girleanu, M.

    2008-04-15

    Ti and Al K-edge x-ray absorption spectroscopy is used to investigate the electronic structure of Ti{sub 1-x}Al{sub x}N thin films deposited by reactive magnetron sputtering. The experimental near edge spectra of TiN and AlN are interpreted in the light of unoccupied density of state band structure calculations. The comparison of the structural parameters derived from x-ray absorption fine structure and x-ray diffraction reveals segregation between Al-rich and Ti-rich domains within the Ti{sub 1-x}Al{sub x}N films. Whereas x-ray diffraction probes only the crystallized domains, the structural information derived from extended x-ray absorption fine structure analysis turns on both crystalline and grainmore » boundaries. The results are discussed by considering the damage behavior of the films depending on the composition.« less

  16. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  18. Determination of copper binding in Pseudomonas putida CZ1 by chemical modifications and X-ray absorption spectroscopy.

    PubMed

    Chen, XinCai; Shi, JiYan; Chen, YingXu; Xu, XiangHua; Chen, LiTao; Wang, Hui; Hu, TianDou

    2007-03-01

    Previously performed studies have shown that Pseudomonas putida CZ1 biomass can bind an appreciable amount of Cu(II) and Zn(II) ions from aqueous solutions. The mechanisms of Cu- and Zn-binding by P. putida CZ1 were ascertained by chemical modifications of the biomass followed by Fourier transform infrared and X-ray absorption spectroscopic analyses of the living or nonliving cells. A dramatic decrease in Cu(II)- and Zn(II)-binding resulted after acidic methanol esterification of the nonliving cells, indicating that carboxyl functional groups play an important role in the binding of metal to the biomaterial. X-ray absorption spectroscopy was used to determine the speciation of Cu ions bound by living and nonliving cells, as well as to elucidate which functional groups were involved in binding of the Cu ions. The X-ray absorption near-edge structure spectra analysis showed that the majority of the Cu was bound in both samples as Cu(II). The fitting results of Cu K-edge extended X-ray absorption fine structure spectra showed that N/O ligands dominated in living and nonliving cells. Therefore, by combining different techniques, our results indicate that carboxyl functional groups are the major ligands responsible for the metal binding in P. putida CZ1.

  19. Temperature dependence of the Urbach optical absorption edge: A theory of multiple phonon absorption and emission sidebands

    NASA Astrophysics Data System (ADS)

    Grein, C. H.; John, Sajeev

    1989-01-01

    The optical absorption coefficient for subgap electronic transitions in crystalline and disordered semiconductors is calculated by first-principles means with use of a variational principle based on the Feynman path-integral representation of the transition amplitude. This incorporates the synergetic interplay of static disorder and the nonadiabatic quantum dynamics of the coupled electron-phonon system. Over photon-energy ranges of experimental interest, this method predicts accurate linear exponential Urbach behavior of the absorption coefficient. At finite temperatures the nonlinear electron-phonon interaction gives rise to multiple phonon emission and absorption sidebands which accompany the optically induced electronic transition. These sidebands dominate the absorption in the Urbach regime and account for the temperature dependence of the Urbach slope and energy gap. The physical picture which emerges is that the phonons absorbed from the heat bath are then reemitted into a dynamical polaronlike potential well which localizes the electron. At zero temperature we recover the usual polaron theory. At high temperatures the calculated tail is qualitatively similar to that of a static Gaussian random potential. This leads to a linear relationship between the Urbach slope and the downshift of the extrapolated continuum band edge as well as a temperature-independent Urbach focus. At very low temperatures, deviations from these rules are predicted arising from the true quantum dynamics of the lattice. Excellent agreement is found with experimental data on c-Si, a-Si:H, a-As2Se3, and a-As2S3. Results are compared with a simple physical argument based on the most-probable-potential-well method.

  20. Revealing the Bonding Environment of Zn in ALD Zn(O,S) Buffer Layers through X-ray Absorption Spectroscopy

    PubMed Central

    2017-01-01

    Zn(O,S) buffer layer electronic configuration is determined by its composition and thickness, tunable through atomic layer deposition. The Zn K and L-edges in the X-ray absorption near edge structure verify ionicity and covalency changes with S content. A high intensity shoulder in the Zn K-edge indicates strong Zn 4s hybridized states and a preferred c-axis orientation. 2–3 nm thick films with low S content show a subdued shoulder showing less contribution from Zn 4s hybridization. A lower energy shift with film thickness suggests a decreasing bandgap. Further, ZnSO4 forms at substrate interfaces, which may be detrimental for device performance. PMID:29083141

  1. Role of HfO 2/SiO 2 thin-film interfaces in near-ultraviolet absorption and pulsed laser damage

    DOE PAGES

    Papernov, Semyon; Kozlov, Alexei A.; Oliver, James B.; ...

    2016-07-15

    Here, the role of thin-film interfaces in the near-ultraviolet (near-UV) absorption and pulsed laser-induced damage was studied for ion-beam-sputtered and electron-beam-evaporated coatings comprised from HfO 2 and SiO 2 thin-film pairs. To separate contributions from the bulk of the film and from interfacial areas, absorption and damage threshold measurements were performed for a one-wave (355-nm wavelength) thick, HfO 2 single-layer film and for a film containing seven narrow HfO 2 layers separated by SiO 2 layers. The seven-layer film was designed to have a total optical thickness of HfO 2 layers, equal to one wave at 355 nm and anmore » E-field peak and average intensity similar to a single-layer HfO 2 film. Absorption in both types of films was measured using laser calorimetry and photothermal heterodyne imaging. The results showed a small contribution to total absorption from thin-film interfaces as compared to HfO 2 film material. The relevance of obtained absorption data to coating near-UV, nanosecond-pulse laser damage was verified by measuring the damage threshold and characterizing damage morphology. The results of this study revealed a higher damage resistance in the seven-layer coating as compared to the single-layer HfO 2 film in both sputtered and evaporated coatings. The results are explained through the similarity of interfacial film structure with structure formed during the codeposition of HfO 2 and SiO 2 materials.« less

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

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

    Fulton, John L.; Govind, Niranjan; Huthwelker, Thomas

    2015-07-02

    We probe, at high energy resolution, the double electron excitation (KL II&II) x-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of α-alumina and sodium aluminate. The two solid standards, α-alumina (octahedral) and sodium aluminate (tetrahedral) are compared to aqueous species that have the same Al coordination symmetries, Al³⁺•6H₂O (octahedral) and Al(OH)₄⁻ (tetrahedral). For the octahedral species, the edge height of the KL II&III-edge is approximately 10% of the main K-edge however the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the α-alumina and aqueous Al³⁺•6H₂Omore » the KL II&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KL II&III-edge feature interferes with an important region of the extended-XAFS region of the spectra for the K-edge of the crystalline and aqueous standards. The K-edge spectra and K-edge positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge XANES spectra reproduce the observed transitions in the experimental spectra of the four Al species. The KL II&III and KL I onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (ΔSCF) method. Research by JLF, NG, EJB, AV, TDS was supported by U.S. Department of Energy’s (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. NG thanks Amity Andersen for help with the α-Al₂O₃ and tetrahedral sodium aluminate (NaAlO₂) clusters. All the calculations were performed using the Molecular Science Computing Capability at EMSL, a national scientific user facility sponsored by the U.S. Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL

  3. Effects of a power and photon energy of incident light on near-field etching properties

    NASA Astrophysics Data System (ADS)

    Yatsui, T.; Saito, H.; Nishioka, K.; Leuschel, B.; Soppera, O.; Nobusada, K.

    2017-12-01

    We developed a near-field etching technique for realizing an ultra-flat surfaces of various materials and structures. To elucidate the near-field etching properties, we have investigated the effects of power and the photon energy of the incident light. First, we established theoretically that an optical near-field with photon energy lower than the absorption edge of the molecules can induce molecular vibrations. We used nanodiamonds to study the power dependence of the near-field etching properties. From the topological changes of the nanodiamonds, we confirmed the linear-dependence of the etching volume with the incident power. Furthermore, we studied the photon energy dependence using TiO2 nanostriped structures, which revealed that a lower photon energy results in a lower etching rate.

  4. Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study

    NASA Astrophysics Data System (ADS)

    Helmbrecht, C.; Lützenkirchen-Hecht, D.; Frank, W.

    2015-03-01

    Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES

  5. 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.

  6. Near-band-edge optical responses of solution-processed organic-inorganic hybrid perovskite CH3NH3PbI3 on mesoporous TiO2 electrodes

    NASA Astrophysics Data System (ADS)

    Yamada, Yasuhiro; Nakamura, Toru; Endo, Masaru; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

    2014-03-01

    We studied the near-band-edge optical responses of solution-processed CH3NH3PbI3 on mesoporous TiO2 electrodes, which is utilized in mesoscopic heterojunction solar cells. Photoluminescence (PL) and PL excitation spectra peaks appear at 1.60 and 1.64 eV, respectively. The transient absorption spectrum shows a negative peak at 1.61 eV owing to photobleaching at the band-gap energy, indicating a direct band-gap semiconductor. On the basis of the temperature-dependent PL and diffuse reflectance spectra, we clarified that the absorption tail at room temperature is explained in terms of an Urbach tail and consistently determined the band-gap energy to be ˜1.61 eV at room temperature.

  7. Broadband perfect infrared absorption by tuning epsilon-near-zero and epsilon-near-pole resonances of multilayer ITO nanowires.

    PubMed

    Zhou, Kun; Cheng, Qiang; Song, Jinlin; Lu, Lu; Jia, Zhihao; Li, Junwei

    2018-01-01

    We numerically investigate the broadband perfect infrared absorption by tuning epsilon-near-zero (ENZ) and epsilon-near-pole (ENP) resonances of multilayer indium tin oxide nanowires (ITO NWs). The monolayer ITO NWs array shows intensive absorption at ENZ and ENP wavelengths for p polarization, while only at the ENP wavelength for s polarization. Moreover, the ENP resonances are almost omnidirectional and the ENZ resonances are angularly dependent. Therefore, the absorption bandwidth is broader for p polarization than that for s polarization when polarized waves are incident obliquely. The ENZ resonances can be tuned by altering the doping concentration and volume filling factor of ITO NWs. However, the ENP resonances only can be tuned by changing the doping concentration of ITO NWs, and volume filling factor impacts little on the ENP resonances. Based on the strong absorption properties of each layer at their own ENP and ENZ resonances, the tuned absorption of the bilayer ITO NWs with the different doping concentrations can be broader and stronger. Furthermore, multilayer ITO NWs can achieve broadband perfect absorption by controlling the doping concentration, volume filling factor, and length of the NWs in each layer. This study has the potential to apply to applications requiring efficient absorption and energy conversion.

  8. Transient Absorption of Attosecond Pulses by He Atoms in Presence of Near-Infrared Laser Fields: A TDDFT Analysis of Sub-Cycle Temporal Structures

    NASA Astrophysics Data System (ADS)

    Heslar, John; Telnov, Dmitry; Chu, Shih-I.

    2013-05-01

    We study transient absorption of extreme ultraviolet (XUV) attosecond pulses in presence of near-infrared (NIR) laser fields by analyzing the population and photon emission of excited atomic energy levels. We consider He atoms and apply a self-interaction-free fully ab initio time-dependent density functional theory (TDDFT). Our method is based on the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential and incorporates explicitly the self-interaction correction. We focus on the sub-cycle (with respect to NIR field) temporal behavior of the population of the excited energy levels and related dynamics of photon emission. We observe and identify sub-cycle shifts in the photon emission spectrum as a function of the time delay between the XUV and NIR pulses. In the region where the two pulses overlap, the photon emission peaks have an oscillatory structure with a period of 1.3 fs, which is half of the NIR laser optical cycle. Such a structure was also observed in recent experiments on transient absorption. This work was partially supported by DOE and by MOE-NSC-NTU-Taiwan.

  9. 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.

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

    DOE PAGES

    Bagge-Hansen, Michael; Wichmann, Andre; Wittstock, Arne; ...

    2014-02-03

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

  11. Operando Soft X-ray Absorption Spectroscopic Study on a Solid Oxide Fuel Cell Cathode during Electrochemical Oxygen Reduction.

    PubMed

    Nakamura, Takashi; Oike, Ryo; Kimura, Yuta; Tamenori, Yusuke; Kawada, Tatsuya; Amezawa, Koji

    2017-05-09

    An operando soft X-ray absorption spectroscopic technique, which enabled the analysis of the electronic structures of the electrode materials at elevated temperature in a controlled atmosphere and electrochemical polarization, was established and its availability was demonstrated by investigating the electronic structural changes of an La 2 NiO 4+δ dense-film electrode during an electrochemical oxygen reduction reaction. Clear O K-edge and Ni L-edge X-ray absorption spectra could be obtained below 773 K under an atmospheric pressure of 100 ppm O 2 /He, 0.1 % O 2 /He, and 1 % O 2 /He gas mixtures. Considerable spectral changes were observed in the O K-edge X-ray absorption spectra upon changing the PO2 and application of electrical potential, whereas only small spectral changes were observed in Ni L-edge X-ray absorption spectra. A pre-edge peak of the O K-edge X-ray absorption spectra, which reflects the unoccupied partial density of states of Ni 3d-O 2p hybridization, increased or decreased with cathodic or anodic polarization, respectively. The electronic structural changes of the outermost orbital of the electrode material due to electrochemical polarization were successfully confirmed by the operando X-ray absorption spectroscopic technique developed in this study. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Crystal structure and electronic states of Co and Gd ions in a Gd0.4Sr0.6CoO2.85 single crystal

    NASA Astrophysics Data System (ADS)

    Platunov, M. S.; Dudnikov, V. A.; Orlov, Yu. S.; Kazak, N. V.; Solovyov, L. A.; Zubavichus, Ya. V.; Veligzhanin, A. A.; Dorovatovskii, P. V.; Vereshchagin, S. N.; Shaykhutdinov, K. A.; Ovchinnikov, S. G.

    2016-02-01

    X-ray diffraction and X-ray absorption near edge structure (XANES) spectra have been measured at the Co K-edge and Gd L 3-edge in GdCoO3 and Gd0.4Sr0.6CoO2.85 cobaltites. The effect of Sr substitution on the crystal structure and electronic and magnetic states of Co3+ ions in a Gd0.4Sr0.6CoO2.85 single crystal has been analyzed. The XANES measurements at the Co K-edge have not showed a noticeable shift of the absorption edge with an increase in the concentration of Sr. This indicates that the effective valence of cobalt does not change. An increase in the intensity of absorption at the Gd L 3-edge is due to an increase in the degree of hybridization of the Gd(5 d) and O(2 p) states. The effect of hole doping on the magnetic properties results in the appearance of the ferromagnetic component and in a significant increase in the magnetic moment.

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

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

    Song, Zhen; Kenney, Janice P.L.; Fein, Jeremy B.

    2015-02-09

    Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has beenmore » observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.« less

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

    NASA Astrophysics Data System (ADS)

    Song, Zhen; Kenney, Janice P. L.; Fein, Jeremy B.; Bunker, Bruce A.

    2012-06-01

    Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has been observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.

  15. Complex Resonance Absorption Structure in the X-Ray Spectrum of IRAS 13349+2438

    NASA Technical Reports Server (NTRS)

    Sako, M.; Kahn, S. M.; Behar, E.; Kaastra, J. S.; Brinkman, A. C.; Boller, Th.; Puchnarewicz, E. M.; Starling, R.; Liedahl, D. A.; Clavel, J.

    2000-01-01

    The luminous infrared-loud quasar IRAS 13349+2438 was observed with the XMM - Newton Observatory as part of the Performance Verification program. The spectrum obtained by the Reflection Grating Spectrometer (RGS) exhibits broad (FWHM - 1400 km/s) absorption lines from highly ionized elements including hydrogen- and helium-like carbon, nitrogen, oxygen, and neon, and several iron L - shell ions (Fe XVII - XX). Also shown in the spectrum is the first astrophysical detection of a broad absorption feature around lambda = 16 - 17 A identified as an unresolved transition array (UTA) of 2p - 3d inner-shell absorption by iron M-shell ions in a much cooler medium; a feature that might be misidentified as an O VII edge when observed with moderate resolution spectrometers. No absorption edges are clearly detected in the spectrum. We demonstrate that the RGS spectrum of IRAS 13349+2438 exhibits absorption lines from two distinct regions, one of which is tentatively associated with the medium that produces the optical/UV reddening.

  16. Photo-Darkening Kinetics and Structural Anisotropic Modifications in the Chalcogenide Glass Arsenic Trisulfide: a Study of Kinetic X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lee, Jay Min

    1990-08-01

    The purpose of the study is to investigate the mechanisms involved with photo-induced atomic structural modifications in the chalcogenide glass As_2 S_3. This glass exhibits the reversible effects of photo-darkening followed by thermal bleaching. We observed the time behavior of photo-induced properties under the influence of linearly polarized band -gap light. In a macroscopic optical investigation, we monitor optical changes in the photo-darkening process, and in a local structural probe we study kinetic (or time -resolved dispersive) x-ray absorption spectroscopy. Our observations center on kinetic phenomena and structural modifications induced by polarized excitation of lone-pair orbitals in the chalcogenide glass. Experimental results include the following observations: (i) The polarity of the optically induced anisotropy is critically dependent on the intensity and the polarization of the band-gap irradiation beam. (ii) The near edge peak height in x-ray absorption spectra shows subtle but sensitive change during the photo-darkening process. (iii) Photon intensity dependent dichroic kinetics reflect a connection between the optically probed macroscopic property and the x-ray probed local anisotropic structure. Analysis of the x-ray absorption results includes a computer simulation of the polarized absorption spectra. These results suggest that specific structural units tend to orient themselves with respect to the photon polarization. A substantial part of the analysis involves a major effort in dealing with the x-ray kinetic data manipulation and the experimental difficulties caused by a synchrotron instability problem. Based on our observations, we propose a possible mechanism for the observed photo-structural modifications. Through a model of computer relaxed photo-darkening kinetics, we support the notion that a twisting of a specific intermediate range order structure is responsible for local directional variations and global network distortions. In the

  17. X-ray absorption spectroscopy study of Gd3+-loaded ultra-short carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Ma, Q.; Jebb, M.; Tweedle, M. F.; Wilson, L. J.

    2013-04-01

    We present an x-ray absorption spectroscopy study of the local structure around the Gd3+ion loaded in ultra short (20-100 nm) carbon nanotubes (GNTs). X-ray Gd L3 absorption near edge structure data shows that the 31.2-μM GNT suspension exhibits a clear characteristic of hydration at the [GdOn] cluster. Extended x-ray absorption fine structure data show that the Gd3+ ion is coordinated by about 9 oxygen ions and that this first coordination shell exhibits an asymmetry similar to that found in triclinic Gd-acetate or Gd[C2H3O2]3·4H2O or GdAc. After correction for the asymmetry using the cumulant of the third order, the Gd-O bond distance is found to be 2.345 Å, instead of 2.406 Å for a symmetrical (or Gaussian) distribution. It is shorter than that in the Gd-containing MRI contrast agents currently in clinical uses. This may account in part for high proton relaxivity observed for the GNT suspension.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    Delafossite oxides are a family of materials with the form ABO2 , where the A-site is a monovalent cation (Cu , Ag , Au) and the B-site is a trivalent cation (Ga , Al , In). Delafossites typically have a wide optical band gap, this band gap may be tuned by adding a second B-site element forming an AB(1- x) 1B(x)2O2 alloy. We investigate changes in the electronic structure of CuAlO2 , CuGaO2 , and CuInO2 when alloyed with CuFeO2 . Using the FIREBALL program to optimize the atomic structure, calculate the total and partial density of states, calculate the valence band edge for each alloy level, and investigate the clustering factor of the second B-site atom, it is found that alloying with Fe creates midgap states caused by Fe - O interactions. From the partial density of state, each type of atoms contribution to the change in the valence band edge can be seen. Observed changes to the materials include increased optical absorption in the visible range, and symmetry breaking because of the deformation in the crystal structure. The CuFeO2 alloying percentages range from 0-5%. We are synthesizing these alloys to experimentally verify the changes in the optical absorption spectra.

  20. 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

  1. Near band edge emission characteristics of sputtered nano-crystalline ZnO films

    NASA Astrophysics Data System (ADS)

    Kunj, Saurabh; Sreenivas, K.

    2016-05-01

    Sputtered zinc oxide (ZnO) thin films deposited on unheated glass substrate under different sputtering gas mixtures (Ar+O2) have been investigated using X-ray diffraction and photo luminescence spectroscopy. Earlier reported studies on ZnO films prepared by different techniques exhibit either a sharp/broad near band edge (NBE) emission peak depending on the crystalline quality of the film. In the present study zinc oxide films, grown on unheated substrates, are seen to possess a preferred (002) orientation with a microstructure consisting of clustered nano-sized crystallites. The splitting in the near band edge emission (NBE) into three characteristic peaks is attributed to quantum confinement effect, and is observed specifically under an excitation of 270 nm. Deep level emission (DLE) in the range 400 to 700 nm is not observed indicating absence of deep level radiative defects.

  2. 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.

  3. 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.

  4. Interband absorption edge in the topological insulators Bi2(Te1-xSex) 3

    NASA Astrophysics Data System (ADS)

    Dubroka, A.; Caha, O.; Hronček, M.; Friš, P.; Orlita, M.; Holý, V.; Steiner, H.; Bauer, G.; Springholz, G.; Humlíček, J.

    2017-12-01

    We have investigated the optical properties of thin films of topological insulators Bi2Te3 , Bi2Se3 , and their alloys Bi2(Te1-xSex) 3 on BaF2 substrates by a combination of infrared ellipsometry and reflectivity in the energy range from 0.06 to 6.5 eV. For the onset of interband absorption in Bi2Se3 , after the correction for the Burstein-Moss effect, we find the value of the direct band gap of 215 ±10 meV at 10 K. Our data support the picture that Bi2Se3 has a direct band gap located at the Γ point in the Brillouin zone and that the valence band reaches up to the Dirac point and has the shape of a downward-oriented paraboloid, i.e., without a camel-back structure. In Bi2Te3 , the onset of strong direct interband absorption at 10 K is at a similar energy of about 200 meV, with a weaker additional feature at about 170 meV. Our data support the recent G W band-structure calculations suggesting that the direct interband transition does not occur at the Γ point but near the Z -F line of the Brillouin zone. In the Bi2(Te1-xSex) 3 alloy, the energy of the onset of direct interband transitions exhibits a maximum near x =0.3 (i.e., the composition of Bi2Te2Se ), suggesting that the crossover of the direct interband transitions between the two points in the Brillouin zone occurs close to this composition.

  5. Effects of alkyl spacer group length on Vis-NIR absorption behavior in FTC-like guest-host EO polymers

    NASA Astrophysics Data System (ADS)

    Barto, Richard R., Jr.; Bedworth, Peter V.; Epstein, Joseph A.; Ermer, Susan P.; Taylor, Rebecca E.; Frank, Curtis W.

    2003-07-01

    Spectral absorption behavior of a series of FTC-like dyes of varying shape incorporated into amorphous polycarbonate (APC) is characterized by photothermal deflection spectroscopy. Previous Monte Carlo calculations by Dalton and Robinson predict a strong dependence of the macroscopic nonlinear optical susceptibility on the chromophore waist:length aspect ratio in electric field-poled films. This dependence arises from London interactions between chromophores, which are expected to influence the absorption characteristics of the composite both by changing the local polarity of the medium and through dipole interactions. It is expected that these interactions will play a role in the absorption characteristics of unpoled films as well. Of particular interest are the spectral characteristics of the red edge of the main dye electronic absorption peak, and the fine structure in the near-IR, dominated by overtones of fundamental C-H stretching and bending modes. The spectral structure in these key regions can be influenced by inter- and intramolecular interactions and conformational changes in the dye. The near-IR structure, in turn, will dictate absorption loss in optical devices prepared from these materials at key transmission wavelengths (1.3 and 1.55 um). In this study, a homologous series of spacer lengths, ranging from ethyl to hexyl, attached to an FTC-like NLO chromophore, LMCO-46M, is characterized by a combination of photothermal deflection spectroscopy (PDS) and UV-Vis spectroscopy to examine the effects of the molecular environment on near-IR loss at 1090 nm, 1300 nm and 1550 nm.

  6. 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

  7. 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.

  8. Local atomic and electronic structures of epitaxial strained LaCoO3 thin films

    NASA Astrophysics Data System (ADS)

    Sterbinsky, G. E.; Ryan, P. J.; Kim, J.-W.; Karapetrova, E.; Ma, J. X.; Shi, J.; Woicik, J. C.

    2012-01-01

    We have examined the atomic and electronic structures of perovskite lanthanum cobaltite (LaCoO3) thin films using Co K-edge x-ray absorption fine structure (XAFS) spectroscopy. Extended XAFS (EXAFS) demonstrates that a large difference between in-plane and out-of-plane Co-O bond lengths results from tetragonal distortion in highly strained films. The structural distortions are strongly coupled to the hybridization between atomic orbitals of the Co and O atoms, as shown by x-ray absorption near edge spectroscopy (XANES). Our results indicate that increased hybridization is not the cause of ferromagnetism in strained LaCoO3 films. Instead, we suggest that the strain-induced distortions of the oxygen octahedra increase the population of eg electrons and concurrently depopulate t2g electrons beyond a stabilization threshold for ferromagnetic order.

  9. Theoretical X-ray production cross sections at incident photon energies across Li (i=1-3) absorption edges of Br

    NASA Astrophysics Data System (ADS)

    Puri, Sanjiv

    2015-08-01

    The X-ray production (XRP) cross sections, σLk (k = l, η, α, β6, β1, β3, β4, β9,10, γ1,5, γ2,3) have been evaluated at incident photon energies across the Li(i=1-3) absorption edge energies of 35Br using theoretical data sets of different physical parameters, namely, the Li(i=1-3) sub-shell the X-ray emission rates based on the Dirac-Fock (DF) model, the fluorescence and Coster Kronig yields based on the Dirac-Hartree-Slater (DHS) model, and two sets of the photoionisation cross sections based on the relativistic Hartree-Fock-Slater (RHFS) model and the Dirac-Fock (DF) model, in order to highlight the importance of electron exchange effects at photon energies in vicinity of absorption edge energies.

  10. Polarization dependent formation of femtosecond laser-induced periodic surface structures near stepped features

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

    Murphy, Ryan D.; Torralva, Ben; Adams, David P.

    2014-06-09

    Laser-induced periodic surface structures (LIPSS) are formed near 110 nm-tall Au microstructured edges on Si substrates after single-pulse femtosecond irradiation with a 150 fs pulse centered near a 780 nm wavelength. We investigate the contributions of Fresnel diffraction from step-edges and surface plasmon polariton (SPP) excitation to LIPSS formation on Au and Si surfaces. For certain laser polarization vector orientations, LIPSS formation is dominated by SPP excitation; however, when SPP excitation is minimized, Fresnel diffraction dominates. The LIPSS orientation and period distributions are shown to depend on which mechanism is activated. These results support previous observations of the laser polarization vectormore » influencing LIPSS formation on bulk surfaces.« less

  11. High temperature extended x-ray absorption fine structure study of multiferroic BiFeO3

    NASA Astrophysics Data System (ADS)

    Raghavendra Reddy, V.; Meneghini, Carlo; Kothari, Deepti; Gupta, Ajay; Aquilanti, Giuliana

    2012-08-01

    Local atomic structure modifications around Fe atoms in polycrystalline multiferroic BiFeO3 are studied by Fe K edge x-ray absorption spectroscopy as a function of temperature across the Néel temperature (TN = 643 K) in order to reveal local structure modifications related to the magnetic transition. This work demonstrates that on crossing TN the local structure around Fe shows peculiar changes: the Fe-O bond lengths get shorter, the ligand symmetry increases and the Fe-O bond length disorder (σ2) deviates from Debye behaviour. These results suggest that the structural transition at the ferroelectric Curie temperature (TC = 1103 K) is anticipated by early local rearrangement of the structure starting already at TN.

  12. Spiky Fine Structure of Type III-like Radio Bursts in Absorption

    NASA Astrophysics Data System (ADS)

    Chernov, G. P.; Yan, Y. H.; Tan, C. M.; Chen, B.; Fu, Q. J.

    2010-03-01

    An uncommon fine structure in the radio spectrum consisting of bursts in absorption was observed with the Chinese Solar Broadband Radiospectrometer (SBRS) in the frequency range of 2.6 - 3.8 GHz during an X3.4/4B flare on 13 December 2006 in active region NOAA 10930 (S05W33). Usual fine structures in emission such as spikes, zebra stripes, and drifting fibers were observed at the peak of every new flare brightening. Within an hour at the decay phase of the event we observed bursts consisting of spikes in absorption, which pulsated periodically in frequency. Their instantaneous frequency bandwidths were found to be in the 75 MHz range. Moreover, in the strongest Type III-like bursts in absorption, the spikes showed stripes of the zebra-pattern (ZP) that drifted to higher frequencies. All spikes had the duration as short as down to the limit of the instrument resolution of ≈8 ms. The TRACE 195 Å images indicate that the magnetic reconnection at this moment occurred in the western edge of the flare loop arcade. Taking into account the presence of the reverse-drifting bursts in emission, in the course of the restoration of the magnetic structures in the corona, the acceleration of the beams of fast particles must have occurred both upward and downward at different heights. The upward beams will be captured by the magnetic trap, where the loss-cone distribution of fast particles (responsible for the emission of continuum and ZP) were formed. An additional injection of fast particles will fill the loss-cone later, breaking the loss-cone distribution. Therefore, the generation of continuum will be quenched at these moments, which was evidenced by the formation of bursts in absorption.

  13. 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.

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

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

    Advanced Light Source; Schwartz, Craig P.; Uejio, Janel S.

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

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

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

    Schwartz, Craig P.; Uejio, Janel S.; Duffin, Andrew M.

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

  16. An X-ray absorption spectroscopy study of the inversion degree in zinc ferrite nanocrystals dispersed on a highly porous silica aerogel matrix.

    PubMed

    Carta, D; Marras, C; Loche, D; Mountjoy, G; Ahmed, S I; Corrias, A

    2013-02-07

    The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO(2) aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn(2+) ions are at the tetrahedral sites and trivalent Fe(3+) ions occupy octahedral sites (normal spinel). When particle size decreases, Zn(2+) ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix.

  17. Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

    PubMed

    Nguyen, Luan; Tao, Franklin Feng

    2018-02-01

    Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

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

    PubMed

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

    2008-01-21

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

  19. Influence of defects on the absorption edge of InN thin films: The band gap value

    NASA Astrophysics Data System (ADS)

    Thakur, J. S.; Danylyuk, Y. V.; Haddad, D.; Naik, V. M.; Naik, R.; Auner, G. W.

    2007-07-01

    We investigate the optical-absorption spectra of InN thin films whose electron density varies from ˜1017tõ1021cm-3 . The low-density films are grown by molecular-beam-epitaxy deposition while highly degenerate films are grown by plasma-source molecular-beam epitaxy. The optical-absorption edge is found to increase from 0.61to1.90eV as the carrier density of the films is increased from low to high density. Since films are polycrystalline and contain various types of defects, we discuss the band gap values by studying the influence of electron degeneracy, electron-electron, electron-ionized impurities, and electron-LO-phonon interaction self-energies on the spectral absorption coefficients of these films. The quasiparticle self-energies of the valence and conduction bands are calculated using dielectric screening within the random-phase approximation. Using one-particle Green’s function analysis, we self-consistently determine the chemical potential for films by coupling equations for the chemical potential and the single-particle scattering rate calculated within the effective-mass approximation for the electron scatterings from ionized impurities and LO phonons. By subtracting the influence of self-energies and chemical potential from the optical-absorption edge energy, we estimate the intrinsic band gap values for the films. We also determine the variations in the calculated band gap values due to the variations in the electron effective mass and static dielectric constant. For the lowest-density film, the estimated band gap energy is ˜0.59eV , while for the highest-density film, it varies from ˜0.60tõ0.68eV depending on the values of electron effective mass and dielectric constant.

  20. 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

  1. Particle-in-a-box model of exciton absorption and electroabsorption in conjugated polymers

    NASA Astrophysics Data System (ADS)

    Pedersen, Thomas G.

    2000-12-01

    The recently proposed particle-in-a-box model of one-dimensional excitons in conjugated polymers is applied in calculations of optical absorption and electroabsorption spectra. It is demonstrated that for polymers of long conjugation length a superposition of single exciton resonances produces a line shape characterized by a square-root singularity in agreement with experimental spectra near the absorption edge. The effects of finite conjugation length on both absorption and electroabsorption spectra are analyzed.

  2. Nonlinear reconnecting edge localized modes in current-carrying plasmas

    DOE PAGES

    Ebrahimi, F.

    2017-05-22

    Nonlinear edge localized modes in a tokamak are examined using global three-dimensional resistive magnetohydrodynamics simulations. Coherent current-carrying filament (ribbon-like) structures wrapped around the torus are nonlinearly formed due to nonaxisymmetric reconnecting current sheet instabilities, the so-called peeling-like edge localized modes. These fast growing modes saturate by breaking axisymmetric current layers isolated near the plasma edge and go through repetitive relaxation cycles by expelling current radially outward and relaxing it back. The local bidirectional fluctuation-induced electromotive force (emf) from the edge localized modes, the dynamo action, relaxes the axisymmetric current density and forms current holes near the edge. Furthermore, the three-dimensionalmore » coherent current-carrying filament structures (sometimes referred to as 3-D plasmoids) observed here should also have strong implications for solar and astrophysical reconnection.« less

  3. 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.

  4. Near-perfect broadband absorption from hyperbolic metamaterial nanoparticles

    NASA Astrophysics Data System (ADS)

    Riley, Conor T.; Smalley, Joseph S. T.; Brodie, Jeffrey R. J.; Fainman, Yeshaiahu; Sirbuly, Donald J.; Liu, Zhaowei

    2017-02-01

    Broadband absorbers are essential components of many light detection, energy harvesting, and camouflage schemes. Current designs are either bulky or use planar films that cause problems in cracking and delamination during flexing or heating. In addition, transferring planar materials to flexible, thin, or low-cost substrates poses a significant challenge. On the other hand, particle-based materials are highly flexible and can be transferred and assembled onto a more desirable substrate but have not shown high performance as an absorber in a standalone system. Here, we introduce a class of particle absorbers called transferable hyperbolic metamaterial particles (THMMP) that display selective, omnidirectional, tunable, broadband absorption when closely packed. This is demonstrated with vertically aligned hyperbolic nanotube (HNT) arrays composed of alternating layers of aluminum-doped zinc oxide and zinc oxide. The broadband absorption measures >87% from 1,200 nm to over 2,200 nm with a maximum absorption of 98.1% at 1,550 nm and remains large for high angles. Furthermore, we show the advantages of particle-based absorbers by transferring the HNTs to a polymer substrate that shows excellent mechanical flexibility and visible transparency while maintaining near-perfect absorption in the telecommunications region. In addition, other material systems and geometries are proposed for a wider range of applications.

  5. 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.

  6. Electronic Structures and Optical Properties of α-Al2O3Nanowires

    NASA Astrophysics Data System (ADS)

    Wang, Zhiqiang; Li, Chunlei; Liu, Lijia; Sham, Tsun-Kong

    2013-04-01

    The electronic structure and optical properties of α-Al2O3 nanowires (NWs) have been investigated using X-ray absorption near-edge structures (XANES) and X-ray excited optical luminescence (XEOL). The XANES were recorded in total electron yield (TEY) and total fluorescence yield (TFY) across the K- and L3,2-edges of aluminium and the K-edge of oxygen. The results indicate that the NWs are of a core/shell structure with a single-crystalline core and an amorphous shell. The XEOL spectra of the NWs show an intense peak at 404 nm, which comes from the F centre located in the amorphous shell of the NWs. The implication of these findings and the sensitivity of XEOL for defect detection are discussed.

  7. 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

  8. 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

  9. X-ray absorption spectroscopy and photoluminescence study of rare earth ions doped strontium sulphide phosphors

    NASA Astrophysics Data System (ADS)

    Vij, Ankush; Gautam, Sanjeev; Kumar, Vinay; Brajpuriya, R.; Kumar, Ravi; Singh, Nafa; Chae, Keun Hwa

    2013-01-01

    We present here the electronic structure and photoluminescence properties of Sm (0.1-1.0 mol%) doped SrS phosphors. The doping in SrS was probed by near-edge X-ray absorption fine structure (NEXAFS) at M5,4-edges of Sm in total electron yield mode. The simulated absorption edges using atomic multiplet calculations were correlated with experimental results, which clearly reveal the presence of trivalent state of Sm in SrS matrix. However, for Sm (1 mol%), very minor traces of Sm2+ were also observed, which have been explained by comparing the NEXAFS spectra in total electron and florescence yield mode. The PL emission of SrS:Sm comprises of three sharp bands at 567, 602 and 650 nm owing to the well-known intra 4f transitions from 4G5/2 to 6HJ (J = 5/2, 7/2, 9/2) levels of Sm3+ ions in SrS host. The effect of Ce co-doping on SrS:Sm phosphors was also investigated, which exhibits characteristic PL emission of independent ions at their respective excitation wavelengths. However, at an excitation wavelength of 393 nm, SrS:Ce,Sm exhibits the simultaneous characteristic PL emission of both ions spanning into blue-green-red region. The CIE chromaticity coordinates also clearly show the influence of excitation wavelengths on the emission colour of SrS:Ce,Sm.

  10. Consequences of realistic embedding for the L 2,3 edge XAS of α-Fe 2 O 3

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

    Bagus, Paul S.; Nelin, Connie J.; Sassi, Michel

    Cluster models of condensed systems are often used to simulate the core-level spectra obtained with X-ray Photoelectron Spectroscopy, XPS, or with X-ray Absorption Spectroscopy, XAS, especially for near edge features.

  11. 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

  12. 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.

  13. Anomalous nonlinear absorption in epsilon-near-zero materials: optical limiting and all-optical control.

    PubMed

    Vincenti, M A; de Ceglia, D; Scalora, Michael

    2016-08-01

    We investigate nonlinear absorption in films of epsilon-near-zero materials. The combination of large local electric fields at the fundamental frequency and material losses at the harmonic frequencies induce unusual intensity-dependent phenomena. We predict that the second-order nonlinearity of a low-damping, epsilon-near-zero slab produces an optical limiting effect that mimics a two-photon absorption process. Anomalous absorption profiles that depend on low permittivity values at the pump frequency are also predicted for third-order nonlinearities. These findings suggest new opportunities for all-optical light control and novel ways to design reconfigurable and tunable nonlinear devices.

  14. Bond-length relaxation in crystalline Si1-xGex alloys: An extended x-ray-absorption fine-structure study

    NASA Astrophysics Data System (ADS)

    Kajiyama, Hiroshi; Muramatsu, Shin-Ichi; Shimada, Toshikazu; Nishino, Yoichi

    1992-06-01

    Extended x-ray-absorption fine-structure spectra for crystalline Si1-xGex alloys, measured at the K edge of Ge at room temperature, are analyzed with a curve-fitting method based on the spherical-wave approximation. The Ge-Ge and Ge-Si bond lengths, coordination numbers of Ge and Si atoms around a Ge atom, and Debye-Waller factors of Ge and Si atoms are obtained. It is shown that Ge-Ge and Ge-Si bonds relax completely, for all Ge concentrations of their study, while the lattice constant varies monotonically, following Vegard's law. As noted by Bragg and later by Pauling and Huggins, the Ge-Ge and Ge-Si bond lengths are close to the sum of their constituent-element atomic radii: nearly 2.45 Å for Ge-Ge bonds and 2.40 Å for Ge-Si bonds. A study on the coordination around a Ge atom in the alloys revealed that Ge and Si atoms mix randomly throughout the compositional range studied.

  15. Experimental and simulated study of a composite structure metamaterial absorber

    NASA Astrophysics Data System (ADS)

    Li, Shengyong; Ai, Xiaochuan; Wu, Ronghua; Chen, Jiajun

    2017-11-01

    In this paper, a high performance metamaterial absorber is designed and experimental studied. Measured results indicate that a perfect absorption band and a short-wavelength absorption peak are achieved in the near-infrared spectrum. Current strength distributions reveal that the absorption band is excited by the cavity resonance. And electric field distributions show that the short-wavelength absorption peak is excited by the horizontal coupled of localized surface plasmon (LSP) modes near hole edges. On the one hand, the absorption property of the measured metamaterial absorber can be enhanced through optimizing the structural parameters (a, w, and H). On the other hand, the absorption property is sensitive to the change of refractive index of environmental medias. A sensing scheme is proposed for refractive index detecting based on the figure of merit (FOM) value. Measured results indicate that the proposed sensing scheme can achieve high FOM value with different environmental medias (water, glucose solution).

  16. Edge detection based on computational ghost imaging with structured illuminations

    NASA Astrophysics Data System (ADS)

    Yuan, Sheng; Xiang, Dong; Liu, Xuemei; Zhou, Xin; Bing, Pibin

    2018-03-01

    Edge detection is one of the most important tools to recognize the features of an object. In this paper, we propose an optical edge detection method based on computational ghost imaging (CGI) with structured illuminations which are generated by an interference system. The structured intensity patterns are designed to make the edge of an object be directly imaged from detected data in CGI. This edge detection method can extract the boundaries for both binary and grayscale objects in any direction at one time. We also numerically test the influence of distance deviations in the interference system on edge extraction, i.e., the tolerance of the optical edge detection system to distance deviation. Hopefully, it may provide a guideline for scholars to build an experimental system.

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

    DOE PAGES

    Kinsey, Jon E.; Staebler, Gary M.; Candy, Jefferey M.; ...

    2015-01-14

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

  18. 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.

  19. STM/STS investigation of edge structure in epitaxial graphene

    NASA Astrophysics Data System (ADS)

    Ridene, M.; Girard, J. C.; Travers, L.; David, C.; Ouerghi, A.

    2012-08-01

    In this paper, we have used low temperature scanning tunneling microscopy and spectroscopy (LT-STM/STS) to study zigzag or armchair edges of epitaxial graphene on 6H-SiC (0001). The monolayer carbon structures exhibit occasionally one-dimensional ridge (1D) in close vicinity to step edge. This ridge exhibits different edges orientations in armchair-zigzag transition which give rise to different local density of states (LDOS) along this 1D structure. This ridge formation is likely explained by residual compressive in-plane stresses.

  20. X-ray-induced debromination of nucleic acids at the Br K absorption edge and implications for MAD phasing.

    PubMed

    Ennifar, E; Carpentier, P; Ferrer, J L; Walter, P; Dumas, P

    2002-08-01

    Multi-wavelength anomalous dispersion (MAD) using brominated derivatives is considered a common and convenient technique for solving chemically synthesized nucleic acid structures. Here, it is shown that a relatively moderate X-ray dose (of the order of 5 x 10(15) photons mm(-2)) can induce sufficient debromination to prevent structure determination. The decrease in bromine occupancy with radiation dose can be accounted for by a simple exponential, with an estimated rate constant at the absorption-peak wavelength, 7.4 (0.8) MGy, that is not significantly different from its value at the absorption-edge wavelength, 9.2 (2.6) MGy (the given e.s.d.s assess the relative closeness of the two values, not their absolute accuracy, which is probably worse). Chemically, these results (and others) are consistent with bromine cleavage resulting from direct photodissociation and/or from the action of free electrons, rather than from the action of hydroxyl radicals originating from water dissociation. The free bromine species (Br(-)) diffuse too quickly, even in amorphous ice around 100 K, to allow the determination of a diffusion coefficient. From a practical point of view, it is suggested that a single data collection with a crystal consisting of iodinated instead of brominated derivatives could provide both anomalous scattering and SIR phase information by the progressive cleavage of iodine.

  1. 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.

  2. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy below 100 eV: probing first-row transition-metal M-edges in chemical complexes.

    PubMed

    Wang, Hongxin; Young, Anthony T; Guo, Jinghua; Cramer, Stephen P; Friedrich, Stephan; Braun, Artur; Gu, Weiwei

    2013-07-01

    X-ray absorption and scattering spectroscopies involving the 3d transition-metal K- and L-edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M-edges, which are below 100 eV. Synchrotron-based X-ray sources can have higher energy resolution at M-edges. M-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) could therefore provide complementary information to K- and L-edge spectroscopies. In this study, M2,3-edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M2,3-edge RIXS on NiO, NiF2 and two other covalent complexes have been performed and different d-d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M-edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high-sensitivity and high-resolution superconducting tunnel junction X-ray detectors below 100 eV is also illustrated and discussed.

  3. Depth distribution of secondary phases in kesterite Cu 2ZnSnS 4 by angle-resolved X-ray absorption spectroscopy

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

    Just, J.; Lützenkirchen-Hecht, D.; Müller, O.

    The depth distribution of secondary phases in the solar cell absorber material Cu 2ZnSnS 4 (CZTS) is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES) analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

  4. Depth distribution of secondary phases in kesterite Cu 2ZnSnS 4 by angle-resolved X-ray absorption spectroscopy

    DOE PAGES

    Just, J.; Lützenkirchen-Hecht, D.; Müller, O.; ...

    2017-12-12

    The depth distribution of secondary phases in the solar cell absorber material Cu 2ZnSnS 4 (CZTS) is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES) analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

  5. The active site structure of tetanus neurotoxin resolved by multiple scattering analysis in X-Ray absorption spectroscopy.

    PubMed Central

    Meneghini, C; Morante, S

    1998-01-01

    A detailed study of the x-ray absorption spectrum of tetanus neurotoxin in the K-edge EXAFS region of the zinc absorber is presented that allows the complete identification of the amino acid residues coordinated to the zinc active site. A very satisfactory interpretation of the experimental data can be given if multiple scattering contributions are included in the analysis. Comparing the absorption spectrum of tetanus neurotoxin to that of two other structurally similar zinc-endopeptidases, thermolysin and astacin, in which the zinc coordination mode is known from crystallographic data, we conclude that in tetanus neurotoxin, besides a water molecule, zinc is coordinated to two histidines and a tyrosine. PMID:9746536

  6. X-Ray Absorption Spectroscopy Studies of the Atomic Structure of Zirconium-Doped Lithium Silicate Glasses and Glass-Ceramics, Zirconium-Doped Lithium Borate Glasses, and Vitreous Rare-Earth Phosphates

    NASA Astrophysics Data System (ADS)

    Yoo, Changhyeon

    In the first part of this work, the atomic-scale structure around rare-earth (RE = Pr, Nd, Eu, Dy, and Er) cations (RE3+) in rare-earth sodium ultraphosphate (REUP) glasses were investigated using RE LIII -edge (RE = Nd, Er, Dy, and Eu) and K-edge (RE = Pr and Dy) Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. (RE2O 3)x(Na2O)y(P2O5) 1-x-y glasses in the compositional range 0 ≤ x ≤ 0.14 and 0.3 ≤ x + y ≤ 0.4 were studied. For the nearest oxygen shell, the RE-oxygen (RE-O) coordination number decreases from 10.8 to 6.5 with increasing RE content for Pr-, Nd-, Dy-, and Er-doped sodium ultraphosphate glasses. For Eu-doped samples, the Eu-O coordination number was between 7.5 and 8.8. Also, the RE-O mean distance ranges were between 2.43-2.45 A, 2.40-2.43 A, 2.36-2.38 A, 2.30-2.35 A, and 2.28-2.30 A for Pr-, Nd-, Eu-, Dy-, and Er-doped samples, respectively. In the second part, a series of Zr-doped (3-10 mol%) lithium silicate (ZRLS) glass-ceramics and their parent glasses and a series of Zr-doped (2-6 mol% ZrO2) lithium borate (ZRLB) glasses were investigated using Zr K-edge EXAFS and X-ray Absorption Near Edge Structure (XANES) spectroscopy. Immediate coordination environments of all ZRLS glasses are remarkably similar for different compositions. For the nearest oxygen shell, the Zr-O coordination number ranges were between 6.1 and 6.3 for nucleated and crystallized samples, respectively. Also, the Zr-O mean distance remains similar around 2.10 A. For these glasses, the composition dependence of structural parameters was small. Small changes in the coordination environment were observed for ZRLS glass-ceramics after thermal treatments. In contrast, Zr coordination environment in ZRLB glasses appear to depend appreciably on the Zr concentration. For the nearest oxygen shell, the Zr-O coordination number increased from 6.1 to 6.8 and the Zr-O distance decreased from 2.18 A to 2.14 A with decreasing ZrO2 content.

  7. Electronic structure, bonding, charge distribution, and x-ray absorption spectra of the (001) surfaces of fluorapatite and hydroxyapatite from first principles

    NASA Astrophysics Data System (ADS)

    Rulis, Paul; Yao, Hongzhi; Ouyang, Lizhi; Ching, W. Y.

    2007-12-01

    Fluorapatite (FAP) and hydroxyapatite (HAP) are two very important bioceramic crystals. The (001) surfaces of FAP and HAP crystals are studied by ab initio density functional calculations using a supercell slab geometry. It is shown that in both crystals, the O-terminated (001) surface is more stable with calculated surface energies of 0.865 and 0.871J/m2 for FAP and HAP, respectively. In FAP, the two surfaces are symmetric. In HAP, the orientation of the OH group along the c axis reduces the symmetry such that the top and bottom surfaces are no longer symmetric. It is revealed that the atoms near the surface and subsurface are significantly relaxed especially in the case of HAP. The largest relaxations occurred via the lateral movements of the O ions at the subsurface level. The electronic structures of the surface models in the form of layer-by-layer resolved partial density of states for all the atoms show systematic variation from the surface region toward the bulk region. The calculated Mulliken effective charge on each type of atom and the bond order values between cations (Ca, P) and anions (O, F) show different charge transfers and bond strength variations from the bulk crystal values. Electron charge density calculations show that the surfaces of both FAP and HAP crystals are mostly positively charged due to the presence of Ca ions at the surface. The positively charged surfaces have implications for the absorption on apatite surfaces of water and other organic molecules in an aqueous environment which are an important part of its bioactivity. The x-ray absorption near-edge structure (XANES) spectra ( Ca-K , O-K , F-K , P-K , and P-L3 edges) of both the surface models and the bulk crystals are calculated and compared. The calculations use a supercell approach which takes into account the electron-core-hole interaction. It is shown that the site-specific XANES spectra show significant differences between atoms near the surface and in the bulk and are very

  8. Structural, magnetic and electronic structure properties of Co doped ZnO nanoparticles

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

    Kumar, Shalendra, E-mail: shailuphy@gmail.com; School of Materials Science and Engineering, Changwon National University, Changwon, Gyeongnam 641-773; Song, T.K., E-mail: tksong@changwon.ac.kr

    Highlights: • XRD and HR-TEM results show the single phase nature of Co doped ZnO nanoparticles. • XMCD and dc magnetization results indicate the RT-FM in Co doped ZnO nanoparticles. • Co L{sub 3,2} NEXAFS spectra infer that Co ions are in 2+ valence state. • O K edge NEXAFS spectra show that O vacancy increases with Co doping in ZnO. - Abstract: We reported structural, magnetic and electronic structure studies of Co doped ZnO nanoparticles. Doping of Co ions in ZnO host matrix has been studied and confirmed using various methods; such as X-ray diffraction (XRD), field emission scanningmore » electron microscopy (FE-SEM), energy dispersed X-ray (EDX), high resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FT-IR), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, magnetic hysteresis loop measurements and X-ray magnetic circular dichroism (XMCD). From the XRD and HR-TEM results, it is observed that Co doped ZnO nanoparticles have single phase nature with wurtzite structure and exclude the possibility of secondary phase formation. FE-SEM and TEM micrographs show that pure and Co doped nanoparticles are nearly spherical in shape. O K edge NEXAFS spectra indicate that O vacancies increase with Co doping. The Co L{sub 3,2} edge NEXAFS spectra revealed that Co ions are in 2+ valence state. DC magnetization hysteresis loops and XMCD results clearly showed the intrinsic origin of temperature ferromagnetism in Co doped ZnO nanoparticles.« less

  9. 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

  10. Compound formation and superconductivity in Au-Si: X-ray absorption measurements on ion-beam-mixed Au-Si films

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

    Jeon, Y.; Jisrawi, N.; Liang, G.

    Multilayered Au-Si thin films have been deposited with the net compositions ''Au/sub 1-//sub x/Si/sub x/,'' x = 0.29, 0.5, and 0.8. After ion-beam mixing these films exhibited superconductivity in the 0.3--1.2 K range despite the nonsuperconducting character of both Au and Si. Near-edge x-ray absorption spectroscopy (XAS) measurements on the Au L/sub 3/ edge in these films indicate that metastable Au-Si compound formation occurs in these ion-mixed materials. Specifically, the XAS measurements indicate changes in Au 5d-orbital occupancy and changes in the local Au structural environment which are both consistent with local compound formation.

  11. Electronic structure and magnetic properties of Ni-doped SnO2 thin films

    NASA Astrophysics Data System (ADS)

    Sharma, Mayuri; Kumar, Shalendra; Alvi, P. A.

    2018-05-01

    This paper reports the electronic structure and magnetic properties of Ni-doped SnO2 thin film which were grown on Si (100) substrate by PLD (pulse laser deposition) technique under oxygen partial pressure (PO2). For getting electronic structure and magnetic behavior, the films were characterized using near edge X-ray absorption fine structure spectroscopy (NEXAFS) and DC magnetization measurements. The NEXAFS study at Ni L3,2 edge has been done to understand the local environment of Ni and Sn ions within SnO2 lattice. DC magnetization measurement shows that the saturation magnetization increases with the increase in substitution of Ni2+ ions in the system.

  12. Electronic structure, magnetic and structural properties of Ni doped ZnO nanoparticles

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

    Kumar, Shalendra, E-mail: shailuphy@gmail.com; Vats, Prashant; Gautam, S.

    Highlights: • XRD, and HR-TEM results show the single phase nature of Ni doped ZnO nanoparticles. • dc magnetization results indicate the RT-FM in Ni doped ZnO nanoparticles. • Ni L{sub 3,2} edge NEXAFS spectra infer that Ni ions are in +2 valence state. • O K edge NEXAFS spectra show that O vacancy increases with Ni doping in ZnO. - Abstract: We report structural, magnetic and electronic structural properties of Ni doped ZnO nanoparticles prepared by auto-combustion method. The prepared nanoparticles were characterized by using X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), near edge X-ray absorption finemore » structure (NEXAFS) spectroscopy, and dc magnetization measurements. The XRD and HR-TEM results indicate that Ni doped ZnO nanoparticles have single phase nature with wurtzite lattice and exclude the presence of secondary phase. NEXAFS measurements performed at Ni L{sub 3,2}-edges indicates that Ni ions are in +2 valence state and exclude the presence of Ni metal clusters. O K-edge NEXAFS spectra indicate an increase in oxygen vacancies with Ni-doping, while Zn L{sub 3,2}-edge show the absence of Zn-vacancies. The magnetization measurements performed at room temperature shows that pure and Ni doped ZnO exhibits ferromagnetic behavior.« less

  13. ECCENTRICITY TRAP: TRAPPING OF RESONANTLY INTERACTING PLANETS NEAR THE DISK INNER EDGE

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

    Ogihara, Masahiro; Ida, Shigeru; Duncan, Martin J., E-mail: ogihara@geo.titech.ac.j, E-mail: ida@geo.titech.ac.j, E-mail: duncan@astro.queensu.c

    2010-10-01

    Using orbital integration and analytical arguments, we have found a new mechanism (an 'eccentricity trap') to halt type I migration of planets near the inner edge of a protoplanetary disk. Because asymmetric eccentricity damping due to disk-planet interaction on the innermost planet at the disk edge plays a crucial role in the trap, this mechanism requires continuous eccentricity excitation and hence works for a resonantly interacting convoy of planets. This trap is so strong that the edge torque exerted on the innermost planet can completely halt type I migrations of many outer planets through mutual resonant perturbations. Consequently, the convoymore » stays outside the disk edge, as a whole. We have derived a semi-analytical formula for the condition for the eccentricity trap and predict how many planets are likely to be trapped. We found that several planets or more should be trapped by this mechanism in protoplanetary disks that have cavities. It can be responsible for the formation of non-resonant, multiple, close-in super-Earth systems extending beyond 0.1 AU. Such systems are being revealed by radial velocity observations to be quite common around solar-type stars.« less

  14. Improving the opto-microwave performance of SiGe/Si phototransistor through edge-illuminated structure

    NASA Astrophysics Data System (ADS)

    Tegegne, Z. G.; Viana, C.; Polleux, J. L.; Grzeskowiak, M.; Richalot, E.

    2016-03-01

    This paper demonstrates the experimental study of edge and top illuminated SiGe phototransistors (HPT) implemented using the existing industrial SiGe2RF Telefunken GmbH BiCMOS technology for opto-microwave (OM) applications using 850nm Multi-Mode Fibers (MMF). Its technology and structure are described. Two different optical window size HPTs with top illumination (5x5μm2, 10x10μm2) and an edge illuminated HPTs having 5μm x5μm size are presented and compared. A two-step post fabrication process was used to create an optical access on the edge of the HPT for lateral illumination with a lensed MMF through simple polishing and dicing techniques. We perform Opto-microwave Scanning Near-field Optical Microscopy (OM-SNOM) analysis on edge and top illuminated HPTs in order to observe the fastest and the highest sensitive regions of the HPTs. This analysis also allows understanding the parasitic effect from the substrate, and thus draws a conclusion on the design aspect of SiGe/Si HPT. A low frequency OM responsivity of 0.45A/W and a cutoff frequency, f-3dB, of 890MHz were measured for edge illuminated HPT. Compared to the top illuminated HPT of the same size, the edge illuminated HPT improves the f-3dB by a factor of more than two and also improves the low frequency responsivity by a factor of more than four. These results demonstrate that a simple etched HPT is still enough to achieve performance improvements compared to the top illuminated HPT without requiring a complex coupling structure. Indeed, it also proves the potential of edge coupled SiGe HPT in the ultra-low-cost silicon based optoelectronics circuits with a new approach of the optical packaging and system integration to 850nm MMF.

  15. 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

  16. Observation of infrared absorption of InAs quantum dot structures in AlGaAs matrix toward high-efficiency solar cells

    NASA Astrophysics Data System (ADS)

    Yoshikawa, Hirofumi; Watanabe, Katsuyuki; Kotani, Teruhisa; Izumi, Makoto; Iwamoto, Satoshi; Arakawa, Yasuhiko

    2018-06-01

    In accordance with the detailed balance limit model of single-intermediate-band solar cells (IBSCs), the optimum matrix bandgap and IB–conduction band (CB) energy gap are ∼1.9 and 0.7 eV, respectively. We present the room-temperature polarized infrared absorption of 20 stacked InAs quantum dot (QD) structures in the Al0.32Ga0.68As matrix with a bandgap of ∼1.9 eV for the design of high-efficiency IBSCs by using a multipass waveguide geometry. We find that the IB–CB absorption is almost independent of the light polarization, and estimate the magnitude of the absorption per QD layer to be ∼0.01%. We also find that the IB–CB absorption edge of QD structures with a wide-gap matrix is ∼0.41 eV. These results indicate that both the significant increase in the magnitude of IB–CB absorption and the lower energy of the IB state for the higher IB–CB energy gap are necessary toward the realization of high-efficiency IBSCs.

  17. 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

  18. Full-potential theoretical investigations of electron inelastic mean free paths and extended x-ray absorption fine structure in molybdenum.

    PubMed

    Chantler, C T; Bourke, J D

    2014-04-09

    X-ray absorption fine structure (XAFS) spectroscopy is one of the most robust, adaptable, and widely used structural analysis tools available for a range of material classes from bulk solids to aqueous solutions and active catalytic structures. Recent developments in XAFS theory have enabled high-accuracy calculations of spectra over an extended energy range using full-potential cluster modelling, and have demonstrated particular sensitivity in XAFS to a fundamental electron transport property-the electron inelastic mean free path (IMFP). We develop electron IMFP theory using a unique hybrid model that simultaneously incorporates second-order excitation losses, while precisely accounting for optical transitions dictated by the complex band structure of the solid. These advances are coupled with improved XAFS modelling to determine wide energy-range absorption spectra for molybdenum. This represents a critical test case of the theory, as measurements of molybdenum K-edge XAFS represent the most accurate determinations of XAFS spectra for any material. We find that we are able to reproduce an extended range of oscillatory structure in the absorption spectrum, and demonstrate a first-time theoretical determination of the absorption coefficient of molybdenum over the entire extended XAFS range utilizing a full-potential cluster model.

  19. Absorption by Spinning Dust: A Contaminant for High-redshift 21 cm Observations

    NASA Astrophysics Data System (ADS)

    Draine, B. T.; Miralda-Escudé, Jordi

    2018-05-01

    Spinning dust grains in front of the bright Galactic synchrotron background can produce a weak absorption signal that could affect measurements of high-redshift 21 cm absorption. At frequencies near 80 MHz where the Experiment to Detect the Global EoR Signature (EDGES) has reported 21 cm absorption at z≈ 17, absorption could be produced by interstellar nanoparticles with radii a≈ 50 \\mathringA in the cold interstellar medium (ISM), with rotational temperature T ≈ 50 K. Atmospheric aerosols could contribute additional absorption. The strength of the absorption depends on the abundance of such grains and on their dipole moments, which are uncertain. The breadth of the absorption spectrum of spinning dust limits its possible impact on measurement of a relatively narrow 21 cm absorption feature.

  20. Morphology, stability, and X-ray absorption spectroscopic study of iron oxide (Hematite) nanoparticles prepared by micelle nanolithography

    NASA Astrophysics Data System (ADS)

    Bera, Anupam; Bhattacharya, Atanu; Tiwari, N.; Jha, S. N.; Bhattacharyya, D.

    2018-03-01

    Currently, considerable effort is being made towards synthesis and characterization of iron oxide nanoparticles. In this article, we report on the preparation and characterization of iron oxide nanoparticle (NP) arrays supported on natively oxidized Si(100) surface. The NPs are synthesized by reverse micelle nanolithography technique and are then deposited onto natively oxidized Si(100) surface via spin-coating. Plasma oxidation followed by high temperature annealing results in a unimodal size distribution of pseudohexagonally-ordered array of iron oxide NPs (with ∼14 nm mean diameter and ∼5 nm mean height). High temperature annealing does not fragment the NPs. Particles are sinter-resistant: the unimodal arrays are robust with respect to thermal treatment. X-ray absorption spectroscopy (XAS), including X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS), reveals that structure of the iron oxide particle resembles closely the hematite α-Fe2O3 structure. Furthermore, with the help of EXAFS spectra, we eliminate the possibility of γ-Fe2O3, Fe3O4, FeO and FeO(OH) structures for the NPs.

  1. Interface structure in nanoscale multilayers near continuous-to-discontinuous regime

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

    Pradhan, P. C.; Majhi, A.; Nayak, M., E-mail: mnayak@rrcat.gov.in

    2016-07-28

    Interfacial atomic diffusion, reaction, and formation of microstructure in nanoscale level are investigated in W/B{sub 4}C multilayer (ML) system as functions of thickness in ultrathin limit. Hard x-ray reflectivity (XRR) and x-ray diffuse scattering in conjunction with x-ray absorption near edge spectroscopy (XANES) in soft x-ray and hard x-ray regimes and depth profiling x-ray photoelectron spectroscopy (XPS) have been used to precisely evaluate detailed interfacial structure by systematically varying the individual layer thickness from continuous-to-discontinuous regime. It is observed that the interfacial morphology undergoes an unexpected significant modification as the layer thickness varies from continuous-to-discontinuous regime. The interfacial atomic diffusionmore » increases, the physical density of W layer decreases and that of B{sub 4}C layer increases, and further more interestingly the in-plane correlation length decreases substantially as the layer thickness varies from continuous-to-discontinuous regime. This is corroborated using combined XRR and x-ray diffused scattering analysis. XANES and XPS results show formation of more and more tungsten compounds at the interfaces as the layer thickness decreases below the percolation threshold due to increase in the contact area between the elements. The formation of compound enhances to minimize certain degree of disorder at the interfaces in the discontinuous region that enables to maintain the periodic structure in ML. The degree of interfacial atomic diffusion, interlayer interaction, and microstructure is correlated as a function of layer thickness during early stage of film growth.« less

  2. Multi-edge X-ray absorption spectroscopy study of road dust samples from a traffic area of Venice using stoichiometric and environmental references

    NASA Astrophysics Data System (ADS)

    Valotto, Gabrio; Cattaruzza, Elti; Bardelli, Fabrizio

    2017-02-01

    The appropriate selection of representative pure compounds to be used as reference is a crucial step for successful analysis of X-ray absorption near edge spectroscopy (XANES) data, and it is often not a trivial task. This is particularly true when complex environmental matrices are investigated, being their elemental speciation a priori unknown. In this paper, an investigation on the speciation of Cu, Zn, and Sb based on the use of conventional (stoichiometric compounds) and non-conventional (environmental samples or relevant certified materials) references is explored. This method can be useful in when the effectiveness of XANES analysis is limited because of the difficulty in obtaining a set of references sufficiently representative of the investigated samples. Road dust samples collected along the bridge connecting Venice to the mainland were used to show the potentialities and the limits of this approach.

  3. Measurements of near-IR water vapor absorption at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Rieker, G. B.; Liu, X.; Li, H.; Jeffries, J. B.; Hanson, R. K.

    2007-03-01

    Tunable diode lasers (TDLs) are used to measure high resolution (0.1 cm-1), near-infrared (NIR) water vapor absorption spectra at 700 K and pressures up to 30 atm within a high-pressure and -temperature optical cell in a high-uniformity tube furnace. Both direct absorption and wavelength modulation with second harmonic detection (WMS-2f) spectra are obtained for 6 cm-1 regions near 7204 cm-1 and 7435 cm-1. Direct absorption measurements at 700 K and 10 atm are compared with simulations using spectral parameters from HITRAN and a hybrid database combining HITRAN with measured spectral constants for transitions in the two target spectral regions. The hybrid database reduces RMS error between the simulation and the measurements by 45% for the 7204 cm-1 region and 28% for the 7435 cm-1 region. At pressures above 10 atm, the breakdown of the impact approximation inherent to the Lorentzian line shape model becomes apparent in the direct absorption spectra, and measured results are in agreement with model results and trends at elevated temperatures reported in the literature. The wavelength-modulation spectra are shown to be less affected by the breakdown of the impact approximation and measurements agree well with the hybrid database predictions to higher pressures (30 atm).

  4. Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna-Reactor Plasmonic Photocatalysis.

    PubMed

    Li, Kun; Hogan, Nathaniel J; Kale, Matthew J; Halas, Naomi J; Nordlander, Peter; Christopher, Phillip

    2017-06-14

    Efficient photocatalysis requires multifunctional materials that absorb photons and generate energetic charge carriers at catalytic active sites to facilitate a desired chemical reaction. Antenna-reactor complexes are an emerging multifunctional photocatalytic structure where the strong, localized near field of the plasmonic metal nanoparticle (e.g., Ag) is coupled to the catalytic properties of the nonplasmonic metal nanoparticle (e.g., Pt) to enable chemical transformations. With an eye toward sustainable solar driven photocatalysis, we investigate how the structure of antenna-reactor complexes governs their photocatalytic activity in the light-limited regime, where all photons need to be effectively utilized. By synthesizing core@shell/satellite (Ag@SiO 2 /Pt) antenna-reactor complexes with varying Ag nanoparticle diameters and performing photocatalytic CO oxidation, we observed plasmon-enhanced photocatalysis only for antenna-reactor complexes with antenna components of intermediate sizes (25 and 50 nm). Optimal photocatalytic performance was shown to be determined by a balance between maximized local field enhancements at the catalytically active Pt surface, minimized collective scattering of photons out of the catalyst bed by the complexes, and minimal light absorption in the Ag nanoparticle antenna. These results elucidate the critical aspects of local field enhancement, light scattering, and absorption in plasmonic photocatalyst design, especially under light-limited illumination conditions.

  5. Delocalization and occupancy effects of 5f orbitals in plutonium intermetallics using L3-edge resonant X-ray emission spectroscopy

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

    Booth, C. H.; Medling, S. A.; Jiang, Yu

    2014-06-24

    Although actinide (An) L3 -edge X-ray absorption near-edge structure (XANES) spectroscopy has been very effective in determining An oxidation states in insulating, ionically bonded materials, such as in certain coordination compounds and mineral systems, the technique fails in systems featuring more delocalized 5f orbitals, especially in metals. Recently, actinide L3-edge resonant X-ray emission spec- troscopy (RXES) has been shown to be an effective alternative. This technique is further demonstrated here using a parameterized partial unoccupied density of states method to quantify both occupancy and delocalization of the 5f orbital in ?-Pu, ?-Pu, PuCoGa5 , PuCoIn5 , and PuSb2. These newmore » results, supported by FEFF calculations, highlight the effects of strong correlations on RXES spectra and the technique?s ability to differentiate between f-orbital occupation and delocalization.« less

  6. Near-Edge X-ray Absorption Fine Structure within Multilevel Coupled Cluster Theory.

    PubMed

    Myhre, Rolf H; Coriani, Sonia; Koch, Henrik

    2016-06-14

    Core excited states are challenging to calculate, mainly because they are embedded in a manifold of high-energy valence-excited states. However, their locality makes their determination ideal for local correlation methods. In this paper, we demonstrate the performance of multilevel coupled cluster theory in computing core spectra both within the core-valence separated and the asymmetric Lanczos implementations of coupled cluster linear response theory. We also propose a visualization tool to analyze the excitations using the difference between the ground-state and excited-state electron densities.

  7. Electronic structure change of NiS2- x Se x in the metal-insulator transition probed by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Jeong, Jinwon; Park, Kyung Ja; Cho, En-Jin; Noh, Han-Jin; Kim, Sung Baek; Kim, Hyeong-Do

    2018-01-01

    The electronic structure change of NiS2- x Se x as a function of Se concentration x has been studied by Ni L-edge X-ray absorption spectroscopy (XAS). The XAS spectra show distinct features in Ni L 3 edge, indicating whether the system is insulating or metallic. These features can be semi-quantitatively explained within the framework of the configurational interaction cluster model (CICM). In the S-rich region, relatively large charge-transfer energy (Δ 5 eV) from ligand p to Ni 3 d states and a little small p- d hybridization strength ( V pdσ 1.1 eV) can reproduce the experimental spectra in the CICM calculation, and vice versa in the Se-rich region. Our analysis result is consistent with the Zaanen-Sawatzky-Allen scheme that the systems in S-rich side ( x ≤ 0.5) are a charge transfer insulator. However, it also requires that the Δ value must change abruptly in spite of the small change of x near x = 0.5. As a possible microscopic origin, we propose a percolation scenario where a long range connection of Ni[(S,Se)2]6 octahedra with Se-Se dimers plays a key role to gap closure.

  8. Structural, electronic structure and antibacterial properties of graphene-oxide nano-sheets

    NASA Astrophysics Data System (ADS)

    Sharma, Aditya; Varshney, Mayora; Nanda, Sitansu Sekhar; Shin, Hyun Joon; Kim, Namdong; Yi, Dong Kee; Chae, Keun-Hwa; Ok Won, Sung

    2018-04-01

    Correlation between the structural/electronic structure properties and bio-activity of graphene-based materials need to be thoroughly evaluated before their commercial implementation in the health and environment precincts. To better investigate the local hybridization of sp2/sp3 orbitals of the functional groups of graphene-oxide (GO) and their execution in the antimicrobial mechanism, we exemplify the antibacterial activity of GO sheets towards the Escherichia coli bacteria (E. coli) by applying the field-emission scanning electron microscopy (FESEM), near edge X-ray absorption fine structure (NEXAFS) and scanning transmission X-ray microscope (STXM) techniques. C K-edge and O K-edge NEXAFS spectra have revealed lesser sp2 carbon atoms in the aromatic ring and attachment of functional oxygen groups at GO sheets. Entrapment of E. coli bacteria by GO sheets is evidenced by FESEM investigations and has also been corroborated by nano-scale imaging of bacteria using the STXM. Spectroscopy evidence of functional oxygen moieties with GO sheets and physiochemical entrapment of E. coli bacteria have assisted us to elaborate the mechanism of cellular oxidative stress-induced disruption of bacterial membrane.

  9. Statistical Fine Structure of Inhomogeneously Broadened Absorption Lines.

    DTIC Science & Technology

    1987-07-31

    inhomogeneously broadened optical absorption of pentacene n p-terphenyl at liquid helium temperatures... SFS is the actual frequency- ependent, time...statistical fine structure (SFS) in the inhomogeneously broadened optical absorption of pentacene in p-terphenyl at liquid helium temperatures. SFS is the...quite difficult . -2- We have observed for the first time statistical fine structure in the inhomogeneously broadened optical absorption of pentacene

  10. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy below 100 eV: probing first-row transition-metal M-edges in chemical complexes

    PubMed Central

    Wang, Hongxin; Young, Anthony T.; Guo, Jinghua; Cramer, Stephen P.; Friedrich, Stephan; Braun, Artur; Gu, Weiwei

    2013-01-01

    X-ray absorption and scattering spectroscopies involving the 3d transition-metal K- and L-edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M-edges, which are below 100 eV. Synchrotron-based X-ray sources can have higher energy resolution at M-edges. M-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) could therefore provide complementary information to K- and L-edge spectroscopies. In this study, M 2,3-edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M 2,3-edge RIXS on NiO, NiF2 and two other covalent complexes have been performed and different d–d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M-edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high-sensitivity and high-resolution superconducting tunnel junction X-ray detectors below 100 eV is also illustrated and discussed. PMID:23765304

  11. MoS2 edges and heterophase interfaces: energy, structure and phase engineering

    NASA Astrophysics Data System (ADS)

    Zhou, Songsong; Han, Jian; Sun, Jianwei; Srolovitz, David J.

    2017-06-01

    The transition metal dichalcogenides exhibit polymorphism; i.e. both 2H and 1T‧ crystal structures, each with unique electronic properties. These two phases can coexist within the same monolayer microstructure, producing 2H/1T‧ interfaces. Here we report a systematic investigation of the energetics of the experimentally most important MoS2 heterophase interfaces and edges. The stable interface and edge structures change with chemical potential (these edges/interfaces are usually non-stoichiometric). Stable edges tend to be those of highest atomic density and the stable interfaces correspond to those with local atomic structure very similar to the 2H crystal. The interfacial energies are lower than those of the edges, and the 1T‧ edges have lower energy than the 2H edges. Because the 1T‧ edges have much lower energy than the 2H edges, a sufficiently narrow 1T‧ ribbon will be more stable than the corresponding 2H ribbon (this critical width is much larger in MoTe2 than in MoS2). Similarly, a large 2H flake have an equilibrium strip of 1T‧ along its edge (again this effect is much larger in MoTe2 than in MoS2). Application of tensile strains can increase the width of the stable 1T‧ strip or the critical thickness below which a ribbon favors the 1T‧ structure. These effects provide a means to phase engineer transition metal dichalcogenide microstructures.

  12. Thermal emission and absorption of radiation in finite inverted-opal photonic crystals

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

    Florescu, Marian; Stimpson, Andrew J.; Lee, Hwang

    We study theoretically the optical properties of a finite inverted-opal photonic crystal. The light-matter interaction is strongly affected by the presence of the three-dimensional photonic crystal and the alterations of the light emission and absorption processes can be used to suppress or enhance the thermal emissivity and absorptivity of the dielectric structure. We investigate the influence of the absorption present in the system on the relevant band edge frequencies that control the optical response of the photonic crystal. Our study reveals that the absorption processes cause spectral broadening and shifting of the band edge optical resonances, and determine a strongmore » reduction of the photonic band gap spectral range. Using the angular and spectral dependence of the band edge frequencies for stop bands along different directions, we argue that by matching the blackbody emission spectrum peak with a prescribed maximum of the absorption coefficient, it is possible to achieve an angle-sensitive enhancement of the thermal emission/absorption of radiation. This result opens a way to realize a frequency-sensitive and angle-sensitive photonic crystal absorbers/emitters.« less

  13. Investigation of the Structural Stability of Ion-Implanted Gd 2Ti 2-xSn xO 7 Pyrochlore-Type Oxides by Glancing Angle X-ray Absorption Spectroscopy

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

    Aluri, Esther Rani; Hayes, John R.; Walker, James D.S.

    2016-03-24

    Rare-earth titanate and stannate pyrochlore-type oxides have been investigated in the past for the sequestration of nuclear waste elements because of their resistance to radiation-induced structural damage. In order to enhance this property, it is necessary to understand the effect of radioactive decay of the incorporated actinide elements on the local chemical environment. In this study, Gd 2Ti 2–xSn xO 7 materials have been implanted with Au– ions to simulate radiation-induced structural damage. Glancing angle X-ray absorption near-edge spectroscopy (GA-XANES), glancing angle X-ray absorption fine structure (GA-EXAFS) analysis, and powder X-ray diffraction have been used to investigate changes in themore » local coordination environment of the metal atoms in the damaged surface layer. Examination of GA-XANES/EXAFS spectra from the implanted Gd 2Ti 2–xSn xO 7 materials collected at various glancing angles allowed for an investigation of how the local coordination environment around the absorbing atoms changed at different depths in the damaged surface layer. This study has shown the usefulness of GA-XANES to the examination of ion-implanted materials and has suggested that Gd 2Ti 2–xSn xO 7 becomes more susceptible to ion-beam-induced structural damage with increasing Sn concentration.« less

  14. Heterogeneous porous structures for the fastest liquid absorption

    NASA Astrophysics Data System (ADS)

    Shou, Dahua; Ye, Lin; Fan, Jintu

    2013-08-01

    Engineered porous materials, which have fast absorption of liquids under global constraints (e.g. volume, surface area, or cost of the materials), are useful in many applications including moisture management fabrics, medical wound dressings, paper-based analytical devices, liquid molding composites, etc.. The absorption in capillary tubes and porous media is driven by the surface tension of liquid, which is inversely proportional to the pore size. On the contrary, the ability of conduction (or permeability) of liquid in porous materials is linear with the square of pore size. Both mechanisms superimpose with each other leading to a possibility of the fastest absorption for a porous structure. In this work, we explore the flow behaviors for the fastest absorption using heterogeneous porous architectures, from two-portion tubes to two-layer porous media. The absorption time for filling up the voids in these porous materials is expressed in terms of pore size, height and porosity. It is shown that under the given height and void volume, these two-component porous structures with a negative gradient of pore size/porosity against the imbibition direction, have a faster absorption rate than controlled samples with uniform pore size/porosity. Particularly, optimal structural parameters including pore size, height and porosity are found for the minimum absorption time. The obtained results will be used as a priori for the design of porous structures with excellent water absorption and moisture management property in various fields.

  15. L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array

    NASA Astrophysics Data System (ADS)

    Titus, Charles J.; Baker, Michael L.; Lee, Sang Jun; Cho, Hsiao-Mei; Doriese, William B.; Fowler, Joseph W.; Gaffney, Kelly; Gard, Johnathon D.; Hilton, Gene C.; Kenney, Chris; Knight, Jason; Li, Dale; Marks, Ronald; Minitti, Michael P.; Morgan, Kelsey M.; O'Neil, Galen C.; Reintsema, Carl D.; Schmidt, Daniel R.; Sokaras, Dimosthenis; Swetz, Daniel S.; Ullom, Joel N.; Weng, Tsu-Chien; Williams, Christopher; Young, Betty A.; Irwin, Kent D.; Solomon, Edward I.; Nordlund, Dennis

    2017-12-01

    We present X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous ferricyanide. These measurements demonstrate the ability of high-throughput transition-edge-sensor (TES) spectrometers to access the rich soft X-ray (100-2000 eV) spectroscopy regime for dilute and radiation-sensitive samples. Our low-concentration data are in agreement with high-concentration measurements recorded by grating spectrometers. These results show that soft-X-ray RIXS spectroscopy acquired by high-throughput TES spectrometers can be used to study the local electronic structure of dilute metal-centered complexes relevant to biology, chemistry, and catalysis. In particular, TES spectrometers have a unique ability to characterize frozen solutions of radiation- and temperature-sensitive samples.

  16. Subgap Absorption in Conjugated Polymers

    DOE R&D Accomplishments Database

    Sinclair, M.; Seager, C. H.; McBranch, D.; Heeger, A. J; Baker, G. L.

    1991-01-01

    Along with X{sup (3)}, the magnitude of the optical absorption in the transparent window below the principal absorption edge is an important parameter which will ultimately determine the utility of conjugated polymers in active integrated optical devices. With an absorptance sensitivity of < 10{sup {minus}5}, Photothermal Deflection Spectroscopy (PDS) is ideal for determining the absorption coefficients of thin films of transparent'' materials. We have used PDS to measure the optical absorption spectra of the conjugated polymers poly(1,4-phenylene-vinylene) (and derivitives) and polydiacetylene-4BCMU in the spectral region from 0.55 eV to 3 eV. Our spectra show that the shape of the absorption edge varies considerably from polymer to polymer, with polydiacetylene-4BCMU having the steepest absorption edge. The minimum absorption coefficients measured varied somewhat with sample age and quality, but were typically in the range 1 cm{sup {minus}1} to 10 cm{sup {minus}1}. In the region below 1 eV, overtones of C-H stretching modes were observed, indicating that further improvements in transparency in this spectral region might be achieved via deuteration of fluorination.

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

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

    Kim, Do Heui; Szanyi, Janos; Kwak, Ja Hun

    2009-04-03

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

  18. UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

    PubMed

    Ochmann, Miguel; Hussain, Abid; von Ahnen, Inga; Cordones, Amy A; Hong, Kiryong; Lee, Jae Hyuk; Ma, Rory; Adamczyk, Katrin; Kim, Tae Kyu; Schoenlein, Robert W; Vendrell, Oriol; Huse, Nils

    2018-05-30

    We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH 2 S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

  19. A New Look at the Structural and Magnetic Properties of Potassium Neptunate K2NpO4 Combining XRD, XANES Spectroscopy, and Low-Temperature Heat Capacity.

    PubMed

    Smith, Anna L; Colineau, Eric; Griveau, Jean-Christophe; Popa, Karin; Kauric, Guilhem; Martin, Philippe; Scheinost, Andreas C; Cheetham, Anthony K; Konings, Rudy J M

    2017-05-15

    The physicochemical properties of the potassium neptunate K 2 NpO 4 have been investigated in this work using X-ray diffraction, X-ray absorption near edge structure (XANES) spectroscopy at the Np-L 3 edge, and low-temperature heat capacity measurements. A Rietveld refinement of the crystal structure is reported for the first time. The Np(VI) valence state has been confirmed by the XANES data, and the absorption edge threshold of the XANES spectrum has been correlated to the Mössbauer isomer shift value reported in the literature. The standard entropy and heat capacity of K 2 NpO 4 have been derived at 298.15 K from the low-temperature heat capacity data. The latter suggest the existence of a magnetic ordering transition around 25.9 K, most probably of the ferromagnetic type.

  20. High resolution absolute absorption cross sections of the B ̃(1)A'-X ̃(1)A' transition of the CH2OO biradical.

    PubMed

    Foreman, Elizabeth S; Kapnas, Kara M; Jou, YiTien; Kalinowski, Jarosław; Feng, David; Gerber, R Benny; Murray, Craig

    2015-12-28

    Carbonyl oxides, or Criegee intermediates, are formed from the gas phase ozonolysis of alkenes and play a pivotal role in night-time and urban area atmospheric chemistry. Significant discrepancies exist among measurements of the strong B ̃(1)A'-X ̃(1)A' electronic transition of the simplest Criegee intermediate, CH2OO in the visible/near-UV. We report room temperature spectra of the B ̃(1)A'-X ̃(1)A' electronic absorption band of CH2OO acquired at higher resolution using both single-pass broadband absorption and cavity ring-down spectroscopy. The new absorption spectra confirm the vibrational structure on the red edge of the band that is absent from ionization depletion measurements. The absolute absorption cross sections over the 362-470 nm range are in good agreement with those reported by Ting et al. Broadband absorption spectra recorded over the temperature range of 276-357 K were identical within their mutual uncertainties, confirming that the vibrational structure is not due to hot bands.

  1. Structural design of morphing trailing edge actuated by SMA

    NASA Astrophysics Data System (ADS)

    Wang, Qi; Xu, Zhiwei; Zhu, Qian

    2013-09-01

    In this paper, the morphing trailing edge is designed to achieve the up and down deflection under the aerodynamic load. After a detailed and accurate computational analysis to determine the SMA specifications and layout programs, a solid model is created in CATIA and the structures of the morphing wing trailing edge are produced by CNC machining. A set of DSP measurement and control system is designed to accomplish the controlling experiment of the morphing wing trailing edge. At last, via the force analysis, the trailing edge is fabricated with four sections of aluminum alloy, and the arrangement scheme of SMA wires is determined. Experiment of precise control integral has been performed to survey the control effect. The experiment consists of deflection angle tests of the third joint and the integral structure. Primarily, the ultimate deflection angle is tested in these two experiments. Therefore, the controlling experiment of different angles could be performed within this range. The results show that the deflection error is less than 4%and response time is less than 6.7 s, the precise controlling of the morphing trailing edge is preliminary realized.

  2. Quasi-static energy absorption of hollow microlattice structures

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

    Liu, YL; Schaedler, TA; Jacobsen, AJ

    2014-12-01

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

  3. Theoretical X-ray production cross sections at incident photon energies across L{sub i} (i=1-3) absorption edges of Br

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

    Puri, Sanjiv

    The X-ray production (XRP) cross sections, σ{sub Lk} (k = l, η, α, β{sub 6}, β{sub 1}, β{sub 3}, β{sub 4}, β{sub 9,10}, γ{sub 1,5}, γ{sub 2,3}) have been evaluated at incident photon energies across the L{sub i}(i=1-3) absorption edge energies of {sub 35}Br using theoretical data sets of different physical parameters, namely, the L{sub i}(i=1-3) sub-shell the X-ray emission rates based on the Dirac-Fock (DF) model, the fluorescence and Coster Kronig yields based on the Dirac-Hartree-Slater (DHS) model, and two sets of the photoionisation cross sections based on the relativistic Hartree-Fock-Slater (RHFS) model and the Dirac-Fock (DF) model, inmore » order to highlight the importance of electron exchange effects at photon energies in vicinity of absorption edge energies.« less

  4. Swift heavy ion irradiation of Pt nanocrystals: II. Structural changes and H desorption

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

    Giulian, R.; Araujo, L.L.; Kluth, P.

    2014-09-24

    The structural properties and H desorption from embedded Pt nanocrystals (NCs) following irradiation with swift heavy ions were investigated as a function of energy and fluence. From x-ray absorption near-edge spectroscopy analysis, Pt-H bonding was identified in NCs annealed in a forming gas (95% N{sub 2} + 5% H{sub 2}) ambient. The H content decreased upon irradiation and the desorption process was NC-size dependent such that larger NCs required a higher fluence to achieve a H-free state. Pt-H bonding and NC dissolution both perturbed the NC structural parameters (coordination number, bond-length and mean-square relative displacement) as determined with extended x-raymore » absorption fine structure measurements.« less

  5. Multi-edge X-ray absorption spectroscopy study of road dust samples from a traffic area of Venice using stoichiometric and environmental references.

    PubMed

    Valotto, Gabrio; Cattaruzza, Elti; Bardelli, Fabrizio

    2017-02-15

    The appropriate selection of representative pure compounds to be used as reference is a crucial step for successful analysis of X-ray absorption near edge spectroscopy (XANES) data, and it is often not a trivial task. This is particularly true when complex environmental matrices are investigated, being their elemental speciation a priori unknown. In this paper, an investigation on the speciation of Cu, Zn, and Sb based on the use of conventional (stoichiometric compounds) and non-conventional (environmental samples or relevant certified materials) references is explored. This method can be useful in when the effectiveness of XANES analysis is limited because of the difficulty in obtaining a set of references sufficiently representative of the investigated samples. Road dust samples collected along the bridge connecting Venice to the mainland were used to show the potentialities and the limits of this approach. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. PKP Waveform Complexity and Its Implications to Fine Structure Near the Edge of African Large Low Shear Velocity Province

    NASA Astrophysics Data System (ADS)

    Song, Teh-Ru Alex; Tanaka, Satoru; Takeuchi, Nozomu

    2010-05-01

    and receiver-side structure do not play a predominant role in generating these anomalous PKPab waveforms. We then look into structural anomaly near the core-mantle-boundary (CMB) since PKPab grazes the CMB at a very shallow angle and it can effectively interact with it and possibly produce anomalous PKPab waveforms. We first explore 1-D model space by introducing velocity anomaly directly above the CMB, with a velocity perturbation up to a few tens of percents in S wave velocity and P wave velocity. We calculate synthetics up to 2 Hz by Direct Solution Method (DSM) and Reflectivity Method to examine waveform anomaly at long period band (0.01-0.2 Hz) as well as short-period band (0.5-2 Hz). Our preliminary result indicates that the model with a thin (~ 15 km) ultra-low velocity zone (ULVZ, 30% reduction in P wave and S wave velocity) is capable of reproducing characteristics of these anomalous PKPab waveforms at both frequency bands. The pierce points of PKPab in the source side at CMB are near the southeast Indian Ocean where S wave velocity is only slightly faster than PREM. On the other hand, the pierce points in the receiver side are at the eastern edge of the African Large Low Shear Velocity Province (LLSVP). One interesting feature of our ULVZ model is that dlnVs/dlnVp is about 1, which is different from most ULVZ models where dlnVs/dlnVp is about 3.

  7. Detection of metal stress in boreal forest species using the 0.67-micron chlorophyll absorption band

    NASA Technical Reports Server (NTRS)

    Singhroy, Vernon H.; Kruse, Fred A.

    1991-01-01

    Several recent studies have shown that a shift of the red-edge inflection near 0.70 micron in vegetation reflectance spectra is an indicator of metal stress, partially attributable to changes in chlorophyll concentration. This 'red-edge shift', however, is difficult to detect and has been reported both toward longer (red) and shorter (blue) wavelengths. Our work demonstrates that direct measurement of the depth and width of the chlorophyll absorption band at 0.67 micron using digital feature extraction and absorption band characterization procedures developed for the analysis of mineral spectra is a more consistent indicator of metal stress. Additionally, the magnitude of these parameters is generally greater than that of the red edge shift and thus should be more amenable to detection and mapping using field and aircraft spectrometers.

  8. [The photoluminescence and absorption properties of Co/AAO nano-array composites].

    PubMed

    Li, Shou-Yi; Wang, Cheng-Wei; Li, Yan; Wang, Jian; Ma, Bao-Hong

    2008-03-01

    Ordered Co/AAO nano-array structures were fabricated by alternating current (AC) electrodeposition method within the cylindrical pores of anodic aluminum oxide (AAO) template prepared in oxalic acid electrolyte. The photoluminescence (PL) emission and photoabsorption of AAO templates and Co/AAO nano-array structures were investigated respectively. The results show that a marked photoluminescence band of AAO membranes occurs in the wavelength range of 350-550 nm and their PL peak position is at 395 nm. And with the increase in the deposition amount of Co nanoparticles, the PL intensity of Co/AAO nano-array structures decreases gradually, and their peak positions of the PL are invariable (395 nm). Meanwhile the absorption edges of Co/AAO show a larger redshift, and the largest shift from the near ultraviolet to the infrared exceeds 380 nm. The above phenomena caused by Co nano-particles in Co/AAO composite were analyzed.

  9. X-ray absorption edge spectroscopy and computational studies on LCuO2 species: Superoxide-Cu(II) versus peroxide-Cu(III) bonding.

    PubMed

    Sarangi, Ritimukta; Aboelella, Nermeen; Fujisawa, Kiyoshi; Tolman, William B; Hedman, Britt; Hodgson, Keith O; Solomon, Edward I

    2006-06-28

    The geometric and electronic structures of two mononuclear CuO2 complexes, [Cu(O2){HB(3-Ad-5-(i)Prpz)3}] (1) and [Cu(O2)(beta-diketiminate)] (2), have been evaluated using Cu K- and L-edge X-ray absorption spectroscopy (XAS) studies in combination with valence bond configuration interaction (VBCI) simulations and spin-unrestricted broken symmetry density functional theory (DFT) calculations. Cu K- and L-edge XAS data indicate the Cu(II) and Cu(III) nature of 1 and 2, respectively. The total integrated intensity under the L-edges shows that the 's in 1 and 2 contain 20% and 28% Cu character, respectively, indicative of very covalent ground states in both complexes, although more so in 1. Two-state VBCI simulations also indicate that the ground state in 2 has more Cu (/3d8) character. DFT calculations show that the in both complexes is dominated by O2(n-) character, although the O2(n-) character is higher in 1. It is shown that the ligand L plays an important role in modulating Cu-O2 bonding in these LCuO2 systems and tunes the ground states of 1 and 2 to have dominant Cu(II)-superoxide-like and Cu(III)-peroxide-like character, respectively. The contributions of ligand field (LF) and the charge on the absorbing atom in the molecule (Q(mol)M) to L- and K-edge energy shifts are evaluated using DFT and time-dependent DFT calculations. It is found that LF makes a dominant contribution to the edge energy shift, while the effect of Q(mol)M is minor. The charge on the Cu in the Cu(III) complex is found to be similar to that in Cu(II) complexes, which indicates a much stronger interaction with the ligand, leading to extensive charge transfer.

  10. Optical absorption in degenerately doped semiconductors: Mott transition or Mahan excitons?

    NASA Astrophysics Data System (ADS)

    Schleife, André.; Rödl, Claudia; Hannewald, Karsten; Bechstedt, Friedhelm

    2012-02-01

    In the exploration of material properties, parameter-free calculations are a modern, sophisticated complement to cutting-edge experimental techniques. Ab-initio calculations are now capable of providing a deep understanding of the interesting physics underlying the electronic structure and optical absorption, e.g., of the transparent conductive oxides. Due to electron doping, these materials are conductive even though they have wide fundamental band gaps. The degenerate electron gas in the lowest conduction-band states drastically modifies the Coulomb interaction between the electrons and, hence, the optical properties close to the absorption edge. We describe these effects by developing an ab-initio technique which captures also the Pauli blocking and the Fermi-edge singularity at the optical absorption onset, that occur in addition to quasiparticle and excitonic effects. We answer the question whether free carriers induce an excitonic Mott transition or trigger the evolution of Wannier-Mott excitons into Mahan excitons. The prototypical n-type zinc oxide is studied as an example.

  11. Localized modes in optics of photonic liquid crystals with local anisotropy of absorption

    NASA Astrophysics Data System (ADS)

    Belyakov, V. A.; Semenov, S. V.

    2016-05-01

    The localized optical modes in spiral photonic liquid crystals are theoretically studied for the certainty at the example of chiral liquid crystals (CLCs) for the case of CLC with an anisotropic local absorption. The model adopted here (absence of dielectric interfaces in the structures under investigation) makes it possible to get rid of mixing of polarizations on the surfaces of the CLC layer and of the defect structure and to reduce the corresponding equations to only the equations for light with polarization diffracting in the CLC. The dispersion equations determining connection of the edge mode (EM) and defect mode (DM) frequencies with the CLC layer parameters (anisotropy of local absorption, CLC order parameter) and other parameters of the DMS are obtained. Analytic expressions for the transmission and reflection coefficients of CLC layer and DMS for the case of CLC with an anisotropic local absorption are presented and analyzed. It is shown that the CLC layers with locally anisotropic absorption reduce the EM and DM lifetimes (and increase the lasing threshold) in the way different from the case of CLC with an isotropic local absorption. Due to the Borrmann effect revealing of which is different at the opposite stop-band edges in the case of CLC layers with an anisotropic local absorption the EM life-times for the EM frequencies at the opposite stop-bands edges may be significantly different. The options of experimental observations of the theoretically revealed phenomena are briefly discussed.

  12. 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

  13. 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

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

    PubMed

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

    2014-01-14

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

  15. Wrinkling reduction of membrane structure by trimming edges

    NASA Astrophysics Data System (ADS)

    Liu, Mingjun; Huang, Jin; Liu, Mingyue

    2017-05-01

    Thin membranes have negligible bending stiffness, compressive stresses inevitably lead to wrinkling. Therefore, it is important to keep the surface of membrane structures flat in order to guarantee high precision. Edge-trimming is an effective method to passively diminish wrinkles, however a key difficulty in this process is the determination of the optimal trimming level. In this paper, regular polygonal membrane structures subjected to equal radial forces were analyzed, and a new stress field distribution model for arc-edge square membrane structure was proposed to predict the optimal trimming level. This model is simple and applicable to any polygonal membrane structures. Comparison among the results of the finite element analysis, and the experimental and analytical results showed that the proposed model accurately described the stress field distribution and guaranteed that there are no wrinkles appear inside the effective inscribed circle region for the optimal trimming level.

  16. Electronic structure study of Ce1-xAxO2 (A = Zr & Hf) nanoparticles: NEXAFS and EXAFS investigations.

    PubMed

    Sharma, Aditya; Varshney, Mayora; Shin, Hyun-Joon; Park, Yong Jun; Kim, Min-Gyu; Ha, Tae-Kyun; Chae, Keun Hwa; Gautam, Sanjeev

    2014-10-07

    Single phase nanoparticles (NPs) of CeO2, Ce0.5Zr0.5O2, Ce0.5Hf0.5O2 and Ce0.5Hf0.25Zr0.25O2 were successfully synthesized by co-precipitation method at constant pH and temperature. The X-ray diffraction results revealed that the additive atoms did not segregate to form secondary phases but led to grain size variation in the NPs. The 10 Dq values in the near edge X-ray absorption fine structure (NEXAFS) spectra at the O K-edge did not vary in the same way as the average grain size was changed for the doped CeO2 NPs. The deconvolution of Ce M5-edge and detailed analysis of O K pre-edge peak have shown the higher Ce(+3)/(Ce(+3) + Ce(+4)) ratio in the Zr- and Hf-doped samples. The local atomic structure around the Ce, Zr and Hf atoms was investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy at Ce K-edge, Zr K-edge and Hf L3-edge, respectively, and the EXAFS data were fitted with the theoretical calculations. The 4f occupancy, Ce(+3)/(Ce(+3) + Ce(+4)) ratio of Ce ions, coordination number of Ce and Ce-Ce/Ce-O bond distances were sensitive to the additive atoms but not explicitly changed according to the grain size variation in the NPs.

  17. L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array

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

    Titus, Charles J.; Baker, Michael L.; Lee, Sang Jun

    Here, we present X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous ferricyanide. These measurements then demonstrate the ability of high-throughput transition-edge-sensor (TES) spectrometers to access the rich soft X-ray (100–2000 eV) spectroscopy regime for dilute and radiation-sensitive samples. Our low-concentration data are in agreement with high-concentration measurements recorded by grating spectrometers. These results show that soft-X-ray RIXS spectroscopy acquired by high-throughput TES spectrometers can be used to study the local electronic structure of dilute metal-centered complexes relevant to biology, chemistry, and catalysis. In particular, TES spectrometers have a unique abilitymore » to characterize frozen solutions of radiation- and temperature-sensitive samples.« less

  18. L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array

    DOE PAGES

    Titus, Charles J.; Baker, Michael L.; Lee, Sang Jun; ...

    2017-12-07

    Here, we present X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous ferricyanide. These measurements then demonstrate the ability of high-throughput transition-edge-sensor (TES) spectrometers to access the rich soft X-ray (100–2000 eV) spectroscopy regime for dilute and radiation-sensitive samples. Our low-concentration data are in agreement with high-concentration measurements recorded by grating spectrometers. These results show that soft-X-ray RIXS spectroscopy acquired by high-throughput TES spectrometers can be used to study the local electronic structure of dilute metal-centered complexes relevant to biology, chemistry, and catalysis. In particular, TES spectrometers have a unique abilitymore » to characterize frozen solutions of radiation- and temperature-sensitive samples.« less

  19. Gyrokinetic simulations of DIII-D near-edge L-mode plasmas

    NASA Astrophysics Data System (ADS)

    Neiser, Tom; Jenko, Frank; Carter, Troy; Schmitz, Lothar; Merlo, Gabriele; Told, Daniel; Banon Navarro, Alejandro; McKee, George; Yan, Zheng

    2017-10-01

    In order to understand the L-H transition, a good understanding of the L-mode edge region is necessary. We perform nonlinear gyrokinetic simulations of a DIII-D L-mode discharge with the GENE code in the near-edge, which we define as ρtor >= 0.8 . At ρ = 0.9 , ion-scale simulations reproduce experimental heat fluxes within the uncertainty of the experiment. At ρ = 0 . 8 , electron-scale simulations reproduce the experimental electron heat flux while ion-scale simulations do not reproduce the respective ion heat flux due to a strong poloidal zonal flow. However, we reproduce both electron and ion heat fluxes by increasing the local ion temperature gradient by 80 % . Local fitting to the CER data in the domain 0.7 <= ρ <= 0.9 is compatible with such an increase in ion temperature gradient within the error bars. Ongoing multi-scale simulations are investigating whether radial electron streamers could dampen the poloidal zonal flows at ρ = 0.8 and increase the radial ion-scale flux. Supported by U.S. DOE under Contract Numbers DE-FG02-08ER54984, DE-FC02-04ER54698, and DE-AC02-05CH11231.

  20. Local Fine Structural Insight into Mechanism of Electrochemical Passivation of Titanium.

    PubMed

    Wang, Lu; Yu, Hongying; Wang, Ke; Xu, Haisong; Wang, Shaoyang; Sun, Dongbai

    2016-07-20

    Electrochemically formed passive film on titanium in 1.0 M H2SO4 solution and its thickness, composition, chemical state, and local fine structure are examined by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure. AES analysis reveals that the thickness and composition of oxide film are proportional to the reciprocal of current density in potentiodynamic polarization. XPS depth profiles of the chemical states of titanium exhibit the coexistence of various valences cations in the surface. Quantitative X-ray absorption near edge structure analysis of the local electronic structure of the topmost surface (∼5.0 nm) shows that the ratio of [TiO2]/[Ti2O3] is consistent with that of passivation/dissolution of electrochemical activity. Theoretical calculation and analysis of extended X-ray absorption fine structure spectra at Ti K-edge indicate that both the structures of passivation and dissolution are distorted caused by the appearance of two different sites of Ti-O and Ti-Ti. And the bound water in the topmost surface plays a vital role in structural disorder confirmed by XPS. Overall, the increase of average Ti-O coordination causes the electrochemical passivation, and the dissolution is due to the decrease of average Ti-Ti coordination. The structural variations of passivation in coordination number and interatomic distance are in good agreement with the prediction of point defect model.

  1. Iron L-edge X-ray Absorption Spectroscopy of Oxy-Picket Fence Porphyrin: Experimental Insight into Fe-O2 Bonding

    PubMed Central

    Wilson, Samuel A.; Kroll, Thomas; Decreau, Richard A.; Hocking, Rosalie K.; Lundberg, Marcus; Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.

    2013-01-01

    The electronic structure of the Fe–O2 center in oxy-hemoglobin and oxy-myoglobin is a long-standing issue in the field of bioinorganic chemistry. Spectroscopic studies have been complicated by the highly delocalized nature of the porphyrin and calculations require interpretation of multi-determinant wavefunctions for a highly covalent metal site. Here, iron L-edge X-ray absorption spectroscopy (XAS), interpreted using a valence bond configuration interaction (VBCI) multiplet model, is applied to directly probe the electronic structure of the iron in the biomimetic Fe–O2 heme complex [Fe(pfp)(1-MeIm)O2] (pfp = meso-tetra(α,α,α,α-o-pivalamidophenyl) porphyrin or TpivPP). This method allows separate estimates of σ-donor, π-donor, and π-acceptor interactions through ligand to metal charge transfer (LMCT) and metal to ligand charge transfer (MLCT) mixing pathways. The L-edge spectrum of [Fe(pfp)(1-MeIm)O2] is further compared to those of [FeII(pfp)(1-MeIm)2], [FeII(pfp)], and [FeIII(tpp)(ImH)2]Cl (tpp = meso-tetraphenylporphyrin) which have FeII S = 0, FeII S = 1 and FeIII S = 1/2 ground states, respectively. These serve as references for the three possible contributions to the ground state of oxy-pfp. The Fe–O2 pfp site is experimentally determined to have both significant σ-donation and a strong π-interaction of the O2 with the iron, with the latter having implications with respect to the spin polarization of the ground state. PMID:23259487

  2. Energy absorption of composite material and structure

    NASA Technical Reports Server (NTRS)

    Farley, Gary L.

    1987-01-01

    Results are presented from a joint research program on helicopter crashworthiness conducted by the U.S. Army Aerostructures Directorate and NASA Langley. Through the ongoing research program an in-depth understanding has been developed on the cause/effect relationships between material and architectural variables and the energy-absorption capability of composite material and structure. Composite materials were found to be efficient energy absorbers. Graphite/epoxy subfloor structures were more efficient energy absorbers than comparable structures fabricated from Kevlar or aluminum. An accurate method of predicting the energy-absorption capability of beams was developed.

  3. Electronic Structures of Silicene Nanoribbons: Two-Edge-Chemistry Modification and First-Principles Study.

    PubMed

    Yao, Yin; Liu, Anping; Bai, Jianhui; Zhang, Xuanmei; Wang, Rui

    2016-12-01

    In this paper, we investigate the structural and electronic properties of zigzag silicene nanoribbons (ZSiNRs) with edge-chemistry modified by H, F, OH, and O, using the ab initio density functional theory method and local spin-density approximation. Three kinds of spin polarized configurations are considered: nonspin polarization (NM), ferromagnetic spin coupling for all electrons (FM), ferromagnetic ordering along each edge, and antiparallel spin orientation between the two edges (AFM). The H, F, and OH groups modified 8-ZSiNRs have the AFM ground state. The directly edge oxidized (O1) ZSiNRs yield the same energy and band structure for NM, FM, and AFM configurations, owning to the same s p (2) hybridization. And replacing the Si atoms on the two edges with O atoms (O2) yields FM ground state. The edge-chemistry-modified ZSiNRs all exhibit metallic band structures. And the modifications introduce special edge state strongly localized at the Si atoms in the edge, except for the O1 form. The modification of the zigzag edges of silicene nanoribbons is a key issue to apply the silicene into the field effect transistors (FETs) and gives more necessity to better understand the experimental findings.

  4. Transport Measurements and Synchrotron-Based X-Ray Absorption Spectroscopy of Iron Silicon Germanide Grown by Molecular Beam Epitaxy

    NASA Astrophysics Data System (ADS)

    Elmarhoumi, Nader; Cottier, Ryan; Merchan, Greg; Roy, Amitava; Lohn, Chris; Geisler, Heike; Ventrice, Carl, Jr.; Golding, Terry

    2009-03-01

    Some of the iron-based metal silicide and germanide phases have been predicted to be direct band gap semiconductors. Therefore, they show promise for use as optoelectronic materials. We have used synchrotron-based x-ray absorption spectroscopy to study the structure of iron silicon germanide films grown by molecular beam epitaxy. A series of Fe(Si1-xGex)2 thin films (2000 -- 8000å) with a nominal Ge concentration of up to x = 0.04 have been grown. X-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) measurements have been performed on the films. The nearest neighbor co-ordination corresponding to the β-FeSi2 phase of iron silicide provides the best fit with the EXAFS data. Temperature dependent (20 < T < 350 K) magneto transport measurements were done on the Fe(Si1-xGex)2 thin films via Van Der Paw (VDP) Hall configuration using a 0.5-1T magnetic field and a current of 10-200 μA through indium ohmic contacts, the Hall coefficient was calculated. Results suggest semiconducting behavior of the films which is consistent with the EXAFS results.

  5. Pushing the limits of CMOS optical parametric amplifiers with USRN:Si7N3 above the two-photon absorption edge

    PubMed Central

    Ooi, K. J. A.; Ng, D. K. T.; Wang, T.; Chee, A. K. L.; Ng, S. K.; Wang, Q.; Ang, L. K.; Agarwal, A. M.; Kimerling, L. C.; Tan, D. T. H.

    2017-01-01

    CMOS platforms operating at the telecommunications wavelength either reside within the highly dissipative two-photon regime in silicon-based optical devices, or possess small nonlinearities. Bandgap engineering of non-stoichiometric silicon nitride using state-of-the-art fabrication techniques has led to our development of USRN (ultra-silicon-rich nitride) in the form of Si7N3, that possesses a high Kerr nonlinearity (2.8 × 10−13 cm2 W−1), an order of magnitude larger than that in stoichiometric silicon nitride. Here we experimentally demonstrate high-gain optical parametric amplification using USRN, which is compositionally tailored such that the 1,550 nm wavelength resides above the two-photon absorption edge, while still possessing large nonlinearities. Optical parametric gain of 42.5 dB, as well as cascaded four-wave mixing with gain down to the third idler is observed and attributed to the high photon efficiency achieved through operating above the two-photon absorption edge, representing one of the largest optical parametric gains to date on a CMOS platform. PMID:28051064

  6. Fluid-structure interaction analysis and lifetime estimation of a natural gas pipeline centrifugal compressor under near-choke and near-surge conditions

    NASA Astrophysics Data System (ADS)

    Ju, Yaping; Liu, Hui; Yao, Ziyun; Xing, Peng; Zhang, Chuhua

    2015-11-01

    Up to present, there have been no studies concerning the application of fluid-structure interaction (FSI) analysis to the lifetime estimation of multi-stage centrifugal compressors under dangerous unsteady aerodynamic excitations. In this paper, computational fluid dynamics (CFD) simulations of a three-stage natural gas pipeline centrifugal compressor are performed under near-choke and near-surge conditions, and the unsteady aerodynamic pressure acting on impeller blades are obtained. Then computational structural dynamics (CSD) analysis is conducted through a one-way coupling FSI model to predict alternating stresses in impeller blades. Finally, the compressor lifetime is estimated using the nominal stress approach. The FSI results show that the impellers of latter stages suffer larger fluctuation stresses but smaller mean stresses than those at preceding stages under near-choke and near-surge conditions. The most dangerous position in the compressor is found to be located near the leading edge of the last-stage impeller blade. Compressor lifetime estimation shows that the investigated compressor can run up to 102.7 h under the near-choke condition and 200.2 h under the near-surge condition. This study is expected to provide a scientific guidance for the operation safety of natural gas pipeline centrifugal compressors.

  7. 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

  8. 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.

  9. 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

  10. Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

    NASA Astrophysics Data System (ADS)

    Zheng, Jian; Zhang, Wei; Wang, Feng; Yu, Xiao-Ying

    2018-05-01

    In this paper, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K3[Fe(CN)6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K3[Fe(CN)6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.

  11. Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor.

    PubMed

    Zheng, Jian; Zhang, Wei; Wang, Feng; Yu, Xiao-Ying

    2018-05-10

    In this paper, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K 3 [Fe(CN) 6 ] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K 3 [Fe(CN) 6 ]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.

  12. Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

    DOE PAGES

    Zheng, Jian; Zhang, Wei; Wang, Feng; ...

    2018-04-11

    In this study, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K 3[Fe(CN) 6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Åmore » and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K 3[Fe(CN) 6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.« less

  13. Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

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

    Zheng, Jian; Zhang, Wei; Wang, Feng

    In this study, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K 3[Fe(CN) 6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Åmore » and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K 3[Fe(CN) 6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.« less

  14. Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

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

    Zheng, Jian; Zhang, Wei; Wang, Feng

    In this paper, a vacuum compatible microfluidic device, System for Analysis at the Liquid Vacuum Interface (SALVI), is integrated to hard x-ray absorption spectroscopy (XAS) to obtain the local structure of K3[Fe(CN)6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel of 500 μm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra show that the complex in water is Fe(III). The complex is present with octahedral geometry coordinated with 6 C atoms in the first shell with a distance ofmore » ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K3[Fe(CN)6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities and it is a viable approach to enable multifaceted measurements of liquids in the future.« less

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

    NASA Astrophysics Data System (ADS)

    Johnson, Phillip S.

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

  16. Utilizing Near-IR Tunable Laser Absorption Spectroscopy to Study Detonation and Combustion Systems

    DTIC Science & Technology

    2014-03-27

    debris, such as soot . Velocity curves for the other equivalence ratios studied in this experiment are shown in Appendix A. Some of these curves show a...James R. Gord. “Measurements of OH mole fraction and temperature up to 20 kHz by using a diode-laser based UV absorption sensor ”. Applied Optics, 44...Davidson, and R.K. Hanson. “CO concentration and temperature sensor for combustion gases using quantum-cascade laser absorption near 4.7µm”. Applied

  17. Development of the surface-sensitive soft x-ray absorption fine structure measurement technique for the bulk insulator

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

    Yonemura, Takumi, E-mail: yonemura-takumi@sei.co.jp; Iihara, Junji; Uemura, Shigeaki

    We have succeeded in measuring X-ray absorption fine structure (TEY-XAFS) spectra of insulating plate samples by total electron yield. The biggest problem is how to suppress the charge-up. We have attempted to deposit a gold stripe electrode on the surface and obtained a TEY-XAFS spectrum. This indicates that the metal stripe electrode is very useful in the TEY-XAFS measurement of the insulating plate samples. In the detailed analysis, we have found that the effective area for suppressing charge-up was approximately 120 μm from the edge of the electrode.

  18. Near unity ultraviolet absorption in graphene without patterning

    NASA Astrophysics Data System (ADS)

    Zhu, Jinfeng; Yan, Shuang; Feng, Naixing; Ye, Longfang; Ou, Jun-Yu; Liu, Qing Huo

    2018-04-01

    Enhancing the light-matter interaction of graphene is an important issue for related photonic devices and applications. In view of its potential ultraviolet applications, we aim to achieve extremely high ultraviolet absorption in graphene without any nanostructure or microstructure patterning. By manipulating the polarization and angle of incident light, the ultraviolet power can be sufficiently coupled to the optical dissipation of graphene based on single-channel coherent perfect absorption in an optimized multilayered thin film structure. The ultraviolet absorbance ratios of single and four atomic graphene layers are enhanced up to 71.4% and 92.2%, respectively. Our research provides a simple and efficient scheme to trap ultraviolet light for developing promising photonic and optoelectronic devices based on graphene and potentially other 2D materials.

  19. Structural motifs of pre-nucleation clusters.

    PubMed

    Zhang, Y; Türkmen, I R; Wassermann, B; Erko, A; Rühl, E

    2013-10-07

    Structural motifs of pre-nucleation clusters prepared in single, optically levitated supersaturated aqueous aerosol microparticles containing CaBr2 as a model system are reported. Cluster formation is identified by means of X-ray absorption in the Br K-edge regime. The salt concentration beyond the saturation point is varied by controlling the humidity in the ambient atmosphere surrounding the 15-30 μm microdroplets. This leads to the formation of metastable supersaturated liquid particles. Distinct spectral shifts in near-edge spectra as a function of salt concentration are observed, in which the energy position of the Br K-edge is red-shifted by up to 7.1 ± 0.4 eV if the dilute solution is compared to the solid. The K-edge positions of supersaturated solutions are found between these limits. The changes in electronic structure are rationalized in terms of the formation of pre-nucleation clusters. This assumption is verified by spectral simulations using first-principle density functional theory and molecular dynamics calculations, in which structural motifs are considered, explaining the experimental results. These consist of solvated CaBr2 moieties, rather than building blocks forming calcium bromide hexahydrates, the crystal system that is formed by drying aqueous CaBr2 solutions.

  20. Soft edges--organizational structure in dental education.

    PubMed

    Chambers, D W

    1995-03-01

    There is no one best organizational structure for dental schools or for their major subunits. The classical alternatives of functional and divisional organization are discussed in light of the rule that follows function, and the advantages and disadvantages of each are presented. Newer models--decentralization, matrix, and heterarchy--show how features of functional and divisional structure can be blended. Virtual organizations, systems theory, and networks are also considered as new expressions of classical structures. The principle of suboptimization (soft edges) is presented.

  1. 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.

  2. High Confinement Mode and Edge Localized Mode Characteristics in a Near-Unity Aspect Ratio Tokamak.

    PubMed

    Thome, K E; Bongard, M W; Barr, J L; Bodner, G M; Burke, M G; Fonck, R J; Kriete, D M; Perry, J M; Schlossberg, D J

    2016-04-29

    Tokamak experiments at near-unity aspect ratio A≲1.2 offer new insights into the self-organized H-mode plasma confinement regime. In contrast to conventional A∼3 plasmas, the L-H power threshold P_{LH} is ∼15× higher than scaling predictions, and it is insensitive to magnetic topology, consistent with modeling. Edge localized mode (ELM) instabilities shift to lower toroidal mode numbers as A decreases. These ultralow-A operations enable heretofore inaccessible J_{edge}(R,t) measurements through an ELM that show a complex multimodal collapse and the ejection of a current-carrying filament.

  3. High confinement mode and edge localized mode characteristics in a near-unity aspect ratio tokamak

    DOE PAGES

    Thome, Kathreen E.; Bongard, Michael W.; Barr, Jayson L.; ...

    2016-04-27

    Tokamak experiments at near-unity aspect ratio A ≲ 1.2 offer new insights into the self-organized H-mode plasma confinement regime. In contrast to conventional A ~ 3 plasmas, the L–H power threshold P LH is ~15× higher than scaling predictions, and it is insensitive to magnetic topology, consistent with modeling. Edge localized mode (ELM) instabilities shift to lower toroidal mode numbers as A decreases. Furthermore, these ultralow-A operations enable heretofore inaccessible J edge(R,t) measurements through an ELM that show a complex multimodal collapse and the ejection of a current-carrying filament.

  4. Localized modes in optics of photonic liquid crystals with local anisotropy of absorption

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

    Belyakov, V. A., E-mail: bel1937@mail.ru, E-mail: bel@landau.ac.ru; Semenov, S. V.

    2016-05-15

    The localized optical modes in spiral photonic liquid crystals are theoretically studied for the certainty at the example of chiral liquid crystals (CLCs) for the case of CLC with an anisotropic local absorption. The model adopted here (absence of dielectric interfaces in the structures under investigation) makes it possible to get rid of mixing of polarizations on the surfaces of the CLC layer and of the defect structure and to reduce the corresponding equations to only the equations for light with polarization diffracting in the CLC. The dispersion equations determining connection of the edge mode (EM) and defect mode (DM)more » frequencies with the CLC layer parameters (anisotropy of local absorption, CLC order parameter) and other parameters of the DMS are obtained. Analytic expressions for the transmission and reflection coefficients of CLC layer and DMS for the case of CLC with an anisotropic local absorption are presented and analyzed. It is shown that the CLC layers with locally anisotropic absorption reduce the EM and DM lifetimes (and increase the lasing threshold) in the way different from the case of CLC with an isotropic local absorption. Due to the Borrmann effect revealing of which is different at the opposite stop-band edges in the case of CLC layers with an anisotropic local absorption the EM life-times for the EM frequencies at the opposite stop-bands edges may be significantly different. The options of experimental observations of the theoretically revealed phenomena are briefly discussed.« less

  5. 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.

  6. Colloidal quantum dot solar cells exploiting hierarchical structuring.

    PubMed

    Labelle, André J; Thon, Susanna M; Masala, Silvia; Adachi, Michael M; Dong, Haopeng; Farahani, Maryam; Ip, Alexander H; Fratalocchi, Andrea; Sargent, Edward H

    2015-02-11

    Extremely thin-absorber solar cells offer low materials utilization and simplified manufacture but require improved means to enhance photon absorption in the active layer. Here, we report enhanced-absorption colloidal quantum dot (CQD) solar cells that feature transfer-stamped solution-processed pyramid-shaped electrodes employed in a hierarchically structured device. The pyramids increase, by up to a factor of 2, the external quantum efficiency of the device at absorption-limited wavelengths near the absorber band edge. We show that absorption enhancement can be optimized with increased pyramid angle with an appreciable net improvement in power conversion efficiency, that is, with the gain in current associated with improved absorption and extraction overcoming the smaller fractional decrease in open-circuit voltage associated with increased junction area. We show that the hierarchical combination of micron-scale structured electrodes with nanoscale films provides for an optimized enhancement at absorption-limited wavelengths. We fabricate 54.7° pyramid-patterned electrodes, conformally apply the quantum dot films, and report pyramid CQD solar cells that exhibit a 24% improvement in overall short-circuit current density with champion devices providing a power conversion efficiency of 9.2%.

  7. Forests on the edge: Microenvironmental drivers of carbon cycle response to edge effects

    NASA Astrophysics Data System (ADS)

    Reinmann, A.; Hutyra, L.; Smith, I. A.; Thompson, J.

    2017-12-01

    Twenty percent of the world's forest is within 100 m of a forest edge, but much of our understanding of forest carbon (C) cycling comes from large, intact ecosystems, which creates an important mismatch between the landscapes we study and those we aim to characterize. The temperate broadleaf forest is the most heavily fragmented forest biome in the world and its growth and carbon storage responses to forest edge effects appear to be the opposite of those in the tropical and boreal regions. We used field measurements to quantify the drivers of temperate forest C cycling response to edge effects, characterizing vegetative growth, respiration, and forest structure. We find large gradients in air and soil temperature from the forest interior to edge (up to 4 and 10° C, respectively) and the magnitude of this gradient is inversely correlated to the size of the forest edge growth enhancement. Further, leaf area index increases with proximity to the forest edge. While we also find increases in soil respiration between the forest interior and edge, this flux is small relative to aboveground growth enhancement near the edge. These findings represent an important advancement in our understanding of forest C cycle response to edge effects and will greatly improve our capacity to constrain biogenic C fluxes in fragmented and heterogeneous landscapes.

  8. Electromagnetic absorption in a multilayered slab model of tissue under near-field exposure conditions.

    PubMed

    Chatterjee, I; Hagmann, M J; Gandhi, O P

    1980-01-01

    The electromagnetic energy deposited in a semi-infinite slab model consisting of skin, fat, and muscle layers is calculated for both plane-wave and near-field exposures. The plane-wave spectrum (PWS) approach is used to calculate the energy deposited in the model by fields present due to leakage from equipment using electromagnetic energy. This analysis applies to near-field exposures where coupling of the target to the leakage source can be neglected. Calculations were made for 2,450 MHz, at which frequency the layered slab adequately models flat regions of the human body. Resonant absorption due to layering is examined as a function of the skin and fat thicknesses for plane-wave exposure and as a function of the physical extent of the near-field distribution. Calculations show that for fields that are nearly constant over at least a free-space wavelength, the energy deposition (for skin, fat, and muscle combination that gives resonant absorption) is equal to or less than that resulting from plane-wave exposure, but is appreciably greater than that obtained for a homogeneous muscle slab model.

  9. Applications of x ray absorption fine structure to the in situ study of the effect of cobalt in nickel hydrous oxide electrodes for fuel cells and rechargeable batteries

    NASA Technical Reports Server (NTRS)

    Kim, Sunghyun; Tryk, Donald A.; Scherson, Daniel A.; Antonio, Mark R.

    1993-01-01

    Electronic and structural aspects of composite nickel-cobalt hydrous oxides have been examined in alkaline solutions using in situ X-ray absorption fine structure (XAFS). The results obtained have indicated that cobalt in this material is present as cobaltic ions regardless of the oxidation state of nickel in the lattice. Furthermore, careful analysis of the Co K-edge Extended X-ray absorption fine structure data reveals that the co-electrodeposition procedure generates a single phase, mixed metal hydrous oxide, in which cobaltic ions occupy nickel sites in the NiO2 sheet-like layers and not two intermixed phases each consisting of a single metal hydrous oxide.

  10. Transformation-optics description of plasmonic nanostructures containing blunt edges/corners: from symmetric to asymmetric edge rounding.

    PubMed

    Luo, Yu; Lei, Dang Yuan; Maier, Stefan A; Pendry, John B

    2012-07-24

    The sharpness of corners/edges can have a large effect on the optical responses of metallic nanostructures. Here we deploy the theory of transformation optics to analytically investigate a variety of blunt plasmonic structures, including overlapping nanowire dimers and crescent-shaped nanocylinders. These systems are shown to support several discrete optical modes, whose energy and line width can be controlled by tuning the nanoparticle geometry. In particular, the necessary conditions are highlighted respectively for the broadband light absorption effect and the invisibility dips that appear in the radiative spectrum. More detailed discussions are provided especially with respect to the structures with asymmetric edge rounding. These structures can support additional subradiant modes, whose interference with the neighboring dipolar modes results in a rapid change of the scattering cross-section, similar to the phenomenon observed in plasmonic Fano resonances. Finite element numerical calculations are also performed to validate the analytical predictions. The physical insights into blunt nanostructures presented in this work may be of great interest for the design of broadband light-harvesting devices, invisible and noninvasive biosensors, and slowing-light devices.

  11. 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.

  12. A Theory of Oscillating Edge Flames

    NASA Technical Reports Server (NTRS)

    Buckmaster, J.; Zhang, Yi

    1999-01-01

    It has been known for some years that when a near-limit flame spreads over a liquid pool of fuel, the edge of the flame can oscillate relative to a frame moving with the mean speed. Each period of oscillation is characterized by long intervals of modest motion during which the edge gases radiate like those of a diffusion flame, punctuated by bursts of rapid advance during which the edge gases radiate like those in a deflagration. Substantial resources have been brought to bear on this issue within the microgravity program, both experimental and numerical. It is also known that when a near-asphyxiated candle-flame burns at zero gravity, the edge of the (hemispherical) flame can oscillate violently prior to extinction. Thus a web-surfer, turning to the NASA web-site at http://microgravity.msfc.nasa.gov, and following the trail combustion science/experiments/experimental results/candle flame, will find photographs and a description of candle burning experiments carried out on board both the Space-shuttle and the Russian space station Mir. A brief report can also be found in the proceedings of the Fourth Workshop. And recently, in a third microgravity program, the leading edge of the flame supported by injection of ethane through the porous surface of a plate over which air is blown has been found to oscillate when conditions are close to blow-off. A number of important points can be made with respect to these observations: It is the edge itself which oscillates, advancing and retreating, not the diffusion flame that trails behind the edge; oscillations only occur under near limit conditions; in each case the Lewis number of the fuel is significantly larger than 1; and because of the edge curvature, the heat losses from the reacting edge structure are larger than those from the trailing diffusion flame. We propose a general theory for these oscillations, invoking Occam's 'Law of Parsimony' in an expanded form, to wit: The same mechanism is responsible for the

  13. The Red Edge Problem in asteroid band parameter analysis

    NASA Astrophysics Data System (ADS)

    Lindsay, Sean S.; Dunn, Tasha L.; Emery, Joshua P.; Bowles, Neil E.

    2016-04-01

    Near-infrared reflectance spectra of S-type asteroids contain two absorptions at 1 and 2 μm (band I and II) that are diagnostic of mineralogy. A parameterization of these two bands is frequently employed to determine the mineralogy of S(IV) asteroids through the use of ordinary chondrite calibration equations that link the mineralogy to band parameters. The most widely used calibration study uses a Band II terminal wavelength point (red edge) at 2.50 μm. However, due to the limitations of the NIR detectors on prominent telescopes used in asteroid research, spectral data for asteroids are typically only reliable out to 2.45 μm. We refer to this discrepancy as "The Red Edge Problem." In this report, we evaluate the associated errors for measured band area ratios (BAR = Area BII/BI) and calculated relative abundance measurements. We find that the Red Edge Problem is often not the dominant source of error for the observationally limited red edge set at 2.45 μm, but it frequently is for a red edge set at 2.40 μm. The error, however, is one sided and therefore systematic. As such, we provide equations to adjust measured BARs to values with a different red edge definition. We also provide new ol/(ol+px) calibration equations for red edges set at 2.40 and 2.45 μm.

  14. Optical absorption and disorder in delafossites

    DOE PAGES

    Senty, Tess R.; Haycock, Barry; Lekse, Jonathan; ...

    2017-07-06

    Here, we present compelling experimental results of the optical characteristics of transparent oxide CuGaO 2 and related CuGa 1-xFe xO 2 (with 0.00 ≤ x ≤ 0.05) alloys, whereby the forbidden electronic transitions for CuGaO 2 become permissible in the presence of B-site (Ga sites) alloying with Fe. Our computational structural results imply a correlation between the global strain on the system and a decreased optical absorption edge. However, herein, we show that the relatively ordered CuGa 1-xFe xO 2 (for 0.00 ≤ x ≤ 0.04) structures exhibit much weaker vis-absorption compared to the relatively disordered CuGa 0.95Fe 0.05O 2.

  15. Tunable diode laser measurements of HO2NO2 absorption coefficients near 12.5 microns

    NASA Technical Reports Server (NTRS)

    May, R. D.; Molina, L. T.; Webster, C. R.

    1988-01-01

    A tunable diode laser spectrometer has been used to measure absorption coefficients of peroxynitric acid (HO2NO2) near the 803/cm Q branch. HO2NO2 concentrations in a low-pressure flowing gas mixture were determined from chemical titration procedures and UV absorption spectroscopy. The diode laser measured absorption coefficients, at a spectral resolution of better than 0.001/cm, are about 10 percent larger than previous Fourier transform infrared measurements made at a spectral resolution of 0.06/cm.

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

    PubMed

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

    2014-08-30

    The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy.

    PubMed

    Moonshiram, Dooshaye; Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Picón, Antonio; Liu, Cunming; Zhang, Xiaoyi; Karnahl, Michael; Llobet, Antoni

    2018-04-25

    We report the light-induced electronic and geometric changes taking place within a heteroleptic Cu I photosensitizer, namely [(xant)Cu(Me 2 phenPh 2 )]PF 6 (xant=xantphos, Me 2 phenPh 2 =bathocuproine), by time-resolved X-ray absorption spectroscopy in the ps-μs time regime. Time-resolved X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis enabled the elucidation of the electronic and structural configuration of the copper center in the excited state as well as its decay dynamics in different solvent conditions with and without triethylamine acting as a sacrificial electron donor. A three-fold decrease in the decay lifetime of the excited state is observed in the presence of triethylamine, showing the feasibility of the reductive quenching pathway in the latter case. A prominent pre-edge feature is observed in the XANES spectrum of the excited state upon metal to charge ligand transfer transition, showing an increased hybridization of the 3d states with the ligand p orbitals in the tetrahedron around the Cu center. EXAFS and density functional theory illustrate a significant shortening of the Cu-N and an elongation of the Cu-P bonds together with a decrease in the torsional angle between the xantphos and bathocuproine ligand. This study provides mechanistic time-resolved understanding for the development of improved heteroleptic Cu I photosensitizers, which can be used for the light-driven production of hydrogen from water. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Lower hybrid wave edge power loss quantification on the Alcator C-Mod tokamak

    NASA Astrophysics Data System (ADS)

    Faust, I. C.; Brunner, D.; LaBombard, B.; Parker, R. R.; Terry, J. L.; Whyte, D. G.; Baek, S. G.; Edlund, E.; Hubbard, A. E.; Hughes, J. W.; Kuang, A. Q.; Reinke, M. L.; Shiraiwa, S.; Wallace, G. M.; Walk, J. R.

    2016-05-01

    For the first time, the power deposition of lower hybrid RF waves into the edge plasma of a diverted tokamak has been systematically quantified. Edge deposition represents a parasitic loss of power that can greatly impact the use and efficiency of Lower Hybrid Current Drive (LHCD) at reactor-relevant densities. Through the use of a unique set of fast time resolution edge diagnostics, including innovative fast-thermocouples, an extensive set of Langmuir probes, and a Lyα ionization camera, the toroidal, poloidal, and radial structure of the power deposition has been simultaneously determined. Power modulation was used to directly isolate the RF effects due to the prompt ( t < τ E ) response of the scrape-off-layer (SOL) plasma to Lower Hybrid Radiofrequency (LHRF) power. LHRF power was found to absorb more strongly in the edge at higher densities. It is found that a majority of this edge-deposited power is promptly conducted to the divertor. This correlates with the loss of current drive efficiency at high density previously observed on Alcator C-Mod, and displaying characteristics that contrast with the local RF edge absorption seen on other tokamaks. Measurements of ionization in the active divertor show dramatic changes due to LHRF power, implying that divertor region can be a key for the LHRF edge power deposition physics. These observations support the existence of a loss mechanism near the edge for LHRF at high density ( n e > 1.0 × 10 20 (m-3)). Results will be shown addressing the distribution of power within the SOL, including the toroidal symmetry and radial distribution. These characteristics are important for deducing the cause of the reduced LHCD efficiency at high density and motivate the tailoring of wave propagation to minimize SOL interaction, for example, through the use of high-field-side launch.

  19. InAs Band-Edge Exciton Fine Structure

    DTIC Science & Technology

    2015-07-29

    Chapter 1 InAs Band-Edge Exciton Fine Structure 1.1 Contributions This work was carried out in collaboration with Oscar Sandoval, a summer student at...diffusion,1,2 charg- ing,2,3 and excitonic fine structure.1,3–9 While spectral diffusion and charging are most likely photoinduced effects and thus can be...unavoidable. A complete understanding of the excitonic 1 Distribution A: Public Release energy landscape enables us to determine dephasing rates

  20. Beyond edge effects: landscape controls on forest structure in the southeastern US

    NASA Astrophysics Data System (ADS)

    Fagan, M. E.; Morton, D. C.; Cook, B.; Masek, J. G.; Zhao, F. A.; Nelson, R.; Huang, C.

    2016-12-01

    The structure of forest canopies (i.e., their height and complexity) is known to be influenced by a variety of factors, including forest age, species composition, disturbance, edaphic and topographical conditions, and exposure to edge environments. The combined impact of each of these factors on canopy structure is not well characterized for most forest ecosystems, however, which limits our ability to predict the regional impacts of forest fragmentation. The objective of this study was to elucidate the main biophysical drivers of canopy structure across two dominant ecosystems in the southeastern U.S: natural mixed deciduous forests, and industrial conifer plantations. We analyzed spatial changes in canopy structure along aerial transects of LiDAR data ( 3,000 km in all). High-resolution (1 m) LiDAR data from Goddard's LiDAR, Hyperspectral, and Thermal Airborne Imager (G-LiHT) were combined with time series of Landsat imagery to quantify forest type, age, composition, and fragmentation. Forest structural metrics (height, gap fraction, and canopy roughness) were examined across forest types, ages, topography, and decreasing edge exposure. We hypothesized that 1) structural edge effects would be weak in both natural and plantation forest types, and 2) age, composition, and topography would be the dominant influences on natural forest structure. We analyzed all large (>4 ha) fragments from the 8562 distinct forests measured during G-LiHT data collections in 2011 across the southeastern U.S. In general, the relationship between forest structural metrics and edge exposure was highly variable in both natural forests and plantations. However, variability in all structural metrics decreased with distance from an edge. Forest age and topography were strong predictors of canopy structure in natural forests. However plantations tended to be located in sites with limited topographical variation, and thinning disturbances of conifer plantations decreased the strength of the age-structure

  1. Effects of Sulfation Level on the Desulfation Behavior of Presulfated Pt-BaO/Al2O3 Lean NOx Trap Catalysts: A Combined H2 Temperature-Programmed Reaction, in Situ Sulfur K-Edge X-ray Absorption Near-Edge Spectroscopy, X-ray Photoelectron Spectroscopy, and Time-Resolved X-ray Diffraction Study

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

    Kim, D.H.; Hanson, J.; Szanyi, J.

    2009-04-30

    Desulfation by hydrogen of presulfated Pt (2 wt %)-BaO(20 wt %)/Al{sub 2}O{sub 3} with various sulfur loading (S/Ba = 0.12, 0.31, and 0.62) were investigated by combining H{sub 2} temperature programmed reaction (TPRX), X-ray photoelectron spectroscopy (XPS), in situ sulfur K-edge X-ray absorption near-edge spectroscopy (XANES), and synchrotron time-resolved X-ray diffraction (TR-XRD) techniques. We find that the amount of H{sub 2}S desorbed during the desulfation in the H{sub 2} TPRX experiments is not proportional to the amount of initial sulfur loading. The results of both in situ sulfur K-edge XANES and TR-XRD show that at low sulfur loadings, sulfates weremore » transformed to a BaS phase and remained in the catalyst rather than being removed as H{sub 2}S. On the other hand, when the deposited sulfur level exceeded a certain threshold (at least S/Ba = 0.31) sulfates were reduced to form H{sub 2}S, and the relative amount of the residual sulfide species in the catalyst was much less than at low sulfur loading. Unlike samples with high sulfur loading (e.g., S/Ba = 0.62), H{sub 2}O did not promote the desulfation for the sample with S/Ba of 0.12, implying that the formed BaS species originating from the reduction of sulfates at low sulfur loading are more stable to hydrolysis. The results of this combined spectroscopy investigation provide clear evidence to show that sulfates at low sulfur loadings are less likely to be removed as H{sub 2}S and have a greater tendency to be transformed to BaS on the material, leading to the conclusion that desulfation behavior of Pt-BaO/Al{sub 2}O{sub 3} lean NO{sub x} trap catalysts is markedly dependent on the sulfation levels.« less

  2. Water vapour foreign-continuum absorption in near-infrared windows from laboratory measurements.

    PubMed

    Ptashnik, Igor V; McPheat, Robert A; Shine, Keith P; Smith, Kevin M; Williams, R Gary

    2012-06-13

    For a long time, it has been believed that atmospheric absorption of radiation within wavelength regions of relatively high infrared transmittance (so-called 'windows') was dominated by the water vapour self-continuum, that is, spectrally smooth absorption caused by H(2)O--H(2)O pair interaction. Absorption due to the foreign continuum (i.e. caused mostly by H(2)O--N(2) bimolecular absorption in the Earth's atmosphere) was considered to be negligible in the windows. We report new retrievals of the water vapour foreign continuum from high-resolution laboratory measurements at temperatures between 350 and 430 K in four near-infrared windows between 1.1 and 5 μm (9000-2000 cm(-1)). Our results indicate that the foreign continuum in these windows has a very weak temperature dependence and is typically between one and two orders of magnitude stronger than that given in representations of the continuum currently used in many climate and weather prediction models. This indicates that absorption owing to the foreign continuum may be comparable to the self-continuum under atmospheric conditions in the investigated windows. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by approximately 0.46 W m(-2) (or 0.6% of the total clear-sky absorption) by using these new measurements when compared with calculations applying the widely used MTCKD (Mlawer-Tobin-Clough-Kneizys-Davies) foreign-continuum model.

  3. Living on the edge: roads and edge effects on small mammal populations.

    PubMed

    Fuentes-Montemayor, Elisa; Cuarón, Alfredo D; Vázquez-Domínguez, Ella; Benítez-Malvido, Julieta; Valenzuela-Galván, David; Andresen, Ellen

    2009-07-01

    1. Roads may affect wildlife populations through habitat loss and disturbances, as they create an abrupt linear edge, increasing the proportion of edge exposed to a different habitat. Three types of edge effects have been recognized: abiotic, direct biotic, and indirect biotic. 2. We explored the direct biotic edge effects of 3- to 4-m wide roads, and also a previously unrecognized type of edge effect: social. We live-trapped two threatened endemic rodents from Cozumel Island (Oryzomys couesi cozumelae and Reithrodontomys spectabilis) in 16 plots delimited by roads on two sides, to compare edge effects between two adjacent edges (corners), single-edge and interior forest, on life history and social variables. 3. No significant edge effects were observed on the life-history variables, with the exception of differences in body condition between males and females of O. c. cozumelae near edges. Both species showed significant and contrasting effects on their social variables. 4. O. c. cozumelae was distributed according to its age and sex: the proportion of adults and males was higher in interior than near edges, while juveniles and females were more abundant near edges. More nonreproductive females were present in corners than in single-edge and interior, while the opposite distribution was observed for nonreproductive males. 5. The distribution of R. spectabilis was related to its age and reproductive condition, but not to its sex. The proportion of adults was significantly higher in corners, while juveniles were only caught in single-edge and interior quadrants. The proportion of reproductive individuals was higher in edge than interior quadrants, while reproductive females were only present in edge quadrants. 6. We found significant differences between the quadrants with the greatest edge exposure in comparison with other quadrants. The social edge effects we identified complement the typology of edge effects recognized in ecological literature. Our study provides

  4. [INVITED] Coherent perfect absorption of electromagnetic wave in subwavelength structures

    NASA Astrophysics Data System (ADS)

    Yan, Chao; Pu, Mingbo; Luo, Jun; Huang, Yijia; Li, Xiong; Ma, Xiaoliang; Luo, Xiangang

    2018-05-01

    Electromagnetic (EM) absorption is a common process by which the EM energy is transformed into other kinds of energy in the absorber, for example heat. Perfect absorption of EM with structures at subwavelength scale is important for many practical applications, such as stealth technology, thermal control and sensing. Coherent perfect absorption arises from the interplay of interference and absorption, which can be interpreted as a time-reversed process of lasing or EM emitting. It provides a promising way for complete absorption in both nanophotonics and electromagnetics. In this review, we discuss basic principles and properties of a coherent perfect absorber (CPA). Various subwavelength structures including thin films, metamaterials and waveguide-based structures to realize CPAs are compared. We also discuss the potential applications of CPAs.

  5. Optical Kerr effect and two-photon absorption in monolayer black phosphorus

    NASA Astrophysics Data System (ADS)

    Margulis, Vl A.; Muryumin, E. E.; Gaiduk, E. A.

    2018-05-01

    A theoretical treatment of nonlinear refraction and two-photon absorption is presented for a novel two-dimensional material, monolayer black phosphorus (or phosphorene), irradiated by a normally incident and linearly polarized coherent laser beam of frequency ω. It is found that both the nonlinear refractive index n 2(ω) and the two-photon absorption coefficient α 2(ω) of phosphorene depend upon the polarization of the radiation field relative to phosphorene’s crystallographic axes. For the two principal polarization directions considered—viz, the armchair ({ \\mathcal A }{ \\mathcal C }) and zigzag ({ \\mathcal Z }{ \\mathcal Z }), the calculated values of n 2 and α 2 are distinguished by the order of their magnitude, with the n 2 and α 2 values being greater for the { \\mathcal A }{ \\mathcal C } direction. Furthermore, for almost all the incident photon energies below the fundamental absorption edge, except its neighborhood, the signs of n 2 as well as α 2 for the { \\mathcal A }{ \\mathcal C } and { \\mathcal Z }{ \\mathcal Z } polarization directions are opposed to each other. Also, for both the directions, the change of sign of n 2 is predicted to occur in the way between the two-photon absorption edge and the fundamental absorption edge, as well as in the near vicinity of the latter, where the Kerr nonlinearity has a pronounced resonant character and the magnitude of n 2 for the { \\mathcal A }{ \\mathcal C } and { \\mathcal Z }{ \\mathcal Z } polarization directions reaches its largest positive values of the order of 10‑9 and 10‑10 cm2 W‑1, respectively. The implications of the findings for practical all-optical switching applications are discussed.

  6. Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

    PubMed

    Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

    2016-06-22

    Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

  7. 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.

  8. Bifurcations of edge states—topologically protected and non-protected—in continuous 2D honeycomb structures

    NASA Astrophysics Data System (ADS)

    Fefferman, C. L.; Lee-Thorp, J. P.; Weinstein, M. I.

    2016-03-01

    Edge states are time-harmonic solutions to energy-conserving wave equations, which are propagating parallel to a line-defect or ‘edge’ and are localized transverse to it. This paper summarizes and extends the authors’ work on the bifurcation of topologically protected edge states in continuous two-dimensional (2D) honeycomb structures. We consider a family of Schrödinger Hamiltonians consisting of a bulk honeycomb potential and a perturbing edge potential. The edge potential interpolates between two different periodic structures via a domain wall. We begin by reviewing our recent bifurcation theory of edge states for continuous 2D honeycomb structures (http://arxiv.org/abs/1506.06111). The topologically protected edge state bifurcation is seeded by the zero-energy eigenstate of a one-dimensional Dirac operator. We contrast these protected bifurcations with (more common) non-protected bifurcations from spectral band edges, which are induced by bound states of an effective Schrödinger operator. Numerical simulations for honeycomb structures of varying contrasts and ‘rational edges’ (zigzag, armchair and others), support the following scenario: (a) for low contrast, under a sign condition on a distinguished Fourier coefficient of the bulk honeycomb potential, there exist topologically protected edge states localized transverse to zigzag edges. Otherwise, and for general edges, we expect long lived edge quasi-modes which slowly leak energy into the bulk. (b) For an arbitrary rational edge, there is a threshold in the medium-contrast (depending on the choice of edge) above which there exist topologically protected edge states. In the special case of the armchair edge, there are two families of protected edge states; for each parallel quasimomentum (the quantum number associated with translation invariance) there are edge states which propagate in opposite directions along the armchair edge.

  9. Mapping Catalytically Relevant Edge Electronic States of MoS2

    PubMed Central

    2018-01-01

    Molybdenum disulfide (MoS2) is a semiconducting transition metal dichalcogenide that is known to be a catalyst for both the hydrogen evolution reaction (HER) as well as for hydro-desulfurization (HDS) of sulfur-rich hydrocarbon fuels. Specifically, the edges of MoS2 nanostructures are known to be far more catalytically active as compared to unmodified basal planes. However, in the absence of the precise details of the geometric and electronic structure of the active catalytic sites, a rational means of modulating edge reactivity remain to be developed. Here we demonstrate using first-principles calculations, X-ray absorption spectroscopy, as well as scanning transmission X-ray microscopy (STXM) imaging that edge corrugations yield distinctive spectroscopic signatures corresponding to increased localization of hybrid Mo 4d states. Independent spectroscopic signatures of such edge states are identified at both the S L2,3 and S K-edges with distinctive spatial localization of such states observed in S L2,3-edge STXM imaging. The presence of such low-energy hybrid states at the edge of the conduction band is seen to correlate with substantially enhanced electrocatalytic activity in terms of a lower Tafel slope and higher exchange current density. These results elucidate the nature of the edge electronic structure and provide a clear framework for its rational manipulation to enhance catalytic activity. PMID:29721532

  10. 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.

  11. 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

  12. Photoemission and Photoabsorption Investigation of the Electronic Structure of Ytterbium Doped Strontium Fluoroapatite

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

    Nelson, A J; van Buuren, T; Bostedt, C

    X-ray photoemission and x-ray photoabsorption were used to study the composition and the electronic structure of ytterbium doped strontium fluoroapatite (Yb:S-FAP). High resolution photoemission measurements on the valence band electronic structure was used to evaluate the density of occupied states of this fluoroapatite. Element specific density of unoccupied electronic states in Yb:S-FAP were probed by x-ray absorption spectroscopy (XAS) at the Yb 4d (N{sub 4,5}-edge), Sr 3d (M{sub 4,5}-edge), P 2p (L{sub 2,3}-edge), F 1s and O 1s (K-edges) absorption edges. These results provide the first measurements of the electronic structure and surface chemistry of this material.

  13. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    PubMed

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Local 3d Electronic Structures of Co-Based Complexes with Medicinal Molecules Probed by Soft X-ray Absorption

    NASA Astrophysics Data System (ADS)

    Yamagami, Kohei; Fujiwara, Hidenori; Imada, Shin; Kadono, Toshiharu; Yamanaka, Keisuke; Muro, Takayuki; Tanaka, Arata; Itai, Takuma; Yoshinari, Nobuto; Konno, Takumi; Sekiyama, Akira

    2017-07-01

    We have examined the local 3d electronic structures of Co-Au multinuclear complexes with the medicinal molecules d-penicillaminate (d-pen) [Co{Au(PPh3)(d-pen)}2]ClO4 and [Co3{Au3(tdme)(d-pen)3}2] by Co L2,3-edge soft X-ray absorption (XAS) spectroscopy, where PPh3 denotes triphenylphosphine and tdme stands for 1,1,1-tris[(diphenylphosphino)methyl]ethane. The Co L2,3-edge XAS spectra indicate the localized ionic 3d electronic states in both materials. The experimental spectra are well explained by spectral simulation for a localized Co ion under ligand fields with the full multiplet theory, which verifies that the ions are in the low-spin Co3+ state in the former compound and in the high-spin Co2+ state in the latter.

  15. Advanced leading edge thermal-structure concept. Direct bond reusable surface insulation to a composite structure

    NASA Technical Reports Server (NTRS)

    Riccitiello, S. R.; Figueroa, H.; Coe, C. F.; Kuo, C. P.

    1984-01-01

    An advanced leading-edge concept was analyzed using the space shuttle leading edge system as a reference model. The comparison indicates that a direct-bond system utilizing a high temperature (2700 F) fibrous refractory composite insulation tile bonded to a high temperature (PI/graphite) composite structure can result in a weight savings of up to 800 lb. The concern that tile damage or loss during ascent would result in adverse entry aerodynamics if a leading edge tile system were used is addressed. It was found from experiment that missing tiles (as many as 22) on the leading edge would not significantly affect the basic force-and-moment aerodynamic coefficients. Additionally, this concept affords a degree of redundancy to a thermal protection system in that the base structure (being a composite material) ablates and neither melts nor burns through when subjected to entry heating in the event tiles are actually lost or damaged during ascent.

  16. Spontaneous emission near the edge of a photonic band gap

    NASA Astrophysics Data System (ADS)

    John, Sajeev; Quang, Tran

    1994-08-01

    The spectral and dynamical features of spontaneous emission from two and three-level atoms in which one transition frequency lay near the edge of a photonic band gap (PBG) were derived. These features included temporal oscillations, fractionalized steady-state atomic population on the excited state, spectral splitting and subnatural bandwidth. The effect of N-1 unexcited atoms were also taken into account. The direct consequences of photon localization as embodied in the photon-atom bound state were observed. One feasible experimental accomplishment of these effects may ensue from laser-cooled atoms in the void regions of a PBG medium. Another option is the application of an organic impurity molecule such as pentacene. Such molecules were known to show extremely narrow linewidths when placed in fitting solid hosts.

  17. Enhancing acoustic signal response and absorption of an underwater coated plate by embedding periodical inhomogeneities.

    PubMed

    Zhang, Yanni; Pan, Jie

    2017-12-01

    An underwater structure is proposed for simultaneous detection and stealth purposes by embedding periodic signal conditioning plates (SCPs) at the interface of two elastic coatings attached to an elastic plate. Results show that the embedded SCPs can enhance sound absorption at frequencies below the coincidence frequency of the plate (f c ). Significantly enhanced absorption occurs at five peaks, of which the peak due to excited localized bending resonance in the outer coating between SCPs is the most significant. When the dilatational velocity of the outer coating equals that of the inner coating, nearly total absorption occurs in a wideband, owing to strong coupling between the localized waveguide resonance in the outer coating and that in the inner coating, and the diffraction waves by the SCPs. Meanwhile, an amplified acoustic signal of over 14 dB is observed at most frequencies within 0 ∼ f c at the coatings' interface close to the SCPs' edges, owing to focused stress formed there. Peaks in the signal response at maximal 30 dB are also observed. These peak frequencies are coincident with or close to the peak frequencies of absorption, demonstrating that significantly enhanced acoustic signal and absorption can be achieved simultaneously through the use of embedded periodic SCPs.

  18. Structure-activity correlations in a nickel-borate oxygen evolution catalyst.

    PubMed

    Bediako, D Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh; Yano, Junko; Yachandra, Vittal K; Nocera, Daniel G

    2012-04-18

    An oxygen evolution catalyst that forms as a thin film from Ni(aq)(2+) solutions containing borate electrolyte (Ni-B(i)) has been studied by in situ X-ray absorption spectroscopy. A dramatic increase in catalytic rate, induced by anodic activation of the electrodeposited films, is accompanied by structure and oxidation state changes. Coulometric measurements correlated with X-ray absorption near-edge structure spectra of the active catalyst show that the nickel centers in activated films possess an average oxidation state of +3.6, indicating that a substantial proportion of nickel centers exist in a formal oxidation state of Ni(IV). In contrast, nickel centers in nonactivated films exist predominantly as Ni(III). Extended X-ray absorption fine structure reveals that activated catalyst films comprise bis-oxo/hydroxo-bridged nickel centers organized into sheets of edge-sharing NiO(6) octahedra. Diminished long-range ordering in catalyst films is due to their ostensibly amorphous nature. Nonactivated films display a similar oxidic nature but exhibit a distortion in the local coordination geometry about nickel centers, characteristic of Jahn-Teller distorted Ni(III) centers. Our findings indicate that the increase in catalytic activity of films is accompanied by changes in oxidation state and structure that are reminiscent of those observed for conversion of β-NiOOH to γ-NiOOH and consequently challenge the long-held notion that the β-NiOOH phase is a more efficient oxygen-evolving catalyst. © 2012 American Chemical Society

  19. Structural Health Monitoring Analysis for the Orbiter Wing Leading Edge

    NASA Technical Reports Server (NTRS)

    Yap, Keng C.

    2010-01-01

    This viewgraph presentation reviews Structural Health Monitoring Analysis for the Orbiter Wing Leading Edge. The Wing Leading Edge Impact Detection System (WLE IDS) and the Impact Analysis Process are also described to monitor WLE debris threats. The contents include: 1) Risk Management via SHM; 2) Hardware Overview; 3) Instrumentation; 4) Sensor Configuration; 5) Debris Hazard Monitoring; 6) Ascent Response Summary; 7) Response Signal; 8) Distribution of Flight Indications; 9) Probabilistic Risk Analysis (PRA); 10) Model Correlation; 11) Impact Tests; 12) Wing Leading Edge Modeling; 13) Ascent Debris PRA Results; and 14) MM/OD PRA Results.

  20. Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

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

    Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.

    2013-05-30

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

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

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

    Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.

    2013-05-01

    Ruthenium L2,3-edge X-ray absorption (XA) spectroscopy probes transitions from core 2p orbitals to the 4d levels of the atom and is a powerful tool for interrogating the local electronic and molecular structure around the metal atom. However, a molecular-level interpretation of the Ru L2,3-edge spectral lineshapes is often complicated by spin–orbit coupling (SOC) and multiplet effects. In this study, we develop spin-free time-dependent density functional theory (TDDFT) as a viable and predictive tool to simulate the Ru L3-edge spectra. We successfully simulate and analyze the ground state Ru L3-edge XA spectra of a series of RuII and RuIII complexes: [Ru(NH3)6]2+/3+,more » [Ru(CN)6]4-/3-, [RuCl6]4-/3-, and the ground (1A1) and photoexcited (3MLCT) transient states of [Ru(bpy)3]2+ and Ru(dcbpy)2(NCS)2 (termed N3). The TDDFT simulations reproduce all the experimentally observed features in Ru L3-edge XA spectra. The advantage of using TDDFT to assign complicated Ru L3-edge spectra is illustrated by its ability to identify ligand specific charge transfer features in complex molecules. We conclude that the B3LYP functional is the most reliable functional for accurately predicting the location of charge transfer features in these spectra. Experimental and simulated Ru L3-edge XA spectra are presented for the transition metal mixed-valence dimers [(NC)5MII-CN-RuIII(NH3)5]- (where M = Fe or Ru) dissolved in water. We explore the spectral signatures of electron delocalization in Ru L3-edge XA spectroscopy and our simulations reveal that the inclusion of explicit solvent molecules is crucial for reproducing the experimentally determined valencies, highlighting the importance of the role of the solvent in transition metal charge transfer chemistry.« less

  2. X-ray absorption fine structure and X-ray excited optical luminescence studies of II-VI semiconducting nanostructures

    NASA Astrophysics Data System (ADS)

    Murphy, Michael Wayne

    2010-06-01

    of 0, 1,3, and 10% and annealed at 400, 600 and 800°C in air. XAFS spectra show that low dopant concentrations and low processing temperatures limit the amount of secondary phase formation. The nanopowders did not show roomtemperature ferromagnetism and increased secondary phase formation increases the paramagnetic character of the hysteresis curves at 5°K. Keywords: X-ray absorption fine structures (XAFS), X-ray absorption near-edge structures (XANES), extended X-ray absorption fine structure (EXAFS), X-ray absorption spectroscopy(XAS), X-ray excited optical luminescence (XEOL), time-resolved, II-VI semiconductors, nanostructure, nanomaterial, nanoribbon, nanowire, nanopartic1e, heterostructure, ZnO, ZnS, ZnO-ZnS, CdS, CdSe, CdSSe, ZnO:Mn, ZnO:Co, ZnS:Mn, dilute magnetic semiconductor (DMS), dilute magnetic oxide (DMO), spintronics, magnetism, paramagnetism, ferromagnetism.

  3. Quantitative Measurement of Local Infrared Absorption and Dielectric Function with Tip-Enhanced Near-Field Microscopy.

    PubMed

    Govyadinov, Alexander A; Amenabar, Iban; Huth, Florian; Carney, P Scott; Hillenbrand, Rainer

    2013-05-02

    Scattering-type scanning near-field optical microscopy (s-SNOM) and Fourier transform infrared nanospectroscopy (nano-FTIR) are emerging tools for nanoscale chemical material identification. Here, we push s-SNOM and nano-FTIR one important step further by enabling them to quantitatively measure local dielectric constants and infrared absorption. Our technique is based on an analytical model, which allows for a simple inversion of the near-field scattering problem. It yields the dielectric permittivity and absorption of samples with 2 orders of magnitude improved spatial resolution compared to far-field measurements and is applicable to a large class of samples including polymers and biological matter. We verify the capabilities by determining the local dielectric permittivity of a PMMA film from nano-FTIR measurements, which is in excellent agreement with far-field ellipsometric data. We further obtain local infrared absorption spectra with unprecedented accuracy in peak position and shape, which is the key to quantitative chemometrics on the nanometer scale.

  4. 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.

  5. 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

  6. Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

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

    Ganguly, Sumit; MCormick, Laura J.; Conradie, Jeanet

    Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal Mn IV oxidation state. The Soret maxima of Mn[T pXPC]Cl (T pXPC = meso-tris( p-X-phenyl)corrole, where X = CF 3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T pXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole •2–-like ligand for the MnCl complexes and an innocent corrole 3– ligand for the MnPh complexes. Single-crystalmore » X-ray structures of three Mn[T pXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[T pOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled Mn III-corrole •2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially Mn IV-corrole 3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[T pCF 3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[T pCF 3PC]Cl, consistent with a more oxidized, i.e., Mn IV, center in Mn[T pCF 3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[T pCF 3PC]Ph results from the extra 3d z2 hole, which mixes strongly with the Mn 4p z orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction

  7. Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

    DOE PAGES

    Ganguly, Sumit; MCormick, Laura J.; Conradie, Jeanet; ...

    2018-06-06

    Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal Mn IV oxidation state. The Soret maxima of Mn[T pXPC]Cl (T pXPC = meso-tris( p-X-phenyl)corrole, where X = CF 3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T pXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole •2–-like ligand for the MnCl complexes and an innocent corrole 3– ligand for the MnPh complexes. Single-crystalmore » X-ray structures of three Mn[T pXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[T pOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled Mn III-corrole •2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially Mn IV-corrole 3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[T pCF 3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[T pCF 3PC]Cl, consistent with a more oxidized, i.e., Mn IV, center in Mn[T pCF 3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[T pCF 3PC]Ph results from the extra 3d z2 hole, which mixes strongly with the Mn 4p z orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction

  8. 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.

  9. Wide angle and narrow-band asymmetric absorption in visible and near-infrared regime through lossy Bragg stacks

    PubMed Central

    Shu, Shiwei; Zhan, Yawen; Lee, Chris; Lu, Jian; Li, Yang Yang

    2016-01-01

    Absorber is an important component in various optical devices. Here we report a novel type of asymmetric absorber in the visible and near-infrared spectrum which is based on lossy Bragg stacks. The lossy Bragg stacks can achieve near-perfect absorption at one side and high reflection at the other within the narrow bands (several nm) of resonance wavelengths, whereas display almost identical absorption/reflection responses for the rest of the spectrum. Meanwhile, this interesting wavelength-selective asymmetric absorption behavior persists for wide angles, does not depend on polarization, and can be ascribed to the lossy characteristics of the Bragg stacks. Moreover, interesting Fano resonance with easily tailorable peak profiles can be realized using the lossy Bragg stacks. PMID:27251768

  10. Intergalactic Helium Absorption toward High-Redshift Quasars

    NASA Technical Reports Server (NTRS)

    Giroux, Mark L.; Fardal, Mark A.; Shull, J. Michael

    1995-01-01

    The recent Hubble Space Telescope (HST) observations of the z(q) = 3.286 quasar Q0302-003 (Jakobsen et at. 1994) and the z(q) = 3.185 quasar Q1935-67 by Tytler (1995) show absorption edges at the redshifted wavelength of He II 304 A. A key goal is to distinguish between contributions from discrete Ly-alpha forest clouds and a smoothly distributed intergalactic medium (IGM). We model the contributions from each of these sources of He II absorption, including the distribution of line Doppler widths and column densities, the 'He II proximity effect' from the quasar, and a self-consistent derivation of the He II opacity of the universe as a function of the spectrum of ionizing sources, with the assumption that both the clouds and the IGM are photoionized. The He II edge can be fully accounted for by He II line blanketing for reasonable distributions of line widths and column densities in the Ly-alpha forest, provided that the ionizing sources have spectral index alpha(s) greater than 1.5, and any He II proximity effect is neglected. Even with some contribution from a diffuse IGM, it is difficult to account for the edge observed by Jakobsen et al. (1994) with a 'hard' source spectrum (alpha(s) less than 1.3). The proximity effect modifies the relative contributions of the clouds and IGM to tau(He II) near the quasar (z approx. less than z(q)) and markedly increases the amount of He II absorption required. This implies, for example, that to account for the He II edge with line blanketing alone, the minimum spectral index alpha(s) must be increased from 1.5 to 1.9. We demonstrate the need for higher resolution observations that characterize the change in transmission as z approaches z(q) and resolve line-free gaps in the continuum. We set limits on the density of the diffuse IGM and suggest that the IGM and Ly-alpha clouds are likely to be a significant repository for dark baryons.

  11. 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

  12. Non-Destructive and Discriminating Identification of Illegal Drugs by Transient Absorption Spectroscopy in the Visible and Near-IR Wavelength Range

    NASA Astrophysics Data System (ADS)

    Sato, Chie; Furube, Akihiro; Katoh, Ryuzi; Nonaka, Hidehiko; Inoue, Hiroyuki

    2008-11-01

    We have tested the possibility of identifying illegal drugs by means of nanosecond transient absorption spectroscopy with a 10-ns UV-laser pulse for the excitation light and visible-to-near-IR light for the probe light. We measured the transient absorption spectra of acetonitrile solutions of d-methamphetamine, dl-3,4-methylenedioxymethamphetamine hydrochloride (MDMA), and dl-N-methyl-1-(1,3-benzodioxol-5-yl)-2-butanamine hydrochloride (MBDB), which are illegal drugs widely consumed in Japan. Transient absorption signals of these drugs were observed between 400 and 950 nm, a range in which they are transparent in the ground state. By analyzing the spectra in terms of exponential and Gaussian functions, we could identify the drugs and discriminate them from chemical substances having similar structures. We propose that transient absorption spectroscopy will be a useful, non-destructive method of inspecting for illegal drugs, especially when they are dissolved in liquids. Such a method may even be used for drugs packed in opaque materials if it is further extended to utilize intense femtosecond laser pulses.

  13. Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge

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

    Zubarev, Dmitry Yu.; Austin, Brian M.; Lester, William A. Jr.

    Fixed-node diffusion Monte Carlo (FNDMC) is used to simulate the x-ray absorption spectrum of a gas-phase pyrrole molecule at the nitrogen K-edge. Trial wave functions for core-excited states are constructed from ground-state Kohn-Sham determinants substituted with singly occupied natural orbitals from configuration interaction with single excitations calculations of the five lowest valence-excited triplet states. The FNDMC ionization potential (IP) is found to lie within 0.3 eV of the experimental value of 406.1 {+-} 0.1 eV. The transition energies to anti-bonding virtual orbitals match the experimental spectrum after alignment of IP values and agree with the existing assignments.

  14. Investigating the local structure of B-site cations in (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 using X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Blanchard, Peter E. R.; Grosvenor, Andrew P.

    2018-05-01

    The structural properties of (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 were investigated using powder X-ray diffraction and X-ray absorption spectroscopy. Diffraction measurements confirmed that substituting small amounts of BiScO3 into BaTiO3 initially stabilizes a cubic phase at x = 0.2 before impurity phases begin to form at x = 0.5. BiScO3 substitution also resulted in noticeable changes in the local coordination environment of Ti4+. X-ray absorption near-edge spectroscopy (XANES) analysis showed that replacing Ti4+ with Sc3+ results in an increase in the off-centre displacement of Ti4+ cations. Surprisingly, BiScO3 substitution has no effect on the displacement of the Ti4+ cation in the (1-x)PbTiO3-xBiScO3 solid solution.

  15. Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

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

    Dyar, M. Darby; McCanta, Molly; Breves, Elly

    2016-03-01

    Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yield accurate resultsmore » from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less

  16. Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

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

    Dyar, M. Darby; McCanta, Molly; Breves, Elly

    2016-03-01

    Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe 3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe 3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yieldmore » accurate results from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less

  17. Magneto-electronic properties of graphene nanoribbons with various edge structures passivated by phosphorus and hydrogen atoms.

    PubMed

    Yu, Z L; Wang, D; Zhu, Z; Zhang, Z H

    2015-10-07

    The electronic and magnetic structures of graphene nanoribbons (GNRs) with various edge structures passivated by P atoms are investigated systematically, and compared with H passivation as well. GNRs with the entire reconstructed Klein edge or armchair edge are found to be nonmagnetic regardless of P or H passivation. However, if the edge of GNRs is a mixture of zigzag edge and reconstructed Klein edge, they are nonmagnetic for H passivation but significantly magnetic for P passivation, which could be attributed to the "charge transfer doping" effect. And the corresponding magnetic device shows a noticeable negative differential resistance phenomenon and an excellent spin filtering effect under AP configuration, which originate from the special energy band structure. The GNRs with zigzag edge, reconstructed Klein edge, or mixed edge shapes are all metals in the nonmagnetic state regardless of the H or P atoms involved. The relationship between the energy gap and the width in armchair-edged GNRs by P passivation with a dimer structure also satisfies the 3p periodicity, but different in detail from the case of H passivation. The calculated edge formation energy indicates that P-passivated GNRs are energetically more favorable, suggesting that they can stably exist in the experiment.

  18. Edge-localized mode avoidance and pedestal structure in I-mode plasmasa)

    NASA Astrophysics Data System (ADS)

    Walk, J. R.; Hughes, J. W.; Hubbard, A. E.; Terry, J. L.; Whyte, D. G.; White, A. E.; Baek, S. G.; Reinke, M. L.; Theiler, C.; Churchill, R. M.; Rice, J. E.; Snyder, P. B.; Osborne, T.; Dominguez, A.; Cziegler, I.

    2014-05-01

    I-mode is a high-performance tokamak regime characterized by the formation of a temperature pedestal and enhanced energy confinement, without an accompanying density pedestal or drop in particle and impurity transport. I-mode operation appears to have naturally occurring suppression of large Edge-Localized Modes (ELMs) in addition to its highly favorable scalings of pedestal structure and overall performance. Extensive study of the ELMy H-mode has led to the development of the EPED model, which utilizes calculations of coupled peeling-ballooning MHD modes and kinetic-ballooning mode (KBM) stability limits to predict the pedestal structure preceding an ELM crash. We apply similar tools to the structure and ELM stability of I-mode pedestals. Analysis of I-mode discharges prepared with high-resolution pedestal data from the most recent C-Mod campaign reveals favorable pedestal scalings for extrapolation to large machines—pedestal temperature scales strongly with power per particle Pnet/n ¯e, and likewise pedestal pressure scales as the net heating power (consistent with weak degradation of confinement with heating power). Matched discharges in current, field, and shaping demonstrate the decoupling of energy and particle transport in I-mode, increasing fueling to span nearly a factor of two in density while maintaining matched temperature pedestals with consistent levels of Pnet/n ¯e. This is consistent with targets for increased performance in I-mode, elevating pedestal βp and global performance with matched increases in density and heating power. MHD calculations using the ELITE code indicate that I-mode pedestals are strongly stable to edge peeling-ballooning instabilities. Likewise, numerical modeling of the KBM turbulence onset, as well as scalings of the pedestal width with poloidal beta, indicates that I-mode pedestals are not limited by KBM turbulence—both features identified with the trigger for large ELMs, consistent with the observed suppression of

  19. New method in muon-hadron absorption on Thx DUO2 nano material structure at 561 MHz quantum gyro-magnetic

    NASA Astrophysics Data System (ADS)

    Hardiyanto, M.; Ermawaty, I. R.

    2018-01-01

    We present an experimental of muan-hadron tunneling chain investigation with new methods of Thx DUO2 nano structure based on Josephson’s tunneling and Abrikosov-Balseiro-Russel (ABR) formulation with quantum quadrupole interacting with a strongly localized high gyro-magnetic optical field as encountered in high-resolution near-field optical microscopy for 1.2 nano meter lambda-function. The strong gradients of these localized gyro-magnetic fields suggest that higher-order multipolar interactions will affect the standard magnetic quadrupole transition rates in 1.8 x 103 currie/mm fuel energy in nuclear moderator pool and selection rules with quatum dot. For muan-hadron absorption in Josephson’s tunnelling quantum quadrupole in the strong confinement limit we calculated the inter band of gyro-magnetic quadrupole absorption rate and the associated selection rules. Founded that the magnetic quadrupole absorption rate is comparable with the absorption rate calculated in the gyro-magneticdipole approximation of ThxDUO2 nano material structure. This implies that near-field optical techniques can extend the range of spectroscopic measurements for 545 MHz at quantum gyro-magnetic field until 561 MHz deployment quantum field at B around 455-485 tesla beyond the standard dipole approximation. However, we also show that spatial resolution could be improved by the selective excitation of ABR formulation in quantum quadrupole transitions.

  20. Hybrid plasmonic electro-optical absorption modulator based on epsilon-near-zero characteristics of ITO

    NASA Astrophysics Data System (ADS)

    Abdelatty, M. Y.; Badr, M. M.; Swillam, M. A.

    2018-03-01

    Using transparent conducting oxides (TCOs), like indium-tin-oxide (ITO), for optical modulation attracted research interest because of their epsilon-near-zero (ENZ) characteristics at telecom wavelengths. Utilizing indium-tin-oxide (ITO) in multilayer structure modulators, optical absorption of the active ITO layer can be electrically modulated over a large spectrum range. Although they show advances over common silicon electro-optical modulators (EOMs), they suffer from high insertion losses. To reduce insertion losses and device footprints without sacrificing bandwidth and modulation strength, slot waveguides are promising options because of their high optical confinement. In this paper, we present the study and the design of an electro-optical absorption modulator based on electrically tuning ITO carrier density inside a MOS structure. The device structure is based on dielectric slot waveguide with an ITO plasmonic waveguide modulation section. By changing the dimensions, the effective refractive indices for the slot mode and the off-sate mode of the plasmonic section can be matched. When applying electric field to the plasmonic section (on-state), carriers are generated at the ITO-dielectric interface that result in changing the layer where the electric field is confined from a transparent layer into a lossy layer. A finite difference time domain method with perfect matching layer (PML) absorbing boundary conditions is taken up to simulate and analyze this design. An extinction ratio of 2.3 dB is achieved for a 1-μm-short modulation section, at the telecommunications wavelength (1.55 μm). This EOM has advantages of simple design, easy fabrication, compact size, compatibility with existing silicon photonics platforms, as well as broadband performance.

  1. Coexistence of strongly and weakly confined energy levels in (Cd,Zn)Se quantum dots: Tailoring the near-band-edge and defect-levels for white light emission

    NASA Astrophysics Data System (ADS)

    Das, Tapan Kumar; Ilaiyaraja, P.; Sudakar, C.

    2017-05-01

    We demonstrate white light emission (WLE) from (Cd,Zn)Se system, which is a composite of Zn alloyed CdSe quantum dot and ZnSe-amorphous (ZnSe-a) phase. Detailed structural and photoluminescence emission studies on pure CdSe and (Cd,Zn)Se show cubic zinc blende structure in the size range of 2.5 to 5 nm. (Cd,Zn)Se quantum dots (QDs) also have a significant fraction of ZnSe-a phase. The near-band-edge green-emission in crystalline CdSe and (Cd,Zn)Se is tunable between 500 to 600 nm. The (Cd,Zn)Se system also exhibits a broad, deep defect level (DL) red-emission in the range 600 to 750 nm and a sharp ZnSe near-band-edge blue-emission (ZS-NBE) between 445 to 465 nm. While DL and CdSe near-band-edge (CS-NBE) emissions significantly shift with the size of QD due to strong confinement effect, the ZS-NBE show minimal change in peak position indicating a weak confinement effect. The intensities of ZS-NBE and DL emissions also exhibit a strong dependence on the QD size. A gamut of emission colors is obtained by combining the CS-NBE with the ZS-NBE emission and broad DL emission in (Cd,Zn)Se system. Interestingly, we find the convergence of Commission Internationale de l'Eclairage (CIE) coordinates towards the white light with increasing Zn concentration in CdSe. We demonstrate by combining these three emissions in a proper weight ratio WLE can be achieved. Cd1-yZnySe (y = 0. 5; QD size ˜4.9 nm) alloy with a maximum quantum yield of 57% exhibits CIE coordinates of (0.39, 0.4), color rendering index (CRI) of 82, correlated color temperature (CCT) of 3922 K, and Duv of 0.0078 which is very promising for white light applications.

  2. XRD and XAS structural study of CuAlO2 under high pressure.

    PubMed

    Pellicer-Porres, J; Segura, A; Ferrer-Roca, Ch; Polian, A; Munsch, P; Kim, D

    2013-03-20

    We present the results of x-ray diffraction and x-ray absorption spectroscopy experiments in CuAlO(2) under high pressure. We discuss the polarization dependence of the x-ray absorption near-edge structure at the Cu K-edge. XRD under high pressure evidences anisotropic compression, the a-axis being more compressible than the c-axis. EXAFS yields the copper-oxygen bond length, from which the only internal parameter of the delafossite structure is deduced. The combination of anisotropic compression and the internal parameter decrease results in a regularization of the AlO(6) octahedra. The anisotropic compression is related to the chemical trends observed in the lattice parameters when Al is substituted by other trivalent cations. Both experiments evidence the existence of an irreversible phase transition that clearly manifests at 35 ± 2 GPa. The structure of the high-pressure polymorph could not be determined, but it implies a change of the Cu environment, which remains anisotropic. Precursor effects are observed from the lowest pressures, which are possibly related to crystal breaking at a submicroscopic scale with partial reorientation of the crystallites.

  3. XRD and XAS structural study of CuAlO2 under high pressure

    NASA Astrophysics Data System (ADS)

    Pellicer-Porres, J.; Segura, A.; Ferrer-Roca, Ch; Polian, A.; Munsch, P.; Kim, D.

    2013-03-01

    We present the results of x-ray diffraction and x-ray absorption spectroscopy experiments in CuAlO2 under high pressure. We discuss the polarization dependence of the x-ray absorption near-edge structure at the Cu K-edge. XRD under high pressure evidences anisotropic compression, the a-axis being more compressible than the c-axis. EXAFS yields the copper-oxygen bond length, from which the only internal parameter of the delafossite structure is deduced. The combination of anisotropic compression and the internal parameter decrease results in a regularization of the AlO6 octahedra. The anisotropic compression is related to the chemical trends observed in the lattice parameters when Al is substituted by other trivalent cations. Both experiments evidence the existence of an irreversible phase transition that clearly manifests at 35 ± 2 GPa. The structure of the high-pressure polymorph could not be determined, but it implies a change of the Cu environment, which remains anisotropic. Precursor effects are observed from the lowest pressures, which are possibly related to crystal breaking at a submicroscopic scale with partial reorientation of the crystallites.

  4. Genetic structure of tree and shrubby species among anthropogenic edges, natural edges, and interior of an atlantic forest fragment.

    PubMed

    Ramos, Flavio Nunes; de Lima, Paula Feliciano; Zucchi, Maria Imaculada; Colombo, Carlos Augusto; Solferini, Vera Nisaka

    2010-04-01

    Two species, Psychotria tenuinervis (shrub, Rubiaceae) and Guarea guidonia (tree, Meliaceae), were used as models to compare the genetic structure of tree and shrubby species among natural edges, anthropogenic edges, and a fragment interior. There were significant differences between two genetic markers. For isozymes, P. tenuinervis presented greater heterozygosity (expected and observed) and a higher percentage of polymorphic loci and median number of alleles than G. guidonia. For microsatellites, there was no difference in genetic variability between the species. Only P. tenuinervis, for isozymes, showed differences in genetic variability among the three habitats. There was no genetic structure (F (ST) < 0.05) among habitats in both plant species for both genetic markers. Isozymes showed great endogamy for both plant species, but not microsatellites. The forest fragmentation may have negative effects on both spatial (among edges and interior) and temporal genetic variability.

  5. Flow Phenomena in the Very Near Wake of a Flat Plate with a Circular Trailing Edge

    NASA Technical Reports Server (NTRS)

    Rai, Man Mohan

    2014-01-01

    The very near wake of a flat plate with a circular trailing edge, exhibiting pronounced shedding of wake vortices, is investigated with data from a direct numerical simulation. The separating boundary layers are turbulent and statistically identical thus resulting in a wake that is symmetric in the mean. The focus here is on the instability of the detached shear layers, the evolution of rib-vortex induced localized regions of reverse flow that detach from the main body of reverse flow in the trailing edge region and convect downstream, and phaseaveraged velocity statistics in the very near wake. The detached shear layers are found to exhibit unstable behavior intermittently, including the development of shear layer vortices as in earlier cylinder flow investigations with laminar separating boundary layers. Only a small fraction of the separated turbulent boundary layers undergo this instability, and form the initial shed vortices. Pressure spectra within the shear layers show a broadband peak at a multiple of shedding frequency. Phase-averaged intensity and shear stress distributions of the randomly fluctuating component of velocity are compared with those obtained in the near wake. The distributions of the production terms in the transport equations for the turbulent stresses are also provided.

  6. Visualization of the separation and subsequent transition near the leading edge of airfoils

    NASA Technical Reports Server (NTRS)

    Arena, A. V.; Mueller, T. J.

    1978-01-01

    A visual study was performed using the low speed smoke wind tunnels with the objective of obtaining a better understanding of the structure of leading edge separation bubbles on airfoils. The location of separation, transition and reattachment for a cylindrical nose constant-thickness airfoil model were obtained from smoke photographs and surface oil flow techniques. These data, together with static pressure distributions along the leading edge and upper surface of the model, produced the influence of Reynolds number, angle of attack, and trailing edge flap angle on the size and characteristics of the bubble. Additional visual insight into the unsteady nature of the separation bubble was provided by high speed 16 mm movies. The 8 mm color movies taken of the surface oil flow supported the findings of the high speed movies and clearly showed the formation of a scalloped spanwise separation line at the higher Reynolds number.

  7. Reddening and He i{sup ∗} λ 10830 Absorption Lines in Three Narrow-line Seyfert 1 Galaxies

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

    Zhang, Shaohua; Zhou, Hongyan; Shi, Xiheng

    We report the detection of heavy reddening and the He i* λ 10830 absorption lines at the active galactic nucleus (AGN) redshift in three narrow-line Seyfert 1 galaxies: SDSS J091848.61+211717.0, SDSS J111354.66+124439.0, and SDSS J122749.13+321458.9. They exhibit very red optical to near-infrared colors, narrow Balmer/Paschen broad emission lines and He i* λ 10830 absorption lines. The ultraviolet-optical-infrared nucleus continua are reddened by the SMC extinction law of E ( B − V ) ∼ 0.74, 1.17, and 1.24 mag for three objects, which are highly consistent with the values obtained from the broad-line Balmer decrements, but larger than those ofmore » narrow emission lines. The reddening analysis suggests that the extinction dust simultaneously obscures the accretion disk, the broad emission-line region, and the hot dust from the inner edge of the torus. It is possible that the dust obscuring the AGN structures is the dusty torus itself. Furthermore, the Cloudy analysis of the He i* λ 10830 absorption lines proposes the distance of the absorption materials to be the extend scale of the torus, which greatly increases probabilities of the obscure and absorption materials being the dusty torus.« less

  8. Asymptotic theory of two-dimensional trailing-edge flows

    NASA Technical Reports Server (NTRS)

    Melnik, R. E.; Chow, R.

    1975-01-01

    Problems of laminar and turbulent viscous interaction near trailing edges of streamlined bodies are considered. Asymptotic expansions of the Navier-Stokes equations in the limit of large Reynolds numbers are used to describe the local solution near the trailing edge of cusped or nearly cusped airfoils at small angles of attack in compressible flow. A complicated inverse iterative procedure, involving finite-difference solutions of the triple-deck equations coupled with asymptotic solutions of the boundary values, is used to accurately solve the viscous interaction problem. Results are given for the correction to the boundary-layer solution for drag of a finite flat plate at zero angle of attack and for the viscous correction to the lift of an airfoil at incidence. A rational asymptotic theory is developed for treating turbulent interactions near trailing edges and is shown to lead to a multilayer structure of turbulent boundary layers. The flow over most of the boundary layer is described by a Lighthill model of inviscid rotational flow. The main features of the model are discussed and a sample solution for the skin friction is obtained and compared with the data of Schubauer and Klebanoff for a turbulent flow in a moderately large adverse pressure gradient.

  9. 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

  10. Probabilistic Structural Health Monitoring of the Orbiter Wing Leading Edge

    NASA Technical Reports Server (NTRS)

    Yap, Keng C.; Macias, Jesus; Kaouk, Mohamed; Gafka, Tammy L.; Kerr, Justin H.

    2011-01-01

    A structural health monitoring (SHM) system can contribute to the risk management of a structure operating under hazardous conditions. An example is the Wing Leading Edge Impact Detection System (WLEIDS) that monitors the debris hazards to the Space Shuttle Orbiter s Reinforced Carbon-Carbon (RCC) panels. Since Return-to-Flight (RTF) after the Columbia accident, WLEIDS was developed and subsequently deployed on board the Orbiter to detect ascent and on-orbit debris impacts, so as to support the assessment of wing leading edge structural integrity prior to Orbiter re-entry. As SHM is inherently an inverse problem, the analyses involved, including those performed for WLEIDS, tend to be associated with significant uncertainty. The use of probabilistic approaches to handle the uncertainty has resulted in the successful implementation of many development and application milestones.

  11. Examination of the Measurement of Absorption Using the Reverberant Room Method for Highly Absorptive Acoustic Foam

    NASA Technical Reports Server (NTRS)

    Hughes, William O.; McNelis, Anne M.; Chris Nottoli; Eric Wolfram

    2015-01-01

    The absorption coefficient for material specimens are needed to quantify the expected acoustic performance of that material in its actual usage and environment. The ASTM C423-09a standard, "Standard Test Method for Sound Absorption and Sound Absorption Coefficients by the Reverberant Room Method" is often used to measure the absorption coefficient of material test specimens. This method has its basics in the Sabine formula. Although widely used, the interpretation of these measurements are a topic of interest. For example, in certain cases the measured Sabine absorption coefficients are greater than 1.0 for highly absorptive materials. This is often attributed to the diffraction edge effect phenomenon. An investigative test program to measure the absorption properties of highly absorbent melamine foam has been performed at the Riverbank Acoustical Laboratories. This paper will present and discuss the test results relating to the effect of the test materials' surface area, thickness and edge sealing conditions. A follow-on paper is envisioned that will present and discuss the results relating to the spacing between multiple piece specimens, and the mounting condition of the test specimen.

  12. A Fourier transform spectrometer for visible and near ultra-violet measurements of atmospheric absorption

    NASA Technical Reports Server (NTRS)

    Parsons, C. L.; Gerlach, J. C.; Whitehurst, M.

    1982-01-01

    The development of a prototype, ground-based, Sun-pointed Michelson interferometric spectrometer is described. Its intended use is to measure the atmospheric amount of various gases which absorb in the near-infrared, visible, and near-ultraviolet portions of the electromagnetic spectrum. Preliminary spectra which contain the alpha, 0.8 micrometer, and rho sigma tau water vapor absorption bands in the near-infrared are presented to indicate the present capability of the system. Ultimately, the spectrometer can be used to explore the feasible applications of Fourier transform spectroscopy in the ultraviolet where grating spectrometers were used exclusively.

  13. 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.

  14. The Dynamics of Turbulent Scalar Mixing near the Edge of a Shear Layer

    NASA Astrophysics Data System (ADS)

    Taveira, R. M. R.; da Silva, C. B.; Pereira, J. C. F.

    2011-12-01

    In free shear flows a sharp and convoluted turbulent/nonturbulent (T/NT) interface separates the outer fluid region, where the flow is essentially irrotational, from the shear layer turbulent region. It was found recently that the entrainment mechanism is mainly caused by small scale ("nibbling") motions (Westerweel et al. (2005)). The dynamics of this interface is crucial to understand important exchanges of enstrophy and scalars that can be conceived as a three-stage process of entrainment, dispersion and diffusion (Dimotakis (2005)). A thorough understanding of scalar mixing and transport is of indisputable relevance to control turbulent combustion, propulsion and contaminant dispersion (Stanley et al. (2002)). The present work uses several DNS of turbulent jets at Reynolds number ranging from Reλ = 120 to Reλ = 160 (da Silva & Taveira (2010)) and a Schmidt number Sc = 0.7 to analyze the "scalar interface" and turbulent mixing of a passive scalar. Specifically, we employ conditional statistics, denoted by langlerangleI, in order to eliminate the intermittency that affects statistics close to the jet edge. The physical mechanisms behind scalar mixing near the T/NT interfaces, their scales and topology are investigated detail. Analysis of the instantaneous fields showed intense scalar gradient sheet-like structures along regions of persistent strain, in particular at the T/NT interface. The scalar gradient transport equation, at the jet edge, showed that almost all mixing mechanisms are taking place in a confined region, beyond which they become reduced to an almost in perfect balance between production and dissipation of scalar variance. At the T/NT interface transport mechanisms are the ones responsible for the growth in the scalar fluctuations to the entrained fluid, where convection plays a dominant role, smoothing scalar gradients inside the interface and boosting them as far as

  15. Discriminating the Drivers of Edge Effects on Nest Predation: Forest Edges Reduce Capture Rates of Ship Rats (Rattus rattus), a Globally Invasive Nest Predator, by Altering Vegetation Structure

    PubMed Central

    Ruffell, Jay; Didham, Raphael K.; Barrett, Paul; Gorman, Nic; Pike, Rhonda; Hickey-Elliott, Andrée; Sievwright, Karin; Armstrong, Doug P.

    2014-01-01

    Forest edges can strongly affect avian nest success by altering nest predation rates, but this relationship is inconsistent and context dependent. There is a need for researchers to improve the predictability of edge effects on nest predation rates by examining the mechanisms driving their occurrence and variability. In this study, we examined how the capture rates of ship rats, an invasive nest predator responsible for avian declines globally, varied with distance from the forest edge within forest fragments in a pastoral landscape in New Zealand. We hypothesised that forest edges would affect capture rates by altering vegetation structure within fragments, and that the strength of edge effects would depend on whether fragments were grazed by livestock. We measured vegetation structure and rat capture rates at 488 locations ranging from 0–212 m from the forest edge in 15 forest fragments, seven of which were grazed. Contrary to the vast majority of previous studies of edge effects on nest predation, ship rat capture rates increased with increasing distance from the forest edge. For grazed fragments, capture rates were estimated to be 78% lower at the forest edge than 118 m into the forest interior (the farthest distance for grazed fragments). This relationship was similar for ungrazed fragments, with capture rates estimated to be 51% lower at the forest edge than 118 m into the forest interior. A subsequent path analysis suggested that these ‘reverse’ edge effects were largely or entirely mediated by changes in vegetation structure, implying that edge effects on ship rats can be predicted from the response of vegetation structure to forest edges. We suggest the occurrence, strength, and direction of edge effects on nest predation rates may depend on edge-driven changes in local habitat when the dominant predator is primarily restricted to forest patches. PMID:25412340

  16. Discriminating the drivers of edge effects on nest predation: forest edges reduce capture rates of ship rats (Rattus rattus), a globally invasive nest predator, by altering vegetation structure.

    PubMed

    Ruffell, Jay; Didham, Raphael K; Barrett, Paul; Gorman, Nic; Pike, Rhonda; Hickey-Elliott, Andrée; Sievwright, Karin; Armstrong, Doug P

    2014-01-01

    Forest edges can strongly affect avian nest success by altering nest predation rates, but this relationship is inconsistent and context dependent. There is a need for researchers to improve the predictability of edge effects on nest predation rates by examining the mechanisms driving their occurrence and variability. In this study, we examined how the capture rates of ship rats, an invasive nest predator responsible for avian declines globally, varied with distance from the forest edge within forest fragments in a pastoral landscape in New Zealand. We hypothesised that forest edges would affect capture rates by altering vegetation structure within fragments, and that the strength of edge effects would depend on whether fragments were grazed by livestock. We measured vegetation structure and rat capture rates at 488 locations ranging from 0-212 m from the forest edge in 15 forest fragments, seven of which were grazed. Contrary to the vast majority of previous studies of edge effects on nest predation, ship rat capture rates increased with increasing distance from the forest edge. For grazed fragments, capture rates were estimated to be 78% lower at the forest edge than 118 m into the forest interior (the farthest distance for grazed fragments). This relationship was similar for ungrazed fragments, with capture rates estimated to be 51% lower at the forest edge than 118 m into the forest interior. A subsequent path analysis suggested that these 'reverse' edge effects were largely or entirely mediated by changes in vegetation structure, implying that edge effects on ship rats can be predicted from the response of vegetation structure to forest edges. We suggest the occurrence, strength, and direction of edge effects on nest predation rates may depend on edge-driven changes in local habitat when the dominant predator is primarily restricted to forest patches.

  17. Tetrahalide complexes of the [U(NR)2]2+ ion: synthesis, theory, and chlorine K-edge X-ray absorption spectroscopy.

    PubMed

    Spencer, Liam P; Yang, Ping; Minasian, Stefan G; Jilek, Robert E; Batista, Enrique R; Boland, Kevin S; Boncella, James M; Conradson, Steven D; Clark, David L; Hayton, Trevor W; Kozimor, Stosh A; Martin, Richard L; MacInnes, Molly M; Olson, Angela C; Scott, Brian L; Shuh, David K; Wilkerson, Marianne P

    2013-02-13

    Synthetic routes to salts containing uranium bis-imido tetrahalide anions [U(NR)(2)X(4)](2-) (X = Cl(-), Br(-)) and non-coordinating NEt(4)(+) and PPh(4)(+) countercations are reported. In general, these compounds can be prepared from U(NR)(2)I(2)(THF)(x) (x = 2 and R = (t)Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl(-), the [U(NMe)(2)](2+) cation also reacts with Br(-) to form stable [NEt(4)](2)[U(NMe)(2)Br(4)] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO(2)](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh(4)](2)[U(N(t)Bu)(2)Cl(4)] and [PPh(4)](2)[UO(2)Cl(4)]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

  18. Accurate Modeling of X-ray Extinction by Interstellar Grains

    NASA Astrophysics Data System (ADS)

    Hoffman, John; Draine, B. T.

    2016-02-01

    Interstellar abundance determinations from fits to X-ray absorption edges often rely on the incorrect assumption that scattering is insignificant and can be ignored. We show instead that scattering contributes significantly to the attenuation of X-rays for realistic dust grain size distributions and substantially modifies the spectrum near absorption edges of elements present in grains. The dust attenuation modules used in major X-ray spectral fitting programs do not take this into account. We show that the consequences of neglecting scattering on the determination of interstellar elemental abundances are modest; however, scattering (along with uncertainties in the grain size distribution) must be taken into account when near-edge extinction fine structure is used to infer dust mineralogy. We advertise the benefits and accuracy of anomalous diffraction theory for both X-ray halo analysis and near edge absorption studies. We present an open source Fortran suite, General Geometry Anomalous Diffraction Theory (GGADT), that calculates X-ray absorption, scattering, and differential scattering cross sections for grains of arbitrary geometry and composition.

  19. ACCURATE MODELING OF X-RAY EXTINCTION BY INTERSTELLAR GRAINS

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

    Hoffman, John; Draine, B. T., E-mail: jah5@astro.princeton.edu, E-mail: draine@astro.princeton.edu

    Interstellar abundance determinations from fits to X-ray absorption edges often rely on the incorrect assumption that scattering is insignificant and can be ignored. We show instead that scattering contributes significantly to the attenuation of X-rays for realistic dust grain size distributions and substantially modifies the spectrum near absorption edges of elements present in grains. The dust attenuation modules used in major X-ray spectral fitting programs do not take this into account. We show that the consequences of neglecting scattering on the determination of interstellar elemental abundances are modest; however, scattering (along with uncertainties in the grain size distribution) must bemore » taken into account when near-edge extinction fine structure is used to infer dust mineralogy. We advertise the benefits and accuracy of anomalous diffraction theory for both X-ray halo analysis and near edge absorption studies. We present an open source Fortran suite, General Geometry Anomalous Diffraction Theory (GGADT), that calculates X-ray absorption, scattering, and differential scattering cross sections for grains of arbitrary geometry and composition.« less

  20. Lower Hybrid wave edge power loss quantification on the Alcator C-Mod tokamak

    NASA Astrophysics Data System (ADS)

    Faust, I. C.

    2015-11-01

    For the first time, the power deposition of Lower Hybrid RF waves into the edge plasma of a diverted tokamak has been systematically quantified. Edge deposition represents a parasitic loss of power that can greatly impact the use and efficiency of Lower Hybrid Current Drive (LHCD) at reactor-relevant densities. Through the use of a unique set of fast time resolution edge diagnostics, including innovative fast-thermocouples, an extensive set of Langmuir probes, and a Lyα ionization camera, the toroidal, poloidal and radial structure of the power deposition has been simultaneously determined. Power modulation was used to directly isolate the RF effects due to the prompt (t <τE) response of the scrape-off-layer (SOL) plasma to LHRF power. LHRF power was found to absorb more strongly in the edge at higher densities. It is found that a majority of this edge-deposited power is promptly conducted to the divertor. This correlates with the loss of current drive efficiency at high density previously observed on Alcator C-Mod, and displaying characteristics that contrast with the local RF edge absorption seen on other tokamaks. Measurements of ionization in the active divertor show dramatic changes due to LHRF power, implying that divertor region can be key for the LHRF edge power deposition physics. These observations support the existence a loss mechanism near the edge for LHRF at high density (ne > 1 . 0 .1020 [m-3]). Results will be shown addressing the distribution of power within the SOL, including the toroidal symmetry and radial distribution. These characteristics are important for deducing the cause of the reduced LHCD efficiency at high density and motivates the tailoring of wave propagation to minimize SOL interaction, for example, through the use of high-field-side launch. This work was performed on the Alcator C-Mod tokamak, a DoE Office of Science user facility, and is supported by USDoE award DE-FC02-99ER54512.